JP2011080055A - Polyamide composition and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide composition which is excellent in toughness and fluidity and further is excellent in heat discoloration resistance and workability. <P>SOLUTION: The polyamide composition comprises (A) a polyamide and (B) titanium oxide having a number-average particle size of 0.1-0.8 μm, wherein the polyamide is obtained by polymerizing (a) a dicarboxylic acid which contains an alicyclic dicarboxylic acid of at least 50 mol% and (b) a diamine which contains a branched main chain of a diamine at least 50 mol%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polyamide composition and a molded article comprising the polyamide composition.

  Polyamides represented by polyamide 6 and polyamide 66 (hereinafter sometimes abbreviated as “PA6” and “PA66”, respectively) and the like are excellent in molding processability, mechanical properties, and chemical resistance. Widely used as various parts materials for automobiles, electric and electronic, industrial materials, industrial materials, daily products and household products.

  In the automobile industry, as an environmental measure, there is a demand for reducing the weight of the vehicle body by replacing metal in order to reduce exhaust gas. In order to meet this requirement, polyamides are increasingly used for exterior materials and interior materials, and the required properties such as heat resistance, strength, and appearance of polyamide materials are further improved. Above all, since the temperature in the engine room is also increasing, there is an increasing demand for higher heat resistance for the polyamide material.

  Further, in the electrical and electronic industries such as home appliances, in order to cope with the lead-free surface mount (SMT) solder, it is required to increase the heat resistance of the polyamide material that can withstand the rise in the melting point of the solder.

  Polyamides such as PA6 and PA66 have a low melting point and cannot satisfy these requirements in terms of heat resistance.

  Therefore, in order to solve the above-mentioned problems of conventional polyamides such as PA6 and PA66, high melting point polyamides have been proposed. Specifically, a polyamide composed of terephthalic acid and hexamethylenediamine (hereinafter sometimes abbreviated as “PA6T”) has been proposed.

  However, since PA6T is a high-melting-point polyamide having a melting point of about 370 ° C., even if an attempt is made to obtain a molded product by melt molding, the polyamide undergoes severe thermal decomposition, making it difficult to obtain a molded product having sufficient characteristics.

  In order to solve the above-mentioned problems of PA6T, PA6T may be abbreviated as aliphatic polyamide such as PA6 and PA66, or amorphous aromatic polyamide (hereinafter referred to as “PA6I”) composed of isophthalic acid and hexamethylenediamine. ) And the like, and a high melting point semi-aromatic polyamide mainly composed of terephthalic acid and hexamethylenediamine (hereinafter referred to as “6T copolymer polyamide”) whose melting point is lowered to about 220 to 340 ° C. Have been proposed).

  As a 6T copolymer polyamide, Patent Document 1 discloses an aromatic polyamide (hereinafter referred to as “a mixture of hexamethylene diamine and 2-methylpentamethylene diamine”), which is composed of an aromatic dicarboxylic acid and an aliphatic diamine. May be abbreviated as “PA6T / 2MPDT”).

  Further, in contrast to an aromatic polyamide composed of an aromatic dicarboxylic acid and an aliphatic diamine, a high melting point aliphatic polyamide composed of adipic acid and tetramethylene diamine (hereinafter sometimes abbreviated as “PA46”) or an alicyclic ring. An alicyclic polyamide composed of an aliphatic dicarboxylic acid and an aliphatic diamine has been proposed.

  Patent Documents 2 and 3 disclose semialicyclic polyamides of alicyclic polyamides (hereinafter sometimes referred to as “PA6C”) composed of 1,4-cyclohexanedicarboxylic acid and hexamethylenediamine and other polyamides. (Hereinafter, it may be abbreviated as “PA6C copolymer polyamide”).

  Patent Document 2 discloses that the heat and heat resistance of semi-alicyclic polyamide blended with 1 to 40% of 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit is improved in solder heat resistance. Is disclosed to be excellent in fluidity, toughness and the like in an automobile part.

  Furthermore, Patent Document 4 discloses that a polyamide comprising a dicarboxylic acid unit containing 1,4-cyclohexanedicarboxylic acid and a diamine unit containing 2-methyl-1,8-octanediamine is light resistance, toughness, moldability, lightness, And excellent heat resistance and the like. In addition, as a method for producing the polyamide, 1,4-cyclohexanedicarboxylic acid and 1,9-nonanediamine are reacted at 230 ° C. or less to form a prepolymer, and the prepolymer is solid-phase polymerized at 230 ° C. to have a melting point of 311 ° C. The production of polyamides is disclosed.

  In Patent Document 5, a polyamide using 1,4-cyclohexanedicarboxylic acid having a trans / cis ratio of 50/50 to 97/3 as a raw material is excellent in heat resistance, low water absorption, light resistance, and the like. It is disclosed.

JP-T 6-503590 Japanese National Patent Publication No. 11-512476 Special table 2001-514695 gazette Japanese Patent Laid-Open No. 9-12868 International Publication No. 2002/048239 Pamphlet

  Although 6T copolymer polyamide certainly has the characteristics of low water absorption, high heat resistance, and high chemical resistance, it has low flowability and insufficient moldability and molded product surface appearance, and toughness. Inferior to light resistance. Therefore, the appearance of a molded product such as an exterior part is required, or improvement is desired in applications where it is exposed to sunlight or the like. In addition, the specific gravity is large, and improvement in lightness is also desired.

  The PA6T / 2MPDT disclosed in Patent Document 1 can partially improve the problems of the conventional PA6T copolymer polyamide, but in terms of fluidity, moldability, toughness, molded product surface appearance, and light resistance. The level of improvement is insufficient.

  PA46 has good heat resistance and moldability, but has a high water absorption rate, and has a problem that dimensional change due to water absorption and deterioration of mechanical properties are remarkably large. Dimensional change required for automobile applications, etc. There are cases where the demand cannot be met.

  The PA6C copolymer polyamides disclosed in Patent Documents 2 and 3 also have problems such as high water absorption and insufficient fluidity. Furthermore, the polyamides disclosed in Patent Documents 4 and 5 are also insufficiently improved in terms of toughness, rigidity, and fluidity.

  The problem to be solved by the present invention is to provide a polyamide composition which is excellent in toughness and fluidity, and further excellent in heat discoloration and processability.

  As a result of intensive studies to solve the above problems, the present inventors have found that a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid and a diamine having a substituent branched from the main chain of at least 50 mol%. The present inventors have found that a polyamide composition containing a polyamide obtained by polymerizing a diamine containing bismuth and a specific titanium oxide can solve the above problems, and has completed the present invention.

  That is, the present invention is as follows.

[1] (A) (a) a polyamide obtained by polymerizing a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid and (b) a diamine containing at least 50 mol% of a diamine having a branched main chain;
(B) A polyamide composition containing a titanium oxide having a number average particle diameter (according to an electron micrograph) of 0.1 to 0.8 μm.

  [2] The polyamide composition according to [1], wherein the diamine having a branched structure in the main chain is 2-methylpentamethylenediamine.

  [3] The polyamide composition according to [1] or [2], wherein the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.

  [4] The polyamide composition according to any one of [1] to [3], wherein (a) the dicarboxylic acid further contains an aliphatic dicarboxylic acid having 10 or more carbon atoms.

  [5] The polyamide composition according to any one of [1] to [4], wherein (A) the melting point of the polyamide is 270 to 350 ° C.

  [6] The polyamide composition according to any one of [1] to [5], wherein the trans isomer ratio in the polyamide (A) is 50 to 85%.

  [7] The polyamide composition according to any one of [1] to [6], wherein (B) titanium oxide is coated with an inorganic coating and / or an organic coating.

  [8] The polyamide composition according to [7], wherein the inorganic coating is a metal oxide coating.

  [9] The polyamide composition according to [7] or [8], wherein the organic coating is at least one coating selected from the group consisting of carboxylic acids, polyols, alkanolamines and organosilicon compounds.

  [10] The polyamide composition according to any one of [1] to [9], wherein the ignition loss of (B) titanium oxide is 0.7 to 2.5 mass%.

  [11] The polyamide composition according to any one of [1] to [10], further comprising (C) an amine light stabilizer.

  [12] The polyamide composition according to [11], wherein the molecular weight of the (C) amine light stabilizer is less than 1,000.

  [13] The polyamide composition according to any one of [1] to [12], further comprising (D) a phenol-based heat stabilizer.

  [14] The polyamide composition according to any one of [1] to [13], further comprising (E) an inorganic filler.

  [15] (14) The inorganic filler is at least one selected from the group consisting of glass fiber, potassium titanate fiber, talc, wollastonite, kaolin, mica, calcium carbonate, and clay. Polyamide composition.

[16] Based on the total mass (based on 100% by mass of the polyamide composition)
(A) 55 to 95% by mass of a polyamide obtained by polymerizing (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid and (b) a diamine containing at least 50 mol% of a diamine having a branched main chain;
(B) 5 to 45% by mass of titanium oxide having a number average particle size of 0.1 to 0.8 μm,
(C) 0 to 1% by mass of an amine light stabilizer,
(D) 0 to 1% by mass of a phenol-based heat stabilizer,
(E) 0 to 25 mass% of inorganic filler,
Containing polyamide composition.

  [17] The polyamide composition according to any one of [1] to [16], wherein the polyamide (A) has a cyclic amino group bonded to a polymer terminal in an amount of 30 μequivalent / g to 65 μequivalent / g.

  [18] A molded article comprising the polyamide composition according to any one of [1] to [17].

  ADVANTAGE OF THE INVENTION According to this invention, the polyamide composition which is excellent in toughness and fluidity | liquidity, and is excellent in heat discoloration property and workability can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The polyamide composition of the present embodiment is
(A) polyamide,
(B) containing titanium oxide.

[(A) Polyamide]
The polyamide (A) used in the present embodiment is a polyamide obtained by polymerizing the following (a) and (b).
(A) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid,
(B) A diamine containing at least 50 mol% of a diamine having a branched structure as a main chain (a diamine having a structure in which a chain between _two amino groups (—NH ₂ groups) has a side chain instead of a linear structure). .

  In the present embodiment, the polyamide means a polymer having an amide (—NHCO—) bond in the main chain.

(A) Dicarboxylic acid (a) The dicarboxylic acid used in the present embodiment contains at least 50 mol% of alicyclic dicarboxylic acid (based on the total number of moles of dicarboxylic acid), but the mol% of alicyclic dicarboxylic acid is By being the said value, polyamide which satisfies heat resistance, fluidity | liquidity, toughness, low water absorption, rigidity, etc. simultaneously can be obtained.

  (A-1) Examples of alicyclic dicarboxylic acids (also referred to as alicyclic dicarboxylic acids) include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentane. Examples thereof include alicyclic dicarboxylic acids having 3 to 10, preferably 5 to 10 carbon atoms in the alicyclic structure, such as dicarboxylic acids.

  The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent. Examples of this substituent include alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.

  The alicyclic dicarboxylic acid is preferably 1,4-cyclohexanedicarboxylic acid from the viewpoints of heat resistance, low water absorption, rigidity, and the like.

  As the alicyclic dicarboxylic acid, one kind may be used, or two or more kinds may be used in combination.

  An alicyclic dicarboxylic acid has a trans isomer and a cis geometric isomer. As the alicyclic dicarboxylic acid as a raw material monomer, either a trans isomer or a cis isomer may be used, or a mixture of various ratios of a trans isomer and a cis isomer may be used.

  The alicyclic dicarboxylic acid is isomerized at a high temperature to a certain ratio, and the cis isomer has a higher water solubility in the equivalent salt with the diamine than the trans isomer. The cis-isomer ratio is preferably 50/50 to 0/100, more preferably 40/60 to 10/90, and still more preferably 35/65 to 15/85 as a molar ratio.

  The trans / cis ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR).

  Examples of dicarboxylic acids other than (a-2) alicyclic dicarboxylic acids in (a) dicarboxylic acids used in the present embodiment include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.

  Examples of the aliphatic dicarboxylic acid include malonic acid, dimethyl malonic acid, succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl glutaric acid, 2,2-diethyl succinic acid, and 2,3-diethyl glutaric acid. , Glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecane Examples thereof include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as diacid, eicosane diacid, and diglycolic acid.

  Examples of the aromatic dicarboxylic acid include unsubstituted or various terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. And aromatic dicarboxylic acids having 8 to 20 carbon atoms substituted with the above-mentioned substituents.

  Examples of the various substituents include, for example, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, a halogen group such as a chloro group and a bromo group, and 1 carbon atom. ˜6 silyl groups, sulfonic acid groups and salts thereof (sodium salts, etc.) and the like.

  When copolymerizing dicarboxylic acids other than alicyclic dicarboxylic acids, it is preferable to use aliphatic dicarboxylic acids in terms of heat resistance, fluidity, toughness, low water absorption, rigidity, etc., more preferably, An aliphatic dicarboxylic acid having 6 or more carbon atoms is used.

  Among these, aliphatic dicarboxylic acids having 10 or more carbon atoms are preferable from the viewpoints of heat resistance and low water absorption. Examples of the aliphatic dicarboxylic acid having 10 or more carbon atoms include sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid. Of these, sebacic acid and dodecanedioic acid are preferable from the viewpoint of heat resistance and the like.

  As dicarboxylic acid other than alicyclic dicarboxylic acid, you may use by 1 type and may be used in combination of 2 or more types.

  (A) As the dicarboxylic acid component, a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid may be further included within the range not impairing the object of the present embodiment. As the polyvalent carboxylic acid, one kind may be used, or two or more kinds may be used in combination.

  The proportion (mol%) of (a-1) alicyclic dicarboxylic acid in (a) dicarboxylic acid is at least 50 mol%. The proportion of the alicyclic dicarboxylic acid is 50 to 100 mol%, preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and particularly preferably 100 mol%. When the proportion of the alicyclic dicarboxylic acid is at least 50 mol%, a polyamide having excellent heat resistance, low water absorption, rigidity and the like can be obtained.

  (A) The ratio (mol%) of dicarboxylic acid other than (a-2) alicyclic dicarboxylic acid in dicarboxylic acid is 0 to 50 mol%, and preferably 0 to 40 mol%.

  When (a) the dicarboxylic acid component contains an aliphatic dicarboxylic acid having 10 or more carbon atoms, (a-1) 50-99.9 mol% of the alicyclic dicarboxylic acid and (a-2) 10 carbon atoms. The aliphatic dicarboxylic acid is preferably 0.1 to 50 mol%, (a-1) 60 to 95 mol% of alicyclic dicarboxylic acid and (a-2) aliphatic dicarboxylic acid having 10 or more carbon atoms. The acid is more preferably 5 to 40 mol%, (a-1) alicyclic dicarboxylic acid is 80 to 95 mol%, and (a-2) aliphatic dicarboxylic acid having 10 or more carbon atoms is 5 to 20 mol. % Is more preferable.

  In the present embodiment, the (a) dicarboxylic acid is not limited to the compounds described as the dicarboxylic acid, and may be a compound equivalent to the dicarboxylic acid. The compound equivalent to the dicarboxylic acid is not particularly limited as long as it can be a dicarboxylic acid structure similar to the dicarboxylic acid structure derived from the dicarboxylic acid, and examples thereof include anhydrides and halides of dicarboxylic acids. Can be mentioned.

(B) Diamine (b) The diamine used in the present embodiment contains at least 50 mol% of a diamine having a branched main chain (a diamine having a substituent branched from the main chain) (based on the total number of diamine moles).

  (B) By containing at least 50 mol% of a diamine having a branched structure as the main chain, a polyamide that simultaneously satisfies fluidity, toughness, rigidity, and the like can be obtained.

  Examples of the substituent branched from the main chain include alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Is mentioned.

  (B-1) Examples of the diamine having a branched main chain include 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane), 2,2,4-trimethylhexamethylene. Examples thereof include branched saturated aliphatic diamines having 3 to 20 carbon atoms such as diamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctamethylenediamine.

  The diamine having a branched main chain is preferably 2-methylpentamethylenediamine from the viewpoint of heat resistance and rigidity. As the diamine having a branched main chain, one kind may be used, or two or more kinds may be used in combination.

  Examples of the diamine other than the (b-2) diamine having a branched structure (b-2) of (b) diamine used in the present embodiment include aliphatic diamines, alicyclic diamines, and aromatic diamines.

  Examples of the aliphatic diamine include ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, And straight-chain saturated aliphatic diamines having 2 to 20 carbon atoms such as tridecamethylenediamine.

  Examples of the alicyclic diamine (also referred to as alicyclic diamine) include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-cyclopentanediamine, and the like.

  The aromatic diamine is an aromatic diamine, such as metaxylylenediamine.

  The diamine other than the diamine having a branched main chain is preferably an aliphatic diamine or an alicyclic diamine, more preferably carbon, from the viewpoints of heat resistance, fluidity, toughness, low water absorption, rigidity, and the like. It is a linear saturated aliphatic diamine having 4 to 13 carbon atoms, more preferably a linear saturated aliphatic diamine having 6 to 10 carbon atoms, and still more preferably hexamethylene diamine. As the diamine other than the diamine having a branched main chain, one kind may be used, or two or more kinds may be used in combination.

  (B) As the diamine component, a trivalent or higher polyvalent aliphatic amine such as bishexamethylene triamine may be further included within a range not impairing the object of the present embodiment. As the polyvalent aliphatic amine, one kind may be used, or two or more kinds may be used in combination.

  (B) The ratio (mol%) of the diamine having a branched structure of (b-1) main chain in the diamine is at least 50 mol%. That is, the proportion of the diamine having a branched structure of the main chain is 50 to 100 mol%, and preferably 60 to 100 mol%. More preferably, this ratio is 80 to 100 mol%, more preferably 85 to 100 mol%, particularly preferably 90 to 100 mol%, and most preferably 100 mol%. When the diamine having a branched structure of the main chain is at least 50 mol%, a polyamide having excellent fluidity, toughness, and rigidity can be obtained.

  (B) The proportion (mol%) of the diamine other than the diamine having a branched structure (b-2) main chain in the diamine is 0 to 50 mol%, and preferably 0 to 40 mol%.

  The addition amount of (a) dicarboxylic acid and the addition amount of (b) diamine are preferably around the same molar amount. The amount of (b) diamine escaped from the reaction system during the polymerization reaction is also considered in terms of the molar ratio, and (a) the molar amount of (b) diamine as a whole is 0 It is preferable that it is 0.9-1.2, More preferably, it is 0.95-1.1, More preferably, it is 0.98-1.05.

(C) A lactam and / or aminocarboxylic acid (A) polyamide can further copolymerize (c) lactam and / or aminocarboxylic acid from a viewpoint of toughness. In addition, the (c) lactam and / or aminocarboxylic acid used in the present embodiment means a lactam and / or aminocarboxylic acid that can be condensed (condensed).

  When (A) polyamide is a polyamide obtained by polymerizing (a) dicarboxylic acid, (b) diamine, and (c) lactam and / or aminocarboxylic acid, (c) lactam and / or aminocarboxylic acid is A lactam having 4 to 14 carbon atoms and / or an aminocarboxylic acid is preferable, and a lactam having 6 to 12 carbon atoms and / or an aminocarboxylic acid is more preferably used.

  Examples of the lactam include butyrolactam, pivalolactam, ε-caprolactam, caprilactam, enantolactam, undecanolactam, laurolactam (dodecanolactam), and the like. Among these, from the viewpoint of toughness, ε-caprolactam and laurolactam are preferable, and ε-caprolactam is more preferable.

  Examples of the aminocarboxylic acid include ω-aminocarboxylic acid and α, ω-amino acid that are compounds in which the lactam is ring-opened.

  The aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms substituted with an amino group at the ω position, such as 6-aminocaproic acid, 11-aminoundecanoic acid, And 12-aminododecanoic acid and the like, and examples of the aminocarboxylic acid include paraaminomethylbenzoic acid and the like.

  As the lactam and / or aminocarboxylic acid, one kind may be used, or two or more kinds may be used in combination.

  (C) The addition amount (mol%) of the lactam and / or aminocarboxylic acid is 0 to 20 mol% with respect to the molar amount of each monomer in (a), (b) and (c). preferable.

  When the polyamide is polymerized from (a) dicarboxylic acid and (b) diamine, a known end-capping agent can be further added to adjust the molecular weight.

  Examples of the end-capping agent include monocarboxylic acids, monoamines, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like, from the viewpoint of thermal stability. And monocarboxylic acids and monoamines are preferred. As the terminal blocking agent, one kind may be used, or two or more kinds may be used in combination.

  The monocarboxylic acid that can be used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid , Caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; and benzoic acid, toluyl Examples thereof include aromatic monocarboxylic acids such as acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid. As monocarboxylic acid, you may use by 1 type and may be used in combination of 2 or more types.

  The monoamine that can be used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, Aliphatic monoamines such as decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine Is mentioned. Monoamines may be used alone or in combination of two or more.

  The combination of (a) dicarboxylic acid and (b) diamine is not limited to the following, but (a-1) at least 50 mol% of alicyclic dicarboxylic acid and (b-1) at least 50 mol%. A combination of the above 2-methylpentamethylenediamines is preferred, and (a-1) at least 50 mol% or more of 1,4-cyclohexanedicarboxylic acid and (b-1) at least 50 mol% or more of 2-methylpentamethylenediamine are included. More preferred.

  By polymerizing these combinations as polyamide components, it is possible to obtain a polyamide that simultaneously satisfies heat resistance, fluidity, toughness, low water absorption, and rigidity.

  (A) In polyamide, an alicyclic dicarboxylic acid structure exists as a geometric isomer of a trans isomer and a cis isomer.

  The trans isomer ratio of the alicyclic dicarboxylic acid structure in the polyamide represents the ratio of the trans isomer in the entire alicyclic dicarboxylic acid in the polyamide, and the trans isomer ratio is preferably 50 to 85 mol%. More preferably, it is 50-80 mol%, More preferably, it is 60-80 mol%.

  (A-1) As the alicyclic dicarboxylic acid, it is preferable to use an alicyclic dicarboxylic acid having a trans isomer / cis isomer ratio (molar ratio) of 50/50 to 0/100. And (b) the polyamide obtained by polymerization of the diamine preferably has a trans isomer ratio of 50 to 85 mol%.

  When the trans isomer ratio is within the above range, the polyamide is contrary to the characteristics of high melting point, toughness, and rigidity, as well as the thermal rigidity due to the high glass transition temperature (Tg), and usually the heat resistance. It has the properties of satisfying both the fluidity and high crystallinity that are properties.

  These characteristics of the polyamide consist of a combination of (a) at least 50 mol% or more of 1,4-cyclohexanedicarboxylic acid, (b) at least 50 mol% or more of 2-methylpentamethylenediamine, and the trans isomer ratio is This is particularly noticeable with polyamides of 50 to 85 mol%.

  In the present embodiment, the trans isomer ratio can be measured by the method described in the following examples.

  (A) Polyamide is not particularly limited, and (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid, and (b) at least 50 mol% of a diamine having a branched structure in the main chain. It can manufacture with the manufacturing method of polyamide including the process of superposing | polymerizing with the diamine containing.

  (A) As a manufacturing method of polyamide, it is preferable to further include the process of raising the polymerization degree of polyamide.

  Examples of the method for producing the polyamide include various methods as exemplified below.

  1) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated and polymerized while maintaining a molten state (hereinafter sometimes referred to as “hot melt polymerization method”),

  2) A method of increasing the degree of polymerization while maintaining the solid state of the polyamide obtained by the hot melt polymerization method at a temperature below the melting point (hereinafter, sometimes abbreviated as “hot melt polymerization / solid phase polymerization method”). ,

  3) A method in which an aqueous solution or a suspension of water of a diamine / dicarboxylate salt or a mixture thereof is heated and the precipitated prepolymer is melted again with an extruder such as a kneader to increase the degree of polymerization (hereinafter referred to as “pre-polymerization”). Abbreviated as “polymer / extrusion polymerization method”).

  4) A method of heating an aqueous solution or a suspension of water of a diamine dicarboxylate or a mixture thereof and increasing the degree of polymerization while maintaining the solid state of the precipitated prepolymer at a temperature below the melting point of the polyamide (hereinafter, And may be abbreviated as “prepolymer / solid phase polymerization method”).

  5) A method of polymerizing a diamine dicarboxylate or a mixture thereof while maintaining a solid state (hereinafter sometimes abbreviated as “solid phase polymerization method”),

  6) A “solution method” in which a dicarboxylic acid halide component equivalent to a dicarboxylic acid and a diamine component are used for polymerization.

  In the polyamide production method, from the viewpoint of the fluidity of the polyamide, it is preferable to carry out the polymerization while maintaining the trans isomer ratio of the alicyclic dicarboxylic acid at 85% or less, and particularly by maintaining at 80% or less, A polyamide having excellent color tone and tensile elongation and having a high melting point can be obtained.

  In the production method of polyamide, in order to increase the degree of polymerization and increase the melting point of polyamide, it is necessary to increase the heating temperature or lengthen the heating time. A decrease in tensile elongation due to deterioration may occur. In addition, the rate at which the molecular weight increases may decrease significantly.

  Since it is possible to prevent a decrease in tensile elongation due to polyamide coloring or thermal deterioration, it is preferable to perform polymerization while maintaining the trans isomer ratio at 80% or less.

  As a method for producing polyamide, it is easy to maintain the trans isomer ratio at 85% or less, and because the resulting polyamide has excellent color tone, 1) hot melt polymerization method, and 2) hot melt polymerization. -It is preferable to produce polyamide by a solid phase polymerization method.

  In the method for producing polyamide, the polymerization form may be a batch type or a continuous type.

  The polymerization apparatus is not particularly limited, and examples thereof include known apparatuses such as an autoclave type reactor, a tumbler type reactor, and an extruder type reactor such as a kneader.

  The method for producing the polyamide is not particularly limited, and the polyamide can be produced by a batch-type hot melt polymerization method described below.

  Examples of the batch-type hot melt polymerization method include, for example, a polyamide component ((a) dicarboxylic acid, (b) diamine, and, if necessary, (c) lactam and / or aminocarboxylic acid) using water as a solvent. About 40 to 60% by mass of the contained solution is concentrated to about 65 to 90% by mass in a concentration tank operated at a temperature of 110 to 180 ° C. and a pressure of about 0.035 to 0.6 MPa (gauge pressure). To obtain a concentrated solution. The concentrated solution is then transferred to an autoclave and heating is continued until the pressure in the container is about 1.5-5.0 MPa (gauge pressure). Thereafter, the pressure is maintained at about 1.5 to 5.0 MPa (gauge pressure) while draining water and / or gas components, and when the temperature reaches about 250 to 350 ° C., the pressure is reduced to atmospheric pressure (gauge pressure is , 0 MPa). By reducing the pressure to atmospheric pressure and then reducing the pressure as necessary, by-product water can be effectively removed. Then, it pressurizes with inert gas, such as nitrogen, and extrudes a polyamide melt as a strand. The strand is cooled and cut to obtain pellets.

  The method for producing the polyamide is not particularly limited, and the polyamide can be produced by a continuous hot melt polymerization method described below.

  As the continuous hot melt polymerization method, for example, a solution of about 40 to 60% by mass containing water and a polyamide component as a solvent is preheated to about 40 to 100 ° C. in a container of a preliminary apparatus, and then a concentration tank / Concentrated to about 70-90% at a pressure of about 0.1-0.5 MPa (gauge pressure) and a temperature of about 200-270 ° C. to obtain a concentrated solution. The concentrated solution is discharged into a flasher maintained at a temperature of about 200 to 350 ° C., and then the pressure is reduced to atmospheric pressure (gauge pressure is 0 MPa). After reducing the pressure to atmospheric pressure, reduce the pressure as necessary. The polyamide melt is then extruded into strands, cooled and cut into pellets.

  The polymer terminal of (A) polyamide in the present embodiment is classified and defined as follows. That is, 1) amino terminal, 2) carboxylic acid terminal, 3) cyclic amino terminal, 4) terminal by sealing agent, and 5) other terminal.

1) The amino terminal is an amino group (—NH ₂ group) bonded to the polymer terminal, and is derived from the raw material diamine.

  2) The carboxylic acid terminal is a carboxyl group (—COOH group) bonded to the polymer terminal and is derived from the raw material dicarboxylic acid.

3) The cyclic amino terminus is a cyclic amino group (group represented by Formula 1) bonded to the polymer terminus. In the formula, R represents a substituent bonded to carbon constituting the piperidine ring, and the ring is formed by deammonia reaction of a hydrogen atom, a methyl group, an ethyl group, a t-butyl group, or a diamine having a pentamethylenediamine skeleton as a raw material. Even if the converted piperidine is bonded to the polymer terminal, it becomes the terminal of this cyclic amino group. These structures may be taken when a monomer having a pentamethylenediamine skeleton is included.

  4) The end of the polymer is sealed with a carboxylic acid or an amine added at the time of polymerization.

  5) The other terminal is a polymer terminal not classified into 1) to 4), such as a terminal generated by deammonia reaction at the amino terminal or a terminal generated by decarboxylation from a carboxylic acid terminal.

  In the present embodiment, 3) the amount of the cyclic amino terminus is preferably 30 μeq / g or more and 65 μeq / g or less. Moreover, it is more preferable that they are 30 microequivalent / g or more and 60 microequivalent / g or less, and it is further more preferable that they are 35 microequivalent / g or more and 55 microequivalent / g or less. When the amount of the cyclic amino terminal is within the above range, the toughness, hydrolysis resistance, and processability of the polyamide can be improved.

The amount of the cyclic amino terminus can be measured using ¹ H-NMR. For example, it can be calculated based on the integral ratio of hydrogen bonded to carbon adjacent to the nitrogen atom of the nitrogen heterocycle and hydrogen bonded to carbon adjacent to the nitrogen atom of the amide bond of the polyamide main chain.

  The cyclic amino terminus is generated by dehydration reaction between the cyclic amine and the carboxylic acid terminus, or the amino terminus is generated by deammonia reaction in the polymer molecule.

  The cyclic amine can be added as a terminal blocking agent, or the diamine having a pentamethylenediamine skeleton, which is a polyamide raw material, can be deammoniated and cyclized to form in the reaction system. In this Embodiment, it is preferable that the cyclic amino terminal originates in the raw material diamine. Adding an end-capping agent at the initial stage of polymerization causes the low molecular weight carboxylic acid end to be capped at the initial stage of polymerization, causing a lower polymerization reaction rate of the polyamide, resulting in difficulty in obtaining a high molecular weight product. On the other hand, if it is a cyclic amine produced in the middle of the reaction, it becomes easier to obtain a polyamide high molecular weight product by producing it later in the polymerization.

Cyclic amines, which produce a cyclic amino terminus, are produced as a by-product during the polyamide polymerization reaction. About the production | generation of this cyclic amine, reaction rate improves, so that reaction temperature is high. Therefore, in order to make the cyclic amino terminal of the polyamide (A) in this embodiment constant, it is necessary to promote the generation of cyclic amine, and the reaction temperature of the polymerization of the polyamide is preferably 300 ° C. or higher. More preferably, it is 320 ° C. or higher.
In order to adjust these cyclic amino ends to a certain amount, it is possible to control by appropriately adjusting the polymerization temperature, the time of 300 ° C. or more during the polymerization step, the addition amount of the amine forming the cyclic structure, and the like. it can.

  In the present embodiment, it is preferable that 2) the amount of the amino terminal is 20 to 100 μeq / g. More preferably, it is 25-70 microequivalent / g. When the amount of the amino terminal is within the above range, the hydrolysis resistance and heat retention stability of the polyamide can be improved.

  As the molecular weight of the polyamide (A) in the present embodiment, sulfuric acid relative viscosity ηr at 25 ° C. can be used as an index.

  The molecular weight of the polyamide (A) in the present embodiment is as follows: mechanical properties such as toughness and rigidity, and moldability, etc., measured in accordance with JIS-K6920 at a concentration of 1% in 98% sulfuric acid and a relative viscosity ηr of sulfuric acid at 25 ° C. , Preferably it is 1.5-7.0, More preferably, it is 1.7-6.0, More preferably, it is 1.9-5.5.

  The measurement of sulfuric acid relative viscosity at 25 ° C. can be performed according to JIS-K6920 as described in the following examples.

  The melting point of the polyamide (A) in the present embodiment is preferably 270 to 350 ° C. from the viewpoint of heat resistance as Tm2 described in detail below. Melting | fusing point Tm2 becomes like this. Preferably it is 270 degreeC or more, More preferably, it is 275 degreeC or more, More preferably, it is 280 degreeC or more. The melting point Tm2 is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, further preferably 335 ° C. or lower, and still more preferably 330 ° C. or lower.

  (A) By setting the melting point Tm2 of the polyamide to 270 ° C. or higher, a polyamide having excellent heat resistance can be obtained. Further, by setting the melting point Tm2 of the polyamide (A) to 350 ° C. or lower, it is possible to suppress the thermal decomposition of the polyamide in the melt processing such as extrusion and molding.

  The heat of fusion ΔH of the polyamide (A) in the present embodiment is preferably 10 J / g or more, more preferably 14 J / g or more, further preferably 18 J / g or more, from the viewpoint of heat resistance. More preferably, it is 20 J / g or more.

  In the present embodiment, (A) the melting point of polyamide (Tm1 or Tm2 described in detail below) and the heat of fusion ΔH can be measured according to JIS-K7121.

  Examples of the measuring device for the melting point and the heat of fusion include Diamond-DSC manufactured by PERKIN-ELMER.

  The glass transition temperature Tg of the (A) polyamide in the present embodiment is preferably 90 to 170 ° C. The glass transition temperature is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 110 ° C. or higher. Further, the glass transition temperature is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.

  (A) By setting the glass transition temperature of polyamide to 90 ° C. or higher, a polyamide having excellent heat resistance and chemical resistance can be obtained. Moreover, the molded article with a good external appearance can be obtained by setting the glass transition temperature of (A) polyamide to 170 ° C. or lower.

  The glass transition temperature can be measured according to JIS-K7121 as described in the following examples.

  Examples of the glass transition temperature measuring device include Diamond-DSC manufactured by PERKIN-ELMER.

[(B) Titanium oxide]
Examples of (B) titanium oxide include titanium oxide (TiO), dititanium trioxide (Ti ₂ O 3), and titanium dioxide (TiO ₂ ). Of these, titanium dioxide is preferable.

  The crystal structure of these titanium oxides is not particularly limited, but is preferably a rutile type from the viewpoint of light resistance.

  The number average particle size of titanium oxide is 0.1 to 0.8 μm, more preferably 0.15 to 0.4 μm, and still more preferably 0.15 to 0.4 μm from the viewpoint of toughness and extrusion processability. 3 μm.

  The number average particle diameter of these titanium oxides can be measured by electron micrograph. For example, the polyamide resin composition is put into an electric furnace, the contained organic matter is incinerated, and, for example, 100 or more titanium oxides are arbitrarily selected from the residue, and observed with an electron microscope to measure the particle diameter. Thus, the number average particle diameter can be measured and determined.

  Titanium oxide may be obtained, for example, by a so-called sulfuric acid method in which a titanium sulfate solution is hydrolyzed, or by a so-called chlorine method in which titanium halide is vapor-phase oxidized, and there is no particular limitation.

  The surface of the titanium oxide particles is preferably coated. More preferably, it is first coated with an inorganic coating and then with an organic coating applied over the inorganic coating. The titanium oxide particles may be coated using any method known in the art. The inorganic coating preferably contains a metal oxide. The organic coating preferably includes one or more of carboxylic acids, polyols, alkanolamines and / or organosilicon compounds. Of these, polyols and organosilicon compounds are more preferred from the viewpoints of light resistance and film processability, and organosilicon compounds are even more preferred from the viewpoint of reducing generated gas during processing.

  Examples of carboxylic acids that can be used in the present invention for use as an organic coating include adipic acid, terephthalic acid, lauric acid, myristic acid, palmitic acid, stearic acid, polyhydroxystearic acid, oleic acid, salicylic acid, Malic acid and maleic acid are included. These carboxylic acid esters and metal salts may be used. Examples of the metal salt include aluminum salt, zinc salt, magnesium salt, calcium salt, barium salt and the like.

  Examples of alkanolamines that can be used in the present invention for use as an organic coating include monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, triethanolamine, and tripropanolamine. And organic acid salts such as acetate, oxalate, tartrate, formate and benzoate.

  Specific examples of polyols that can be used in the present invention for use as an organic coating include trimethylolpropane, trimethylolethane, ditrimethylolpropane, trimethylolpropane ethoxylate, pentaerythritol, and the like. Methylolpropane and trimethylolethane are preferred.

  Examples of organosilicon compounds that can be used in the present invention for use as an organic coating include organosilanes, organopolysiloxanes, and organosilazanes.

  Specifically, organosilanes include (a) aminosilane (aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc.), (b) Epoxy silane (γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.), (c) Methacrylsilane (γ- (methacryloyloxypropyl) trimethoxysilane, etc. ), (D) vinylsilane (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), (e) mercaptosilane (3-mercaptopropyltrimethoxysilane, etc.), (f) chloroalkylsilane (3-chloropropyltriethoxysilane, etc.) ), (G) alkylsilane (n-butyltriethoxysilane, isobuty Rutrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexylmethyldimethoxysilane, hexylmethyldiethoxysilane, cyclohexylmethyldiethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, etc.) (h ) Phenylsilane (such as phenyltriethoxysilane), (i) fluoroalkylsilane (such as trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane), or the like, or a hydrolysis product thereof.

  Organopolysiloxanes include (a) straight polysiloxane (dimethylpolysiloxane, methylhydrogen polysiloxane, methylmethoxypolysiloxane, methylphenylpolysiloxane, etc.), (b) modified polysiloxane (dimethylpolysiloxane diol, Dimethylpolysiloxane dihydrogen, side-chain or both-end amino-modified polysiloxane, side-chain or both-end or one-end epoxy-modified polysiloxane, both-end or one-end methacryl-modified polysiloxane, side-chain or both-end carboxyl-modified polysiloxane, Side-chain or both-end or one-end carbinol-modified polysiloxane, both-end phenol-modified polysiloxane, side-chain or both-end mercapto-modified polysiloxane, both-end or side-chain polyether-modified polysiloxane, side-chain alkyl-modified polysiloxane Xan, side chain methylstyryl modified polysiloxane, side chain higher carboxylic acid ester modified polysiloxane, side chain fluoroalkyl modified polysiloxane, side chain alkyl / carbinol modified polysiloxane, side chain amino / both end carbinol modified polysiloxane, etc. Etc.) or their copolymers. Furthermore, examples of organosilazanes include hexamethylsilazane and hexamethylcyclotrisilazane.

Among the organosilicon compounds, hydrophobic functional groups such as a methacryl group (—OCOC (CH ₃ ) ═CH ₂ ), a vinyl group (—CH═CH ₂ ), an alkyl group (—R), an aryl group (— Ph, -Ar, etc.), a carboxylic acid ester group (-OCOR), an acyl group (-COR), a polyether group _{(- (R 1 O) n} (R 2 O) mR 3), the fluorine-containing group (- (CH _{2) n CF 3, - (} CF 2) an organosilicon compound having an n CF _3, etc.) and the like, and still more preferably if organosilanes or organopolysiloxanes having a hydrophobic functional group.

  Among these organosilicon compounds, at least one selected from alkylsilanes having 4 to 10 carbon atoms, hydrolysis products thereof, dimethylpolysiloxane, and methylhydrogenpolysiloxane is more preferable. When an alkylsilane having 6 (hexyl group) having the largest number of carbon atoms in the alkyl group is used as the alkylsilane, the dispersibility and heat resistance are further improved. The hydrolyzed products of organosilanes are those in which hydrolyzable groups of organosilanes are hydrolyzed to form silanols, and those in which silanols are condensed to form dimers, oligomers, and polymers. To tell.

  Examples of inorganic coatings include metal oxides and hydrated oxides including oxides and hydrated oxides of silicon, aluminum, zirconium, phosphorus, zinc, rare earth elements and the like. Among these, preferred metal oxides are silica, alumina, and zirconia from the viewpoint of light resistance, and more preferred are silica and alumina. These inorganic coatings may be one type of metal oxide or a combination of two or more types.

  As an inorganic coating, it is preferable that it is 0.25-50 mass% with respect to 100 mass% of this titanium oxide whole quantity, It is more preferable that it is 0.25-10 mass%, It is 1-10 mass% Is more preferable.

  Although there is no restriction | limiting in particular in a titanium oxide, ignition loss does not have a restriction | limiting, It is preferable from a viewpoint of extrusion workability that it is the range of 0.7-2.5 mass% with respect to 100 mass% of titanium oxide whole quantity. More preferably, it is 0.7-2.0 mass%, More preferably, it is 0.8-1.5 mass%. Here, the loss on ignition can be calculated from the weight loss rate when titanium oxide is dried at 120 ° C. for 4 hours to remove moisture adhering to the surface and then heat-treated at 650 ° C. for 2 hours. .

  In addition, as these titanium oxides, one type may be used or two or more types may be used in combination.

  (A) As for the compounding quantity of polyamide and (B) titanium oxide, it is 55-95 mass% of (A) polyamide and 5-45 mass% of (B) titanium oxide with respect to 100 mass% of polyamide compositions. Is preferable from the viewpoint of whiteness, and more preferably, (A) polyamide is 65 to 85% by mass, and (B) titanium oxide is 15 to 35% by mass.

  In the present embodiment, from the viewpoint of light stability, (C) an amine light stabilizer may further be contained.

[(C) amine light stabilizer]
Examples of amine light stabilizers include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4 -Acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethyl Piperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethyl Piperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2, 2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis ( 2,2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4) -Piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pentamethyl- -Piperidyl) carbonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) oxalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6-pentamethyl-4) -Piperidyl) terephthalate, N, N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, 1,2-bis (2,2,6,6- Tetramethyl-4-piperidyloxy) ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl) -4 Piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetra Methyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-)) 2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N , N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine Polycondensate, poly [{6- (1, , 3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2, 2,6,6-tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis ( 1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene- 1,3,4-tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5- Di-t-butyl-4-h Droxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β , Β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol. In this Embodiment, these may be used individually by 1 type and may be used in combination of 2 or more type.

  Among these amine-based light stabilizers, a low molecular type having a molecular weight of less than 2,000 is preferable from the viewpoint of further improving the light stability. More preferably, the molecular weight is less than 1,000.

  In addition, the amine light stabilizers are NH type (indicating that hydrogen is bonded to the amino group), NR type (indicating that the alkyl group is bonded to the amino group), NOR type. There are types such as (indicating that an alkoxy group is bonded to an amino group). Among them, the NH type is preferable from the viewpoint of further improving the light stability.

  Among these amine light stabilizers, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2 , 2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4- Piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzene Dicarboxyamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate is preferred, and bis (2,2,6,6-tetra Methyl-4-piperidyl) sebacate, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, tetrakis (2,2,6,6-tetra More preferred is methyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzene More preferred is dicarboxamide.

  The compounding amount of the amine light stabilizer in the polyamide composition is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass, and still more preferably 100% by mass of the polyamide composition. 0.1 to 1% by mass. In the above range, light stability and heat aging resistance can be further improved, and the amount of generated gas can be reduced.

  In the present embodiment, from the viewpoint of heat stability, (D) a phenol-based heat stabilizer may be further contained.

[(D) Phenolic heat stabilizer]
Although it does not restrict | limit as a phenol type heat stabilizer below, For example, a hindered phenol compound is mentioned. Phenol-based heat stabilizers, particularly hindered phenol compounds, have the property of imparting heat resistance and light resistance to resins such as polyamide and fibers.

  Examples of the hindered phenol compound include, but are not limited to, for example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide), Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t-butyl) -4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxapyro [5,5] undecane, 3,5- -T-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, and 1, 3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid. In this Embodiment, these may be used individually by 1 type and may be used in combination of 2 or more type. Among these, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide)] is preferable from the viewpoint of improving heat aging resistance.

  The blending amount of the phenol-based heat stabilizer in the polyamide composition is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass, and still more preferably 100% by mass of the polyamide composition. 0.1 to 1% by mass. When it is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be further reduced.

  In the present embodiment, (E) an inorganic filler may be further contained from the viewpoint of mechanical properties such as strength and rigidity.

[(E) Inorganic filler]
(E) Although it does not specifically limit as an inorganic filler, For example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, kaolin, mica, Hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, calcium silicate, aluminosilicate Sodium, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, mica, montmorillonite, swellable fluorinated mica, and aluminum Tight, and the like. Among these, it is at least one selected from the group consisting of glass fiber, potassium titanate fiber, talc, wollastonite, kaolin, mica, calcium carbonate and clay, such as mechanical strength, appearance, whiteness, etc. It is preferable from the viewpoint.

  The glass fiber or carbon fiber may have a round or flat cross section. Examples of the flat cross section include a rectangle, an oval close to a rectangle, an ellipse, and a bowl shape with a narrowed central portion in the longitudinal direction. The flatness ratio is expressed by D2 / D1, where D2 is the major axis of the fiber cross section and D1 is the minor axis of the fiber cross section. (A perfect circle has a flatness ratio of about 1)

  Among glass fibers and carbon fibers, from the viewpoint that excellent mechanical strength characteristics can be imparted to the polyamide resin composition, the number average fiber diameter is 3 to 30 μm, and the resin composition has a weight average fiber length of 100. Those having a weight average fiber length and number average fiber diameter (L / D) of 10 to 100 are more preferably used.

  Further, from the viewpoints of reduction of warpage, heat resistance, toughness, low water absorption, and heat aging resistance of the plate-shaped molded product, the flatness is preferably 1.5 or more. More preferably, it is 1.5-10.0, More preferably, it is 2.5-10.0, Most preferably, it is 3.1-6.0. When the aspect ratio is extremely large, in addition to mixing with other components, it may be crushed during processing such as kneading and molding, and the desired effect may be reduced.

  The thickness of the glass fiber or carbon fiber having an aspect ratio of 1.5 or more is arbitrary, but the minor axis D1 of the fiber cross section is 0.5 to 25 μm, and the major axis D2 of the fiber cross section is 1.25 to 250 μm. Preferably there is. If it is too thin, it may be difficult to spin the fiber. If it is too thick, the strength of the molded product may decrease due to a decrease in the contact area with the resin. The short diameter D1 is preferably 3 μm or more. Furthermore, it is preferable that the minor axis D1 is 3 μm or more and the flatness is a value larger than 3.

  These glass fibers and carbon fibers having a flatness ratio of 1.5 or more are produced, for example, by the method described in Japanese Patent Publication No. 3-59019, Japanese Patent Publication No. 4-13300, Japanese Patent Publication No. 4-32775, and the like. I can do it. Particularly, in an orifice plate having a large number of orifices on the bottom surface, an orifice plate that surrounds a plurality of orifice outlets and has a convex edge extending downward from the bottom surface of the orifice plate, or a nozzle tip having one or more orifice holes. A glass fiber having a flatness ratio of 1.5 or more produced using a nozzle chip for deformed cross-section glass fiber spinning provided with a plurality of convex edges extending downward from the front end of the outer peripheral portion is preferable. In these fibrous reinforcing materials, fiber strands may be used as rovings as they are, or a cutting step may be obtained and used as chopped glass strands.

  Here, the number average fiber diameter and the weight average fiber length in this specification are, for example, putting the polyamide resin composition in an electric furnace, incinerating the organic matter contained, and, for example, 100 or more glass fibers from the residue. Select arbitrarily, observe with SEM, measure the fiber diameter of these glass fibers, measure the number average fiber diameter, and measure the fiber length using the SEM photograph at a magnification of 1000 times. There is a method for obtaining an average fiber length.

  You may surface-treat said glass fiber and carbon fiber with a silane coupling agent etc. Although it does not restrict | limit especially as said silane coupling agent, For example, aminosilanes, such as (gamma) -aminopropyl triethoxysilane, (gamma) -aminopropyl trimethoxysilane, and N- (beta)-(aminoethyl) -gamma-aminopropylmethyldimethoxysilane. And the like; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes. Especially, it is preferable that it is 1 or more types selected from said enumeration component, and aminosilanes are more preferable.

  In addition, for the above glass fiber and carbon fiber, as a sizing agent, an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer; Copolymer, epoxy compound, polyurethane resin, homopolymer of acrylic acid, copolymer of acrylic acid and other copolymerizable monomers, and these primary, secondary and tertiary amines A salt, a copolymer containing an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer, and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer may be included. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among them, from the viewpoint of the mechanical strength of the polyamide resin composition, the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer are structural units. Copolymer, epoxy compound and polyurethane resin, and combinations thereof are preferably used, and unsaturated vinyl monomer containing carboxylic acid anhydride-containing unsaturated vinyl monomer and unsaturated vinyl monomer containing carboxylic acid anhydride More preferred are copolymers and polyurethane resins containing a polymer as a structural unit, and combinations thereof.

  Among the copolymers containing carboxylic acid anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers excluding the carboxylic acid anhydride-containing unsaturated vinyl monomers as constituent units, the carboxylic acid anhydride-containing copolymer Examples of the unsaturated vinyl monomer include, but are not limited to, maleic anhydride, itaconic anhydride, and citraconic anhydride. Among them, maleic anhydride is preferable. On the other hand, the unsaturated vinyl monomer excluding the carboxylic anhydride-containing unsaturated vinyl monomer means an unsaturated vinyl monomer different from the carboxylic anhydride-containing unsaturated vinyl monomer. Examples of the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer include, but are not limited to, for example, styrene, α-methylstyrene, ethylene, propylene, butadiene, isoprene, chloroprene, 2, Examples include 3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, and ethyl methacrylate. Of these, styrene and butadiene are preferred.

  Among these combinations, selected from the group consisting of a copolymer of maleic anhydride and butadiene, a copolymer of maleic anhydride and ethylene, a copolymer of maleic anhydride and styrene, and a mixture thereof. It is more preferable that it is 1 type or more.

  In addition, a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units has a weight average molecular weight of 2 1,000 or more. Moreover, from a viewpoint of the fluidity | liquidity improvement of a polyamide resin composition, More preferably, it is 2,000-1,000,000, More preferably, it is 2,000-500,000. In addition, the weight average molecular weight in this specification is a value measured by GPC.

  Examples of the epoxy compound include, but are not limited to, ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, decene oxide, undecene oxide, dodecene oxide, penta Aliphatic epoxy compounds such as decene oxide and eicosene oxide; glycidol, epoxypentanol, 1-chloro-3,4-epoxybutane, 1-chloro-2-methyl-3,4-epoxybutane, 1 , 4-dichloro-2,3-epoxybutane, cyclopentene oxide, cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, methylcyclohexene oxide, vinylcyclohexene oxide And alicyclic epoxy compounds such as epoxidized cyclohexene methyl alcohol; terpene epoxy compounds such as pinene oxide; aromatic epoxy compounds such as styrene oxide, p-chlorostyrene oxide and m-chlorostyrene oxide; epoxidized soybean oil; And epoxidized linseed oil.

  The polyurethane resin is not particularly limited as long as it is generally used as a sizing agent. For example, m-xylylene diisocyanate (XDI), 4,4′-methylenebis (cyclohexyl isocyanate) (HMDI), and isophorone diester are used. Those synthesized from isocyanates such as isocyanate (IPDI) and polyester or polyether diols can be suitably used.

  The acrylic acid homopolymer (polyacrylic acid) preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.

  The polyacrylic acid may be in a salt form. Such polyacrylic acid salts include primary, secondary or tertiary amines. Although it does not restrict | limit to the following, For example, a triethylamine, a triethanolamine, glycine etc. are mentioned. The degree of neutralization is preferably 20 to 90% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and from the viewpoint of reducing amine odor, and is preferably 40 to 60%. More preferably.

  The weight average molecular weight of the polyacrylic acid forming the salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. 3,000 or more are preferable from the viewpoint of improving the converging property of glass fiber or carbon fiber, and 50,000 or less are preferable from the viewpoint of improving mechanical properties when a resin composition is obtained.

  The monomer that forms a copolymer with acrylic acid is not limited to the following, but examples include acrylic acid, maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. 1 or more types selected from monomers having a hydroxyl group and / or a carboxyl group such as (except for the case of acrylic acid only). Preferably, it has 1 or more types of ester monomers among the above-mentioned monomers.

  The polymer of acrylic acid may be a copolymer of acrylic acid and other copolymerizable monomers. Examples of the monomer that forms a copolymer with acrylic acid include, but are not limited to, for example, among monomers having a hydroxyl group and / or a carboxyl group, acrylic acid, maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, and isocrotone. One or more selected from the group consisting of acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid are included (except for acrylic acid only). Preferably, it has 1 or more types of ester monomers among the above-mentioned monomers.

  The polymer of polyacrylic acid (including both homopolymer and copolymer) may be in the form of a salt. The salt of the acrylic acid polymer includes, but is not limited to, primary, secondary or tertiary amines. Although not limited to the following, specific examples include triethylamine, triethanolamine, and glycine. The degree of neutralization is preferably 20 to 90%, and preferably 40 to 60% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and reducing the amine odor. Is more preferable.

  The weight average molecular weight of the acrylic acid polymer forming the salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. 3,000 or more are preferable from the viewpoint of improving the converging property of glass fiber or carbon fiber, and 50,000 or less are preferable from the viewpoint of improving mechanical properties when a resin composition is obtained.

  Glass fiber or carbon fiber is a fiber strand produced by applying the above bundling agent to glass fiber or carbon fiber using a known method such as a roller-type applicator in the known glass fiber or carbon fiber production process. Can be obtained by continuous reaction by drying. The fiber strand may be used as a roving as it is, or may be used as a chopped glass strand by further obtaining a cutting step.

  The sizing agent preferably imparts (adds) 0.2 to 3% by mass, more preferably 0.3 to 2% by mass (as a solid fraction), with respect to 100% by mass of glass fiber or carbon fiber. Added. From the viewpoint of maintaining the bundling of the glass fiber or carbon fiber, the addition amount of the bundling agent is preferably 0.2% by mass or more as a solid content with respect to 100% by mass of the glass fiber or carbon fiber. On the other hand, from the viewpoint of improving the thermal stability of the polyamide resin composition, it is preferably 3% by mass or less. The strand may be dried after the cutting step, or may be cut after the strand is dried.

  Inorganic fillers other than glass fibers and carbon fibers are preferably wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate, aluminum borate, and clay from the viewpoint of strength and rigidity, and surface appearance. Can be used. More preferred are wollastonite, kaolin, mica and talc, still more preferred are wollastonite and mica, and most preferred is wollastonite. These inorganic fillers may be used individually by 1 type, and may be used in combination of 2 or more type.

  The particle size of the inorganic filler other than glass fibers and carbon fibers is preferably 0.01 to 38 μm from the viewpoint of toughness and surface appearance. 0.03-30 micrometers is more preferable, 0.05-25 micrometers is more preferable, 0.1-20 micrometers is still more preferable, 0.15-15 micrometers is the most preferable.

  By setting the average particle size to 38 μm or less, a polyamide composition having excellent toughness and surface appearance can be obtained. Further, when the thickness is 0.1 μm or more, the balance between cost, powder handling surface and physical properties is excellent.

  Further, among the inorganic fillers, those having an acicular shape such as wollastonite have an average fiber diameter as an average particle diameter. Furthermore, when the cross section is not a circle, the maximum value of the length is taken as the fiber diameter.

  Regarding the aspect ratio (L / D) between the weight average fiber length and the number average fiber diameter of the needle-shaped shape, from the viewpoint of the appearance of the molded product and the wear of metallic parts such as an injection molding machine, 1.5 to 10 is preferable, 2.0 to 5 is more preferable, and 2.5 to 4 is still more preferable.

  Also, inorganic fillers other than glass fibers and carbon fibers used in the present invention are those subjected to surface treatment with ordinary surface treatment agents such as coupling agents such as silane coupling agents and titanate coupling agents. It doesn't matter. As the silane coupling agent, an epoxy silane coupling agent can be preferably exemplified. Further, a mixture of a polyalkoxysiloxane and an epoxy silane coupling agent and / or a reaction product of a polyalkoxy siloxane and an epoxy silane coupling agent can also be preferably used. Such a surface treating agent can be pretreated on the surface of the inorganic filler, or may be added when the polyamide and the inorganic filler are mixed. Moreover, the quantity of a preferable surface treating agent is the range of 0.05 mass%-1.5 mass% with respect to an inorganic filler.

  The compounding amount of the inorganic filler in the polyamide composition is preferably 0 to 25% by mass, more preferably 1 to 25% by mass, and further preferably 2 to 20% with respect to 100% by mass of the polyamide composition. % By mass. In the case of the above range, the strength, rigidity and toughness can be kept in a good balance.

  In the present embodiment, a phosphorus-based heat stabilizer can be blended within a range that does not impair the purpose of the present embodiment.

[Phosphorus heat stabilizer]
Examples of the phosphorus-based heat stabilizer include, but are not limited to, for example, pentaerythritol type phosphite compound, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl phosphite, phenyl Diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di -T-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4'-butylidene-bis (3- Til-6-tert-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, 4,4′-isopropylidenebis (2-tert-butyl) Phenyl) .di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite , Tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, tris (mono , Dimixed nonylphenyl) phosphite, 4,4′-isopropylidenebis (2- -Butylphenyl) .di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di-t -Butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenyl polyphosphite, bis (octylphenyl) bis (4,4'-butylidenebis (3-methyl-6-tert-butyl) Phenyl)) · 1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) diphosphite, tris (4,4′-isopropyl Redenbis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite, 2, 2 Methylene bis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylene bis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4- And di-t-butyl-5-methylphenyl) -4,4′-biphenylene diphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite. In this Embodiment, these may be used individually by 1 type and may be used in combination of 2 or more type.

  Among those listed above, pentaerythritol phosphite compounds and tris (2,4-di-t-butylphenyl) phosphite are preferable from the viewpoint of further improving the heat aging resistance and reducing the generated gas. Examples of the pentaerythritol phosphite compound include, but are not limited to, for example, 2,6-di-t-butyl-4-methylphenyl phenyl pentaerythritol diphosphite, 2,6-di-t-butyl. -4-methylphenyl methyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl 2-ethylhexyl pentaerythritol diphosphite, 2,6-di-t-butyl-4 -Methylphenyl isodecyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl lauryl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl Isotridecyl pentaerythritol diphosphite, 2,6-di-t-butyl-4 Methylphenyl stearyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl cyclohexyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl benzyl Pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl ethyl cellosolve Pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl butyl carbitol Pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl octylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl nonylphenyl pentaerythritol Diphosphite, bis (2,6-di-t- Til-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl 2,6-di-t-butylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl, 2,4-di-t-butylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl · 2,4-di-t-octylphenyl · pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl · 2-cyclohexyl Phenyl pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl phenyl pentaerythritol Diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphos Fight is mentioned. In this Embodiment, these may be used individually by 1 type and may be used in combination of 2 or more type.

  Among the pentaerythritol type phosphite compounds listed above, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-) Ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) Pentaerythritol diphosphite is preferred, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferred.

  When using a phosphorus heat stabilizer, the compounding quantity of the phosphorus heat stabilizer in a polyamide composition is 0.01-1 mass% with respect to 100 mass% of polyamide compositions, More preferably, it is 0.1. ˜1% by mass. When it is within the above range, the heat aging resistance can be further improved and the amount of generated gas can be further reduced.

  In the present embodiment, a phosphorus compound can be blended within a range that does not impair the purpose of the present embodiment.

[Phosphorus compounds]
Examples of phosphorus compounds include, but are not limited to, 1) phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof, 2) phosphoric acid, phosphorous acid, One or more selected from phosphorous acid and metal salts of intramolecular and / or intermolecular condensates thereof may be mentioned.
Examples of the phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof in 1) include, for example, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, Examples include pyrophosphorous acid and diphosphorous acid.
2) Phosphoric acid, phosphorous acid, hypophosphorous acid, and metal salts of intramolecular and / or intermolecular condensates thereof are the phosphorous compounds of 1) and groups 1 and 2 of the periodic table. And salts with manganese, zinc and aluminum.

  More preferably, the phosphorus compound is at least one selected from metal phosphates, metal phosphites or metal hypophosphites, and intramolecular and / or intermolecular condensates thereof, more preferably phosphorus. Salts of phosphorus compounds selected from acids, phosphorous acid, hypophosphorous acid and metals selected from Groups 1 and 2 of the periodic table, manganese, zinc and aluminum, and their intra- and / or molecules An intercondensate is preferred. Particularly preferred is a metal salt comprising a phosphorus compound selected from phosphoric acid, phosphorous acid and hypophosphorous acid and a metal selected from Groups 1 and 2 of the periodic table, for example, monosodium phosphate, Disodium phosphate, trisodium phosphate, monocalcium phosphate, dicalcium phosphate, tricalcium phosphate, sodium pyrophosphate, sodium metaphosphate, calcium metaphosphate, sodium hypophosphite, calcium hypophosphite, etc. These anhydrous salts and hydrates can be mentioned. Among these, sodium hypophosphite and calcium hypophosphite are most preferable.

  When using a phosphorus compound, the compounding quantity of the phosphorus compound in a polyamide composition is 0.01-1 mass% with respect to 100 mass% of polyamide compositions, More preferably, it is 0.05-1 mass%. . In the above range, the heat discoloration can be further improved.

[Other components that may be included in the polyamide composition]
In addition to the above-described components, other components may be added as necessary within a range not impairing the effects of the present embodiment.

  Although not limited to the following, for example, colorants such as pigments and dyes (including colored master batches), mold release agents, flame retardants, fibrillating agents, lubricants, optical brighteners, plasticizers, copper compounds, halogenated Mixing alkali metal compounds, antioxidants, stabilizers, UV absorbers, antistatic agents, fluidity improvers, fillers, reinforcing agents, spreading agents, nucleating agents, rubber, reinforcing agents and other polymers Also good. Here, since the above-mentioned other components are greatly different in properties, there are various suitable contents for each component that hardly impair the effects of the present embodiment. A person skilled in the art can easily set a suitable content for each of the other components described above.

  The method for producing the polyamide composition in the present embodiment is not particularly limited as long as it is a method of mixing the (A) polyamide and (B) titanium oxide.

  As a mixing method of polyamide and titanium oxide, for example, polyamide and titanium oxide are mixed using a tumbler, a Henschel mixer, etc., supplied to a melt kneader and kneaded, or melted with a single screw or twin screw extruder. The method of mix | blending titanium oxide with polyamide from a side feeder is mentioned.

  (E) The same method can be used when blending the inorganic filler, and it is mixed with polyamide or the like and supplied to a melt-kneader, or it is melted with a single-screw or twin-screw extruder. The method of mix | blending an inorganic filler with a polyamide and titanium oxide from a side feeder is mentioned.

  In the method of supplying the components constituting the polyamide composition to the melt kneader, all the components may be supplied to the same supply port at once, or the components may be supplied from different supply ports.

  The melt kneading temperature is preferably about 250 to 375 ° C. as the resin temperature, and the melt kneading time is preferably about 0.25 to 5 minutes.

  The apparatus for performing melt kneading is not particularly limited, and a known apparatus, for example, a melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, and a mixing roll can be used.

  The 25 ° C. sulfuric acid relative viscosity ηr, the melting point Tm2, the heat of fusion ΔH, and the glass transition temperature Tg of the polyamide composition of the present embodiment can be measured by the same method as that for the polyamide. Moreover, when the measured value in a polyamide composition exists in the range similar to a preferable range as a measured value of the said polyamide, the polyamide composition excellent in heat resistance, a moldability, and chemical resistance can be obtained.

  Molded articles of the polyamide composition of the present embodiment are known molding methods such as press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and melting. It can be obtained using a generally known plastic molding method such as spinning.

  The molded product obtained from the polyamide composition of the present embodiment is excellent in heat resistance, moldability, mechanical strength, and low water absorption. Therefore, the polyamide composition of the present embodiment can be suitably used as various parts materials for automobiles, electrical and electronic products, industrial materials, daily products and household products, and extrusion applications. .

  It is not particularly limited for automobiles, and is used for, for example, intake system parts, cooling system parts, fuel system parts, interior parts, exterior parts, and electrical parts.

  The automobile intake system parts are not particularly limited, and examples include an air intake manifold, an intercooler inlet, an exhaust pipe cover, an inner bush, a bearing retainer, an engine mount, an engine head cover, a resonator, and a throttle body.

  The automobile cooling system component is not particularly limited, and examples thereof include a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an oil netter, and a delivery pipe.

The automobile fuel system parts are not particularly limited, and examples thereof include a fuel delivery pipe and a gasoline tank case.
The interior part is not particularly limited, and examples thereof include an instrument panel, a console box, a glove box, a steering wheel, and a trim.

  The exterior parts are not particularly limited, and examples include a mall, a lamp housing, a front grille, a mud guard, a side bumper, a door mirror stay, and a roof rail.

  The electrical component is not particularly limited, and examples thereof include a connector, a wire harness connector, a motor component, a lamp socket, a sensor on-vehicle switch, and a combination switch.

  The electric and electronic devices are not particularly limited, and are used for connectors, switches, relays, printed wiring boards, electronic component housings, outlets, noise filters, coil bobbins, motor end caps, and the like.

  For industrial equipment, it is not particularly limited. For example, it is used for gears, cams, insulating blocks, valves, electric tool parts, agricultural equipment parts, engine covers, and the like.

It is not specifically limited as for daily use and household goods, for example, it is used for buttons, food containers, office furniture and the like.
The extrusion application is not particularly limited. For example, it is used for a film, a sheet, a filament, a tube, a rod, a hollow molded article, and the like.

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to these examples.

The raw materials and measurement methods used in Examples and Comparative Examples are shown below. In this example, 1 kg / cm ² means 0.098 MPa.
[raw materials]

The following compounds were used in this example.
(A) As a polyamide raw material (a) Dicarboxylic acid (a-1) 1,4-cyclohexanedicarboxylic acid (CHDA) (trade name: 1,4-CHDA HP grade (trans isomer / cis isomer = 25/75) (yeast Man Chemical)))
(A-2) Terephthalic acid (TPA) (manufactured by Wako Pure Chemical Industries, Ltd.)
(A-3) Adipic acid (ADA) (Wako Pure Chemical Industries, Ltd.)
(A-4) Dodecanedioic acid (C12DA) (manufactured by Wako Pure Chemical Industries, Ltd.)
(B) Diamine (b-1) 2-Methylpentamethylenediamine (2MPD) (manufactured by Tokyo Chemical Industry)
(B-2) Hexamethylenediamine (HMD) (manufactured by Wako Pure Chemical Industries, Ltd.)
(B-3) 1,9-nonamethylenediamine (NMD) (manufactured by Aldrich)
(B-4) 2-Methyloctamethylenediamine (2MOD) (manufactured with reference to the production method described in JP-A No. 05-17413)

(B) Titanium oxide (B-1) TiO2-1
Number average particle diameter: 0.21 μm
Coating: Alumina, silica, siloxane compound Loss on ignition: 1.21% by mass
(B-2) TiO2-2
Number average particle diameter: 0.21 μm
Coating: Alumina, silica, polyol compound Loss on ignition: 1.19% by mass
(B-3) TiO2-3
Number average particle diameter: 0.25 μm
Coating: Alumina, zirconia, siloxane compound Loss on ignition: 1.43% by mass
(B-4) TiO2-4
Number average particle diameter: 0.25 μm
Coating: Alumina, silica, siloxane compound Loss on ignition: 2.61% by mass
(B-5) TiO2-5
Product name: Taipei (registered trademark) CR-63 (Ishihara Sangyo Co., Ltd.)
Number average particle diameter: 0.21 μm
Coating: Alumina, silica, siloxane compound Loss on ignition: 0.43% by mass
(B-6) TiO2-6
Number average particle diameter: 1.0 μm
Coating: Alumina, silica, polyol compound Loss on ignition: 1.10% by mass

(C) Amine light stabilizer (HALS)
(C-1) HALS-1
Product name: Nylostab (registered trademark) S-EED (manufactured by Clariant)
Molecular weight: 443
(C-2) HALS-2
Product name: TINUVIN (registered trademark) 770DF (manufactured by Ciba)
Molecular weight: 481
(C-3) HALS-3
Product name: Adeka's Tab (registered trademark) LA-57 (manufactured by ADEKA)
Molecular weight: 791
(C-4) HALS-4
Product name: CHIMASSORB (registered trademark) 119FL (Ciba)
Molecular weight: A mixture of 2286 compound (90% by mass) and 3100-4000 compound (10% by mass)

(D) Phenol-based heat stabilizer Product name: IRGANOX (registered trademark) 1098 (manufactured by Ciba)

(E) Inorganic filler (E-1) Glass fiber Product name: ECS 03T-275H (Nippon Electric Glass Co., Ltd.)
Average fiber diameter 10μmφ, cut length 3mm
(E-2) Wollastonite Product name: NYGLOS8 (manufactured by NYCO)
Average fiber diameter 8μm
(E-3) Talc Product name: PKP-80 (manufactured by Fuji Talc)
Average particle size 14μm

(F) Phosphorus compound Product name: Sodium hypophosphite monohydrate (Wako Pure Chemical Industries, Ltd.)

(G) Nucleating agent (G-1) Boron nitride Product name: DENKABORON NITRIDE SP-7 (manufactured by Denki Kagaku Kogyo Co., Ltd.)

[Calculation of polyamide content]
(A-1) The mol% of the alicyclic dicarboxylic acid is (the number of moles of (a-1) alicyclic dicarboxylic acid added as a raw material monomer / the number of moles of all (a) dicarboxylic acids added as raw material monomers. ) × 100.
(B-1) The mole% of the diamine having a substituent branched from the main chain is ((b-1) mole number of diamine having a branched structure of the main chain / raw monomer added as a raw material monomer) b) Number of moles of diamine) x 100.
In addition, when calculating by the above formula, the denominator and the numerator do not include the number of moles of the diamine having a branched main chain (b-1) added as an additional component.

[Measuring method]
(1) Melting points Tm1, Tm2 (° C.)
According to JIS-K7121, it measured using Diamond-DSC by PERKIN-ELMER. The measurement condition is that the temperature of an endothermic peak (melting peak) that appears when about 10 mg of a sample is heated to 300 to 350 ° C. according to the melting point of the sample at a heating rate of 20 ° C./min in a nitrogen atmosphere is Tm1 (° C.) After maintaining the temperature in the molten state at the highest temperature rise for 2 minutes, the temperature was lowered to 30 ° C. at a temperature drop rate of 20 ° C./min, held at 30 ° C. for 2 minutes, and the same at the temperature rise rate of 20 ° C./min. The maximum peak temperature of the endothermic peak (melting peak) that appears when the temperature is raised to is melting point Tm2 (° C.), and the total peak area is the heat of fusion ΔH (J / g). When there were a plurality of peaks, those having ΔH of 1 J / g or more were regarded as peaks. For example, when there are two peaks of melting point 295 ° C., ΔH = 20 J / g, melting point 325 ° C., ΔH = 5 J / g, the melting point Tm 2 was 325 ° C. and ΔH = 25 J / g.

(2) Trans isomer ratio 30-40 mg of polyamide was dissolved in 1.2 g of hexafluoroisopropanol deuteride and measured by ¹ H-NMR. In the case of 1,4-cyclohexanedicarboxylic acid, the trans isomer ratio was determined from the ratio of the peak area of 1.98 ppm derived from the trans isomer and the peak areas of 1.77 ppm and 1.86 ppm derived from the cis isomer.

(3) Glass transition temperature Tg (° C)
According to JIS-K7121, it measured using Diamond-DSC by PERKIN-ELMER. Measurement conditions were such that a sample in a molten state obtained by melting a sample on a hot stage (EP80 manufactured by Mettler) was rapidly cooled using liquid nitrogen and solidified to obtain a measurement sample. Using 10 mg of the sample, the glass transition temperature was measured by raising the temperature in the range of 30 to 350 ° C. under a temperature raising speed of 20 ° C./min.

(4) Cyclic amino terminal quantity The quantity of the cyclic amino group couple | bonded with the polymer terminal was measured using < ¹ > H-NMR. Signal of hydrogen bonded to carbon adjacent to nitrogen atom of nitrogen heterocycle (chemical shift value 3.5 to 4.0 ppm) and signal of hydrogen bonded to carbon adjacent to nitrogen atom of amide bond of polyamide main chain ( The chemical shift value was calculated using an integration ratio of 3.0 to 3.5 ppm. The total number of terminals used at that time was calculated as 2 / Mn × 1000000 (μ equivalent / g) using Mn measured by GPC (hexafluoropropanol solvent, PMMA standard sample conversion).

(5) Sulfuric acid relative viscosity ηr at 25 ° C
It implemented according to JIS-K6810. Specifically, a 1% concentration solution ((polyamide 1 g) / (98% sulfuric acid 100 mL)) was prepared using 98% sulfuric acid and measured under a temperature condition of 25 ° C.

(6) Loss on ignition of titanium oxide Titanium oxide was dried at 120 ° C. for 4 hours to remove water adhering to the surface, and then allowed to stand for 30 minutes in a desiccator and cooled. Subsequently, about 10 g was precisely weighed in a magnetic crucible and heated in an electric furnace at 650 ° C. for 2 hours. After heating, the mixture was allowed to stand for 30 minutes in a desiccator and cooled, and then the weight was measured. The weight loss rate before and after heating was calculated and used as ignition loss.

(7) Bending amount (mm)
Using the injection molding machine [PS-40E: manufactured by Nissei Resin Co., Ltd.], the polyamide composition pellets obtained in the examples and comparative examples were injected + pressure holding time 10 seconds, cooling time 15 seconds, and mold temperature. A strip-shaped molded piece having a length of 128 mm, a width of 12.8 mm, and a thickness of 0.7 mm was formed by setting the molten resin temperature to 120 ° C. and Tm2 + 20 ° C. of (A) polyamide.
Using the obtained test piece, a bending test was performed at a span distance of 28 mm and a compression speed of 5 mm / min, and the amount of deflection at the maximum load was measured.

(8) Spiral flow length (cm)
Using the injection molding machine [IS-100GN: manufactured by Toshiba Machine Co., Ltd.], the polyamide composition pellets obtained in the examples and comparative examples were injected + holding pressure time 10 seconds, cooling time 15 seconds, and mold temperature. 120 ° C., the molten resin temperature is set to Tm2 + 20 ° C. of (A) polyamide, the injection speed is 100 mm / s, the injection pressure is 100 MPa, the width is 10 mm, and the thickness is 1.0 mm. The flow length was measured.

(9) Whiteness Using the injection molding machine [PS-40E: manufactured by Nissei Plastic Co., Ltd.], the polyamide composition pellets obtained in the examples and comparative examples were injected and held for 10 seconds and cooled for 15 seconds. The mold temperature was set to 120 ° C., the molten resin temperature was set to Tm2 + 20 ° C. of (A) polyamide, and a molded piece having a length of 60 mm × width of 60 mm × thickness of 2.0 mm was formed.
Using the spectral color difference meter [SE6000: made by Nippon Denshoku Industries Co., Ltd.], the obtained molded piece was compliant with JIS Z8730, and brightness (L value), redness (a value), yellow according to Hunter's color difference formula The degree (b value) was obtained, and the whiteness (W) was calculated.
W = 100 − [(100−L) ² + a ² + b ² ] ^1/2

(10) Whiteness after heat treatment The molded piece of length 60 mm x width 60 mm x thickness 2.0 mm obtained above was heat-treated in a hot air dryer at 160 ° C for 24 hours. The test specimen after the treatment was measured for color tone with a color difference meter in the same manner as described above, and the whiteness was calculated.

(11) Extrusion workability 3 kg of the polyamide resin composition pellets obtained in the examples and comparative examples were spread on a metal bat, and the number of foreign matters due to eyes was measured visually.

(12) Gas generated during processing When producing a polyamide composition in Examples and Comparative Examples, the amount of gas generated from a die was visually observed. The case where there was almost no generated gas was indicated as ◯, the case where some gas was generated was indicated as Δ, and the case where there was a large amount of gas was indicated as ×.

(13) Film processability The polyamide composition pellets obtained in the examples and comparative examples were obtained by using a cylinder having a screw diameter of 40 mm and a T die (width: 40 cm) set to (A) polyamide Tm2 + 20 ° C. Extrusion sheet molding was performed using a screw extruder at a screw speed of 30 rpm and a discharge rate of 6 kg / h. At this time, the clearance of the T dice and the sheet take-up speed were adjusted so that the sheet had a thickness of 50 μm. The obtained sheet was cut out to 100 mm × 100 mm, and the thickness at 16 points serving as intersections was measured using lines as markings at intervals of 20 mm in the vertical and horizontal directions, and thickness unevenness was measured. The thickness unevenness was obtained by dividing the difference (y) between the maximum thickness and the minimum thickness by the average thickness value (x).
Thickness unevenness = y / x x 100 (%)
The case where the thickness unevenness was less than 5% was evaluated as ◯, the case where it was 5% or more and less than 10% was Δ, and the case where it was 10% or more was rated as x.

(14) Molding retention stability The polyamide composition pellets obtained in the examples and comparative examples were injected using an injection molding machine [PS-40E: manufactured by Nissei Resin Co., Ltd.], injection + pressure holding time 10 seconds, cooling time. For 15 seconds, the mold temperature was set to 120 ° C., the molten resin temperature was set to Tm2 + 20 ° C. of (A) polyamide, and a strip-shaped molded piece having a length of 128 mm × width of 12.8 mm × thickness of 0.7 mm was molded. After 20 shots of continuous injection molding, the amount of resin dripping from the tip of the molding machine nozzle was measured when the nozzle was left for 30 seconds after being separated from the mold.

Polyamide [Production Example 1]
A polyamide polymerization reaction was carried out by the “hot melt polymerization method” described below.
(A) CHDA 896 g (5.20 mol) and (b) 2MPD 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare an aqueous mixture of 50 mol% equimolar amounts of the raw material monomers.

The obtained water mixture and 21 g (0.18 mol) of 2MPD, which is an additive at the time of melt polymerization, are charged into an autoclave (made by Nitto Koatsu) with an internal volume of 5.4 L, and the liquid temperature (internal temperature) is 50 ° C. The inside of the autoclave was replaced with nitrogen. Heating was continued until the pressure in the autoclave tank was about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank was expressed as gauge pressure) (at this time, the liquid temperature was about 145). Up to ℃). In order to keep the pressure in the tank at about 2.5 Kg / cm ² , heating was continued while removing water out of the system, and the aqueous solution was concentrated to a concentration of about 85%. The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 Kg / cm ² . Heating was continued until the final temperature was −50 ° C. while removing water out of the system in order to keep the pressure in the tank at about 30 Kg / cm ² . Further, while the heating was continued, the pressure in the tank was reduced to atmospheric pressure (gauge pressure was 0 kg / cm ² ) over 60 minutes. The heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 345 ° C. With the resin temperature kept in this state, the inside of the tank was maintained for 10 minutes under a reduced pressure of 100 torr with a vacuum apparatus. Thereafter, it was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain a polyamide. The obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then the measurement results (melting point Tm2, glass transition temperature Tg, trans isomer ratio) performed based on the above measurement method. Table 1 shows the relative viscosity of sulfuric acid at 25 ° C. and the amount of cyclic amino terminals). The polymerization was repeated under the same conditions so as to ensure the amount required for measurement evaluation and examples, and all were mixed and used.

[Production Example 2]
The polyamide obtained using the melt polymerization described in Production Example 1 was further subjected to the “solid phase polymerization” described below.
10 kg of polyamide pellets obtained by melt polymerization were placed in a conical ribbon vacuum dryer (trade name ribocorn RM-10V, manufactured by Okawara Seisakusho Co., Ltd.), and sufficiently substituted with nitrogen. While flowing nitrogen at 1 L / min, heating was performed at 260 ° C. for 6 hours while stirring. Thereafter, the temperature was lowered while flowing nitrogen, and when the temperature reached about 50 ° C., the pellets were taken out from the apparatus to obtain polyamide. Table 1 shows the measurement results of the obtained polyamide based on the above measurement method.

[Production Examples 3 and 6, Comparative Production Examples 1 and 2]
Production Example 1 except that the compounds and amounts shown in Table 1 were used as (a) dicarboxylic acid and (b) diamine, and the final temperature of the resin temperature was changed to the temperature shown in Table 1. Polyamide was polymerized by the method described in Example 1 ("hot melt polymerization method").
Table 1 shows the measurement results of the obtained polyamide based on the above measurement method.

[Production Examples 4 and 5]
Production Example 1 except that the compounds and amounts shown in Table 1 were used as (a) dicarboxylic acid and (b) diamine, and the final temperature of the resin temperature was changed to the temperature shown in Table 1. After performing the melt polymerization of the polyamide by the method described in Example 1, the solid phase polymerization was performed in the same manner as in Production Example 2 except that the solid phase polymerization temperature and the solid phase polymerization time were changed to the conditions described in Table 1. .

Table 1 shows the measurement results of the obtained polyamide based on the above measurement method.

[Comparative Production Example 3]
Polyamide 9T (hereinafter abbreviated as “PA9T”) was produced according to the method described in Example 1 of JP-A-7-228689. At that time, the terephthalic acid unit was a dicarboxylic acid unit. On the other hand, 1,9-nonamethylenediamine unit and 2-methyloctamethylenediamine unit [1,9-nonamethylenediamine unit: 2-methyloctamethylenediamine unit = 80: 20 (molar ratio)] were used as diamine units.

The above raw materials were placed in a 20 liter autoclave and replaced with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 210 ° C. over 2 hours. At that time, the autoclave was pressurized to 22 kg / cm ² . The reaction was continued as it was for 1 hour, then the temperature was raised to 230 ° C., then the temperature was kept constant at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and keeping the pressure at 22 kg / cm ² . Next, the pressure was reduced to 10 kg / cm ² over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer. This was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was subjected to solid phase polymerization at 230 ° C. and 0.1 mmHg for 10 hours to obtain PA9T. Here, ηr was 2.59.

Polyamide composition [Examples 1-6, Comparative Examples 1-3]
The polyamide of the production example or the comparative production example was dried in a nitrogen stream to adjust the moisture content to about 0.2% by mass. L / D (extruder cylinder length / extruder cylinder diameter) having an upstream supply port in the first barrel from the upstream side of the extruder and a downstream supply port in the ninth barrel = 48 (number of barrels: 12) twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] was manufactured from the upstream supply port to the die in the production example. (A) Tm2 + 20 ° C. of polyamide Set at a screw rotation speed of 250 rpm and a discharge rate of 25 kg / h, polyamide, titanium oxide, amine light stabilizer, phenol heat stabilizer, phosphorus compound, A nucleating agent was supplied after dry blending, and glass fibers were supplied from a downstream supply port, and melt-kneaded to prepare polyamide composition pellets.
The obtained polyamide composition was dried in a nitrogen stream to reduce the water content to 500 ppm or less, and then molded and subjected to various evaluations. The physical property values are shown in Table 2 together with the composition.

  From the results in Table 2, the composition containing polyamide and titanium oxide containing at least 50 mol% alicyclic dicarboxylic acid and at least 50 mol% main chain branched chain diamine and titanium oxide has a large amount of bending deflection and excellent toughness. It was confirmed that the spiral flow length was long and the fluidity was excellent. Moreover, since the whiteness and the whiteness after heat processing are high, it was also confirmed that the thermal stability of the color tone is excellent, and there are few foreign substances and generated gas during extrusion. Furthermore, it was confirmed that the retention stability during molding was also excellent.

[Examples 7 to 14, Comparative Example 4]
The polyamide of Production Example was dried in a nitrogen stream and the moisture content was adjusted to about 0.2% by mass. L / D (extrusion) having an upstream supply port in the first barrel from the upstream side of the extruder, a downstream first supply port in the sixth barrel, and a downstream second supply port in the ninth barrel. Using a twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] of 48 (length of cylinder of the machine / cylinder diameter of the extruder) = 48 (number of barrels: 12), from the upstream supply port to the die (A) Polyamide produced in the production example was set to Tm2 + 20 ° C., the rotation speed of the screw was 250 rpm, the discharge rate was 25 kg / h, and the polyamide and amine light stability were obtained from the upstream supply port so that the ratio shown in Table 3 was obtained. The polyamide composition is supplied after dry blending the agent, phenolic heat stabilizer, phosphorus compound, and nucleating agent, supplying titanium oxide from the downstream first supply port, and supplying glass fiber from the downstream second supply port. Pellet It was manufactured.
The obtained polyamide composition was dried in a nitrogen stream to reduce the water content to 500 ppm or less, and then molded and subjected to various evaluations. The physical property values are shown in Table 3 together with the composition.

  From the results in Table 3, it was confirmed that by using titanium oxide having an average particle size of 0.1 to 0.8 μm, the thermal stability of the color tone is excellent, and there are few foreign substances and generated gases during extrusion processing. did. Furthermore, it was confirmed that the residence stability during molding was also excellent.

[Examples 15 to 19, Comparative Examples 5 and 6]
The polyamide of Production Example was dried in a nitrogen stream and the moisture content was adjusted to about 0.2% by mass. L / D (extruder cylinder length / extruder cylinder diameter) having an upstream supply port in the first barrel from the upstream side of the extruder and a downstream supply port in the sixth barrel = 48 (number of barrels: 12) twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] was manufactured from the upstream supply port to the die in the production example. (A) Tm2 + 20 ° C. of polyamide Set and feed after dry blending polyamide and phenol-based heat stabilizer from the upstream supply port so that the screw rotation speed is 250 rpm and the discharge rate is 25 kg / h, and the ratio shown in Table 4 is supplied, from the downstream supply port Titanium oxide was supplied and melt-kneaded to prepare polyamide composition pellets.
The obtained polyamide composition was dried in a nitrogen stream to reduce the water content to 500 ppm or less, and then molded and subjected to various evaluations. The physical property values are shown in Table 4 together with the composition.

  From the results of Table 4, a composition containing at least 50 mol% of an alicyclic dicarboxylic acid, at least 50 mol% of a polyamide containing a branched diamine main chain, and titanium oxide having an average particle size of 0.1 to 0.8 μm. It was confirmed that the product generated less gas during extrusion and was excellent in film processability.

[Examples 20 to 23, Comparative Examples 7 to 9]
The polyamide of Production Example was dried in a nitrogen stream and the moisture content was adjusted to about 0.2% by mass. L / D (extrusion) having an upstream supply port in the first barrel from the upstream side of the extruder, a downstream first supply port in the sixth barrel, and a downstream second supply port in the ninth barrel. Using a twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] of 48 (length of cylinder of the machine / cylinder diameter of the extruder) = 48 (number of barrels: 12), from the upstream supply port to the die (A) Polyamide produced in the production example was set to Tm2 + 20 ° C., the rotation speed of the screw was 250 rpm, and the discharge rate was 25 kg / h. Supply after dry blending agent, phenolic heat stabilizer, phosphorus compound, and nucleating agent, supplying titanium oxide from the downstream first supply port, and supplying wollastonite or talc from the downstream second supply port, and melt-kneading. Polyami The composition pellets were produced.
The obtained polyamide composition was dried in a nitrogen stream to reduce the water content to 500 ppm or less, and then molded and subjected to various evaluations. The physical property values are shown in Table 5 together with the composition.

  From the results of Table 5, even when wollastonite or talc is used as the inorganic filler, at least 50 mol% of the alicyclic dicarboxylic acid and at least 50 mol% of the polyamide containing a diamine having a branched structure It was confirmed that the composition containing titanium oxide had a large amount of bending deflection and excellent toughness, a long spiral flow length and excellent fluidity. It was also confirmed that there was little foreign matter during extrusion.

  According to the present invention, it is possible to provide a polyamide composition which is excellent in toughness and fluidity, and further excellent in heat discoloration and workability. The polyamide composition of the present invention can be suitably used as a molding material for various parts such as automobiles, electricity and electronics, industrial materials, industrial materials, daily products, and household products.

Claims (18)

(A) (a) a polyamide obtained by polymerizing a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid and (b) a diamine containing at least 50 mol% of a diamine having a branched structure as a main chain;
(B) A polyamide composition containing a titanium oxide having a number average particle diameter of 0.1 to 0.8 μm.   The polyamide composition according to claim 1, wherein the diamine having a branched structure as the main chain is 2-methylpentamethylenediamine.   The polyamide composition according to claim 1 or 2, wherein the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.   The polyamide composition according to any one of claims 1 to 3, wherein the (a) dicarboxylic acid further contains an aliphatic dicarboxylic acid having 10 or more carbon atoms.   The polyamide composition according to any one of claims 1 to 4, wherein the (A) polyamide has a melting point of 270 to 350 ° C.   The polyamide composition according to any one of claims 1 to 5, wherein the trans isomer ratio in the polyamide (A) is 50 to 85%.   The polyamide composition according to any one of claims 1 to 6, wherein the (B) titanium oxide is coated with an inorganic coating and / or an organic coating.   The polyamide composition of claim 7, wherein the inorganic coating is a metal oxide coating.   The polyamide composition according to claim 7 or 8, wherein the organic coating is at least one coating selected from the group consisting of carboxylic acids, polyols, alkanolamines, and organosilicon compounds.   The polyamide composition as described in any one of Claims 1-9 whose ignition loss of said (B) titanium oxide is 0.7-2.5 mass%.   The polyamide composition according to any one of claims 1 to 10, further comprising (C) an amine light stabilizer.   The polyamide composition according to claim 11, wherein the molecular weight of the (C) amine light stabilizer is less than 1,000.   The polyamide composition according to any one of claims 1 to 12, further comprising (D) a phenol-based heat stabilizer.   Furthermore, (E) The polyamide composition as described in any one of Claims 1-13 containing an inorganic filler.   The polyamide composition according to claim 14, wherein the (E) inorganic filler is at least one selected from the group consisting of glass fiber, potassium titanate fiber, talc, wollastonite, kaolin, mica, calcium carbonate, and clay. object. 55 to 55 polyamides obtained by polymerizing (A) (a) a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid and (b) a diamine containing at least 50 mol% of a diamine having a branched main chain structure on a total mass basis. 95% by mass,
(B) 5 to 45% by mass of titanium oxide having a number average particle size of 0.1 to 0.8 μm,
(C) 0 to 1% by mass of an amine light stabilizer,
(D) 0 to 1% by mass of a phenol-based heat stabilizer,
(E) 0 to 25 mass% of inorganic filler,
Containing polyamide composition.   The polyamide composition according to any one of claims 1 to 16, wherein the polyamide (A) has a cyclic amino group bonded to a polymer terminal in an amount of 30 µequivalent / g to 65 µequivalent / g.   A molded article comprising the polyamide composition according to any one of claims 1 to 17.