CN104761886B

CN104761886B - Amilan polyamide resin composition and formed products

Info

Publication number: CN104761886B
Application number: CN201410008311.2A
Authority: CN
Inventors: 佐佐木幸义; 栗原哲男; 斋藤大贺; 寺田和范
Original assignee: Asahi Kasei Kogyo KK
Current assignee: Asahi Kasei Corp
Priority date: 2014-01-08
Filing date: 2014-01-08
Publication date: 2018-08-14
Anticipated expiration: 2034-01-08
Also published as: CN104761886A

Abstract

The present invention relates to Amilan polyamide resin composition and formed products.The present invention provides Amilan polyamide resin composition and formed products with creep properties, appearance, release property and the excellent characteristic of mechanical strength under environment in water.A kind of Amilan polyamide resin composition, contains：（A）The ratio between carbon atom number/nitrogen-atoms numbers（C/N ratios）For 7 or more 100 mass parts of aliphatic polyamide resin,（B）1~200 mass parts of glass fibre,（C）0.1~10 mass parts of inorganic filling material other than glass fibre, and（D）0.01~10 mass parts of lubricant.

Description

Amilan polyamide resin composition and formed products

Technical field

The present invention relates to Amilan polyamide resin composition and formed products.

Background technology

Shaping processability, mechanical properties, the chemical-resistant of polyamide are excellent, therefore are used in the past as dress material, production Industry material with, automobile, electric and electronic with or the various parts material such as industrial be widely used.

In recent years, polyamide is largely used in automotive field, especially uses the polyamide of glass fiber reinforcement, Mechanical properties, heat resistance, oil resistivity, good-toughness are accordingly used in the component that radiator tank, water valve etc. are contacted with non-freezing solution and use Material.

But existing glass fiber reinforced polyamide, have due under high temperature environment for a long time and non-freezing solution The shortcomings that contact and intensity decline, and lacked with what intensity under xeothermic state even in a high temperature environment was also remarkably decreased Point.

It is therefore desirable to intensity decline, Yi Jigao caused by contact for a long time with non-freezing solution under inhibiting above-mentioned hot environment The polyamide that intensity under xeothermic state under warm environment declines.

Reply is such to be required, disclosed in the past using polyamide 610 resin Amilan polyamide resin composition (for example, see Patent Documents 1 to 3).

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Application Publication 2010-522259 bulletins

Patent document 2：Japanese Unexamined Patent Publication 2008-222290 bulletins

Patent document 3：Japanese Unexamined Patent Application 60-32847 bulletins

Invention content

Problem to be solved by the invention

But Amilan polyamide resin composition disclosed in aforementioned patent literature 1~3, although being observed for resistance to non-freezing solution To improvement, but for the creep properties under environment in water, sufficient characteristic is not yet obtained, reality is two kinds of spies The excellent polyamide of property is still unknown, therefore it is required that such Amilan polyamide resin composition.

In addition, Amilan polyamide resin composition disclosed in aforementioned patent literature 1~3 does not fill in terms of appearance and release property Point, it is desirable that meet the Amilan polyamide resin composition in terms of these.

Therefore, in the present invention, in view of the above-mentioned problems of the prior art, its purpose is to provide the creep under environment in water is special Property, appearance and the excellent Amilan polyamide resin composition and its formed products of release property.

The means used to solve the problem

The present inventor ties to solve the problems, such as the peculiar research carried out extensively and profoundly of above-mentioned Amilan polyamide resin composition Fruit finds, contains the inorganic fill other than (A) polyamide 610 resin, (B) glass fibre, (C) glass fibre at a specific ratio The Amilan polyamide resin composition of material and (D) lubricant can solve foregoing problems, so as to complete the present invention.

That is, the present invention is as described below.

[1] a kind of Amilan polyamide resin composition, contains：

(A) 100 mass parts of aliphatic polyamide resin that the ratio between carbon atom number/nitrogen-atoms numbers (C/N ratios) are 7 or more,

(B) 1~200 mass parts of glass fibre,

(C) 0.1~10 mass parts of inorganic filling material other than glass fibre, and

(D) 0.01~10 mass parts of lubricant.

[2] Amilan polyamide resin composition as described in aforementioned [1], wherein

The fusing point of (D) lubricant is 110~150 DEG C.

[3] Amilan polyamide resin composition as described in aforementioned [1] or [2], wherein

(D) lubricant is the higher fatty acid metal salt that tenor is 3.5~11.5 mass %.

[4] Amilan polyamide resin composition as described in any one of aforementioned [1] to [3], wherein

By according to the differential scanning calorimetry of JIS K7121 measure (wherein, by cooling velocity be set as 20 DEG C/min into Row cooling) obtained from, the extrapolation of (A) polyamide in the Amilan polyamide resin composition crystallize start temperature (T_ic) it is 200 DEG C or more.

[5] Amilan polyamide resin composition as described in any one of aforementioned [1] to [4], wherein

The relative viscosity of (A) polyamide measured in 98% sulfuric acid is 2.0~3.0.

[6] Amilan polyamide resin composition as described in any one of aforementioned [1] to [5], wherein

(A) polyamide is selected from by polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 1010 and one or more of the group that forms of polyamide 1012.

[7] Amilan polyamide resin composition as described in any one of aforementioned [1] to [6], wherein

(B) glass fibre is to carry out treated glass fibre using collecting agent, and the collecting agent contains copolymer, The copolymer have the alkenyl monomer of unsaturated ethylene containing carboxylic acid anhydrides and in addition to the alkenyl monomer of unsaturated ethylene containing carboxylic acid anhydrides not Unsaturated ethylene base monomer is as polymerized unit.

[8] Amilan polyamide resin composition as described in any one of aforementioned [1] to [7], wherein

Also contain (E) copper compound and halogen compounds (wherein, except copper halide) 0.002~2 mass parts.

[9] Amilan polyamide resin composition as described in aforementioned [8], wherein

Halogen element content x and copper in (E) copper compound and halogen compounds (wherein, except copper halide) The molar ratio x/y of content y is 2/1~50/1.

[10] Amilan polyamide resin composition as described in aforementioned [8] or [9], wherein

(E) copper compound and halogen compounds (wherein, except copper halide) are added in the form of polyamide master-batch.

[11] Amilan polyamide resin composition as described in any one of aforementioned [1] to [10], wherein

Also contain 0.01~5 mass parts of (F) colorant.

[12] a kind of formed products contain the Amilan polyamide resin composition described in any one of aforementioned [1] to [11].

Invention effect

In accordance with the invention it is possible to provide under environment in water creep properties, appearance, release property and mechanical strength it is excellent The Amilan polyamide resin composition and formed products of good characteristic.

Specific implementation mode

Hereinafter, mode for carrying out the present invention (hereinafter referred to as " present embodiment ") is described in detail.

Present embodiment below is the illustration for illustrating the present invention, it is not intended to limit the invention to content below. The present invention can suitably deform in the range of its main idea to implement.

[Amilan polyamide resin composition]

The Amilan polyamide resin composition of present embodiment be containing

(B) 1~200 mass parts of glass fibre,

(C) 0.1~10 mass parts of inorganic filling material other than glass fibre, and

(D) 0.01~10 mass parts of lubricant

Amilan polyamide resin composition.

Hereinafter, being illustrated for the constituent of the Amilan polyamide resin composition of present embodiment.

(aliphatic polyamide resin that the ratio between (A) carbon atom number/nitrogen-atoms numbers (C/N ratios) are 7 or more)

(A) polyamide used in present embodiment is that the ratio between carbon atom number/nitrogen-atoms numbers (C/N ratios) are 7 or more Fatty polyamide.By containing such fatty polyamide, with compacted under obtained formed body in water environment Become characteristic, appearance and the excellent tendency of mechanical strength.The ratio between carbon atom number/nitrogen-atoms numbers of above-mentioned fatty polyamide (C/N Than) it is 7 or more, preferably 8 or more.In addition, the upper limit of the ratio between carbon atom number/nitrogen-atoms numbers (C/N ratios) is not particularly limited, preferably 15 hereinafter, more preferable 12 hereinafter, further preferred 10 or less.Within the above range by the ratio between carbon atom number/nitrogen-atoms numbers, have Have the tendency that creep properties of the obtained formed body in water under environment, appearance and mechanical strength are more excellent.In addition, for The C/N ratios of copolyamide can find out the average value by the molar ratio calculating of copolymerization ratios as C/N ratios.

In addition, in present embodiment, " fatty polyamide " refers to constituting the unit of polyamide (by diamine and binary carboxylic Acid constitute in the case of, using a pair of of diamine and dicarboxylic acids as a unit) 50 mass % or more by aliphatic unit The polyamide of composition.

The fatty polyamide for being 7 or more as the ratio between carbon atom number/nitrogen-atoms numbers (C/N ratios), is not particularly limited, can With enumerate for example selected from by polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 1010, polyamide 1012, Polyamide 410, polyamide 412 and polyamide 69 and contain these as constituent copolyamide constitute groups in More than one.Wherein, it is preferably selected from by polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 1010, polyamides Amine 1012 and contain these one or more of groups constituted as the copolyamide of constituent, is more preferably selected from by gathering Amide 610, polyamide 612, polyamide 1010, polyamide 1012 and contain these copolyamide structures as constituent At one or more of group, further preferably selected from by polyamide 610, polyamide 612, polyamide 1010 and polyamide 1012 One or more of group of composition, particularly preferred polyamide 610.

In the fatty polyamide that the ratio between (A) carbon atom number/nitrogen-atoms numbers (C/N ratios) are 7 or more, this reality is not being damaged In the range of the purpose for applying mode, 6 aliphatic dicarboxylic acid below of carbon atom number, Cycloaliphatic dicarboxylic acids, virtue can be contained Fragrant race's dicarboxylic acids, 6 aliphatic diamine below of carbon atom number, aromatic diamine, can polycondensation amino acid, lactams etc. As polymerized monomer.

As 6 aliphatic dicarboxylic acid below of aforementioned carbon atom number, substance not limited to the following can enumerate such as third Diacid, dimethyl malonic acid, succinic acid, 2,2- dimethyl succinates, 2,2- diethyl succinic acid, glutaric acid and adipic acid.

As aforementioned Cycloaliphatic dicarboxylic acids, substance not limited to the following, can enumerate such as 1,3- cyclohexane cyclohexanedimethanodibasics, The carbon atom number of the alicyclic structures such as 1,4 cyclohexanedicarboxylic acid and 1,3- pentamethylene dioctyl phthalate is 3~10, preferred carbon atom number For 5~10 Cycloaliphatic dicarboxylic acids etc..

Cycloaliphatic dicarboxylic acids unsubstituted can also have substituent group.

As aforementioned fragrance race dicarboxylic acids, substance not limited to the following can enumerate such as terephthalic acid (TPA), isophthalic two Formic acid, naphthalenedicarboxylic acid, 2- chlorine terephthalic acid (TPA), 2- methylterephthalic acids, oreinol dioctyl phthalate and M-phthalic acid- 5- sodium sulfonates etc. are unsubstituted or the aromatic binary carboxylic acid etc. of carbon atom number 8~20 that is replaced by various substituent groups.

As aforementioned various substituent groups, the virtue of such as alkyl of carbon atom number 1~6, carbon atom number 6~12 can be enumerated The halogen radicals such as base, the aralkyl of carbon atom number 7~20, chloro and bromo, carbon atom number 3~10 aIkylsilyl groups and Groups such as sulfonic group and its salt such as sodium salt etc..

As 6 aliphatic diamine below of aforementioned carbon atom number, it is not limited to following substance, such as second two can be enumerated The straight chains such as amine, propane diamine, tetra-methylenedimine, five methylene diamine, hexamethylene diamine and 2- methyl pentamethylene diamines Representative examples of saturated aliphatic diamine etc..

As aforementioned fragrance race diamine, substance not limited to the following can be enumerated such as m-xylene diamine.

As it is aforementioned can polycondensation amino acid, substance not limited to the following can enumerate such as 6-aminocaprolc acid, 11- ammonia Base hendecanoic acid, 12 amino dodecanoic acid, paraaminomethyl benzoic acid etc..

As aforementioned lactams, it is not limited to following substance, such as butyrolactam, new valerolactam, acyl in oneself can be enumerated Amine, spicy inner formyl amine, oenantholcatam, 11 lactams, lauric lactam etc..

Above-mentioned dicarboxylic acids ingredient, diamine component, aminoacid ingredient and lactams ingredient respectively can be used alone One kind can also be used in combination.

<End-capping reagent>

As the ratio between aforementioned carbon atom number/nitrogen-atoms numbers (C/N ratios) be 7 or more aliphatic polyamide resin raw material, In order to adjust molecular weight, improve hot water resistance, end-capping reagent can be also added.

For example, in the polyamide 610 resin polymerization of present embodiment, it, can by further adding well known end-capping reagent To control polymerization amount.

As aforementioned end-capping reagent, it is not limited to following substance, such as monocarboxylic acid, monoamine, phthalic acid can be enumerated The acid anhydrides such as acid anhydride, monoisocyanates, single carboxylic acid halides, monoesters class and unary alcohol etc..

Wherein, from the viewpoint of productivity, preferably monocarboxylic acid and monoamine.

These end-capping reagents can be used alone, and can also be used in combination.

As the monocarboxylic acid that aforementioned end-capping reagent uses, as long as not having then with the reactive monocarboxylic acid with amino Especially limitation, can enumerate for example：Acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, lauric acid, tridecanoic acid, myristic acid, The aliphatic monocarboxylic acid such as palmitic acid, stearic acid, trimethylace tonitric and isobutyric acid；The alicyclic unitary carboxylic such as naphthenic acid Acid；The aromatic series monocarboxylic acids such as benzoic acid, toluic acid, α-naphthoicacid, β-naphthoic acid, methyl naphthoic acid and phenylacetic acid Deng.

These monocarboxylic acids can be used alone, and can also be used in combination.

As the monoamine that aforementioned end-capping reagent uses, as long as with the reactive monoamine with carboxyl then without special Limitation, can enumerate for example：Methylamine, ethamine, propylamine, butylamine, hexylamine, octylame, decyl amine, stearylamine, dimethylamine, diethylamine, two The aliphatic monos such as propylamine and dibutyl amine；The cycloaliphatic monoamines such as cyclohexylamine and dicyclohexyl amine；Aniline, toluidines, diphenylamines And aromatic monoamines such as naphthylamines etc..

These monoamines can be used alone, and can also be used in combination.

(manufacturing method for the aliphatic polyamide resin that the ratio between (A) carbon atom number/nitrogen-atoms numbers (C/N ratios) are 7 or more)

Manufacturer as the aliphatic polyamide resin that the ratio between (A) carbon atom number/nitrogen-atoms numbers (C/N ratios) are 7 or more Method can be enumerated for example：By other ingredients such as dicarboxylic acids, diamine and aftermentioned catalyst as needed, apatite Mixture aqueous solution or water slurry heating, (heat fusing is poly- for the method being polymerize in the case where being kept molten by It is legal)；The polyamide obtained by heat fusing polymerization is kept making in the case of solid state at fusing point temperature below The method (heat fusing polymeric solid-phase polymerization) that the degree of polymerization improves；By dicarboxylic acids, diamine and as needed other The aqueous solution or water slurry of the mixture of ingredient heat, then with extruders such as kneaders the prepolymer of precipitation melted again and The method (prepolymer extruding polymerization method) for making the degree of polymerization improve；By dicarboxylic acids, diamine and it is as needed it is other at The method (solid phase polymerization method) etc. that mixture, solid salt or the condensation polymer divided is polymerize in the case where keeping solid state.

It as polymerization methods, is not particularly limited, can be any one in intermittent, continous way.

In addition, polyplant is it is not also specifically limited, well known device, such as autoclave-type reactor, rolling can be used Extruder type reactors such as cartridge type reactor, kneader etc..

Aliphatic polyamide resin that (A) the ratio between carbon atom number/nitrogen-atoms numbers (C/N ratios) are 7 or more (including polyamide is total In manufacture polymers, similarly hereinafter), defined catalyst can be used.

As catalyst, as long as the well-known catalysts for polyamide are then not particularly limited, can enumerate for example：Phosphorus Acid, phosphorous acid, hypophosphorous acid, ortho-phosphorous acid, pyrophosphorous acid, phenyl phosphinic acid, phenyl-phosphonic acid, 2- methoxyphenyls phosphonic acids, 2- (2 '-pyridyl group) ethylphosphonic acid and their metal salt etc..

As the metal of the metal salt, be not limited to following substance, can enumerate for example potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, Metal salt or ammonium salt of manganese, tin, tungsten, germanium, titanium, antimony etc. etc..

In addition, as aforementioned catalytic agent, ethyl ester, isopropyl ester, butyl ester, own ester, last of the ten Heavenly stems ester, isodecyl ester, 18 can also be used The phosphoric acid esters such as alkyl ester, stearyl ester, phenyl ester.

(physical property for the aliphatic polyamide resin that the ratio between (A) carbon atom number/nitrogen-atoms numbers (C/N ratios) are 7 or more)

(A) 98% sulfuric acid of the aliphatic polyamide resin that the ratio between carbon atom number/nitrogen-atoms numbers (C/N ratios) are 7 or more is molten Fluid viscosity (JIS K 6920) is preferably 2.0~3.0, more preferably 2.0~2.9, further preferably 2.2~2.6.

When sulfuric acid solution viscosity is 2.0 or more, the formed body with practical sufficient mechanical property, sulfuric acid can be obtained When solution viscosity is 3.0 or less, good fluidity when forming can obtain the excellent formed body of appearance.

The Amilan polyamide resin composition of present embodiment can contain C/N than less than 7 polyamide as other polyamide Resin.It as C/N than the polyamide less than 7, is not particularly limited, can enumerate for example selected from by polyamide 4, polyamide 6, poly- Amide 46, polyamide 56, polyamide 66 and contain these as constituent copolyamide constitute groups in one kind More than.Wherein, more preferably using polyamide 6, polyamide 66 as main composition, C/N than the polyamide less than 7, into one Preferred C/N is walked than the fatty polyamide less than 7.By containing such polyamide, the machinery with obtained formed body Tendency rigidly more excellent when intensity, heating.

C/N is preferably 0~50 matter in the 100 mass % of total amount of polyamide than the content of the polyamide less than 7 Measure %, more preferably 0~40 mass %, further preferably 5~20 mass %.Within the above range by content, it does not damage The dimensional accuracy and appearance of obtained formed body, tendency rigidly more excellent when with mechanical strength, heating.

In addition, the Amilan polyamide resin composition of present embodiment can be containing C/N than the semiaromatic polyamide composition for 7 or more As other polyamides.It as C/N than the semiaromatic polyamide composition for 7 or more, is not particularly limited, can enumerate for example Polyamide 6 T, polyamide 9T and polyamide 6 I etc..By containing such semiaromatic polyamide composition, more with rigidity when heating Add excellent tendency.Here, it is aliphatic that " semiaromatic polyamide composition ", which refers to by the side in diamine or dicarboxylic acids, Close object, another party is the polyamide that constitutes of the combination of the compound with aromatic structure and contain these conduct compositions Unit more than 50 mass % in Component units is semiaromatic in the case of copolyamide by the copolyamide of ingredient The case where race's unit referred to as semiaromatic polyamide composition.

C/N than the semiaromatic polyamide composition for 7 or more content in the 100 mass % of total amount of polyamide preferably 0~50 mass %, more preferably 0~40 mass %, further preferably 5~20 mass %.Within the above range by content, The dimensional accuracy and appearance of obtained formed body are not damaged, and there is tendency rigidly more excellent when heating.

((B) glass fibre)

The Amilan polyamide resin composition of present embodiment, relative to the ratio between above-mentioned (A) carbon atom number/nitrogen-atoms numbers (C/N Than) be 7 or more 100 mass parts of aliphatic polyamide resin, contain 1~200 mass parts (B) glass fibre.

By containing aforementioned (B) glass fibre, excellent rigidity can be obtained.

Aforementioned (B) glass fibre, from the viewpoint of it can show excellent mechanical strength, vibration resistance fatigue properties, Number average fiber diameter is preferably 3~30 μm, and more preferably 3~25 μm, further preferably 5~20 μm, weight average fiber length is excellent It is selected as 100~750 μm, more preferably 100~700 μm, further preferably 200~600 μm.

(B) weight average fiber length (L) of glass fibre and the draw ratio (L/D) of number average fiber diameter (D) be preferably 10~ 100, more preferably 10~90, further preferably 20~90.

(B) glass fibre can be used alone, can also by number average fiber diameter, weight average fiber length it is different two Kind combination of the above uses.

The number average fiber diameter (D) and weight average fiber length (L) of above-mentioned (B) glass fibre, can be surveyed by microscopic method It is fixed.

For example, can by by the granular Amilan polyamide resin composition containing glass fibre in the polyamide group It closes the decomposition temperature of object or more to be heated, by remaining (B) glass fibre microscope photographing photo, and measures glass fibre Diameter and the method for length measure.

Number average fiber diameter (D) and weight average fiber length (L) are calculated as by the measured value that is obtained by microscopic method Method can enumerate lower formula (I) and (II).

The total of number average fiber diameter (D)=glass fiber diameter/glass fibers dimension ... (I)

The total ... (II) of quadratic sum/glass fibre length of weight average fiber length (L)=glass fibre length

The content of (B) glass fibre in the Amilan polyamide resin composition of present embodiment, as discussed previously with respect to (A) carbon 100 mass parts of aliphatic polyamide resin that the ratio between atomicity/nitrogen-atoms numbers (C/N ratios) are 7 or more are 1~200 mass parts, excellent It is selected as 2~200 mass parts, more preferably 2~180 mass parts, further preferably 5~100 mass parts.

By relative to the ratio between (A) carbon atom number/nitrogen-atoms numbers (C/N ratios) being 7 or more by the content of (B) glass fibre 100 mass parts of aliphatic polyamide resin are set as 1 mass parts or more, can improve the polyamide combination of present embodiment The mechanical strength etc. of object, in addition, by the way that content is set as 200 parts by weight hereinafter, the polyamide that can be had excellent moldability Resin combination.

In addition, the content of (B) glass fibre can take out remaining (B) glass by the way that Amilan polyamide resin composition burns Glass fiber, and be measured and calculate.

As the concrete composition of aforementioned (B) glass fibre, it is not limited to consisting of, can be enumerated for example：E glass composition, C Glass composition, S glass composition, alkali-proof glass composition etc..

Wherein, calm facile viewpoint considers, preferably E glass.

In addition, from the viewpoint of the mechanical strength of the Amilan polyamide resin composition of present embodiment, (B) glass fibre Tensile strength is preferably 290kg/mm²More than.

Aforementioned (B) glass fibre preferably uses such as gamma-methyl allyl acyloxypropyl trimethoxysilane, the third oxygen of γ-epoxy The silane coupling agents such as base propyl trimethoxy silicane, γ aminopropyltriethoxy silane are surface-treated, but are not limited to These silane coupling agents, adhesion amount are preferably relative to glass fiber weight (total amount of glass fibre and surface conditioning agent) 0.01 mass % or more.

In addition, as needed, aforementioned (B) glass fibre can be handled using collecting agent.As collecting agent, it is not limited to Example below can be enumerated for example：Contain carboxylic acid anhydrides unsaturated ethylene with the alkenyl monomer of unsaturated ethylene containing carboxylic acid anhydrides and except this Unsaturated ethylene alkenyl monomer other than base monomer is as the copolymer of polymerized unit, epoxide, polyurethane resin, acrylic acid Homopolymer, acrylic acid and other copolymerisable monomers copolymer and they and primary amine, the salt of secondary amine and tertiary amine.

These substances can be used alone, and can also be used in combination.

Particularly, from the viewpoint of the mechanical strength of the Amilan polyamide resin composition of present embodiment, preferably have and contain Carboxylic acid anhydrides unsaturated ethylene alkenyl monomer and the unsaturated ethylene alkenyl monomer in addition to the alkenyl monomer of unsaturated ethylene containing carboxylic acid anhydrides are made For the copolymer of polymerized unit, epoxide and polyurethane resin and combination thereof, more preferably have containing carboxylic acid anhydrides not Unsaturated ethylene base monomer and the unsaturated ethylene alkenyl monomer in addition to the alkenyl monomer of unsaturated ethylene containing carboxylic acid anhydrides are used as polymerization single The copolymer and polyurethane resin and combination thereof of member.

(inorganic filling material other than (C) glass fibre)

The Amilan polyamide resin composition of present embodiment, relative to the ratio between above-mentioned (A) carbon atom number/nitrogen-atoms numbers (C/N Than) 100 mass parts of aliphatic polyamide resin that are 7 or more, containing inorganic other than 0.1~10 mass parts (C) glass fibre Packing material.

The content of the inorganic filling material other than (C) glass fibre is somebody's turn to do relative to above-mentioned (A) carbon atom number/nitrogen-atoms numbers The ratio between (C/N ratios) be 7 or more 100 mass parts of aliphatic polyamide resin be preferably 0.18~10 mass parts, more preferably 0.18~8 mass parts, further preferably 0.18~5 mass parts are even more preferably 2.0~5.0 mass parts.

By the way that the content of the inorganic filling material other than (C) glass fibre is set as 0.1 mass parts or more, can show Improve the effect of the intensity of the Amilan polyamide resin composition of present embodiment.On the other hand, by the way that above-mentioned content is set as 10 It is below mass part, extrudability and Amilan polyamide resin composition that is having excellent moldability can be obtained.

As the inorganic filling material other than aforementioned (C) glass fibre, example not limited to the following can be enumerated for example： Wollastonite, kaolin, mica, talcum, calcium carbonate, magnesium carbonate, potassium titanate, aluminium borate and clay are (as silicate layer stacking At lamellar clay montmorillonite etc.).

Inorganic filling material other than (C) glass fibre, can be used alone, two or more can also combine It uses.

It is preferably selected from from the viewpoint of improving intensity etc. as the inorganic filling material other than aforementioned (C) glass fibre One or more of the group being made of wollastonite, kaolin, mica and talcum, further preferably selected from by wollastonite, kaolin One or more of the group constituted with talcum.In addition, from the formed products for the Amilan polyamide resin composition for improving present embodiment From the viewpoint of appearance, even more preferably wollastonite and talcum.

The average grain diameter of inorganic filling material other than aforementioned (C) glass fibre is preferably 0.01~38 μm.More preferably 0.03~30 μm, further preferably 0.05~25 μm are even more preferably 0.10~20 μm, are still more preferably 0.15 ~13 μm.

By the way that the average grain diameter of the inorganic filling material other than aforementioned (C) glass fibre is set as 38 μm hereinafter, can be with Obtain the excellent Amilan polyamide resin composition of the appearance of toughness and formed products.

On the other hand, by the way that average grain diameter is set as 0.01 μm or more, the behaviour of cost aspect and powder can be obtained The Amilan polyamide resin composition excellent with the balance of mechanical properties (intensity, toughness etc.) in terms of work.

In addition, in inorganic filling material other than (C) glass fibre, there is the material of needle-like shape about wollastonite etc., It regard number average fiber diameter (hereinafter referred to as " avarage fiber diameter ") as average grain diameter.In addition, in the case that section is not rounded, it will The maximum value of its length will use the number average fiber diameter that it is obtained as average grain diameter as fibre diameter.

Average grain diameter (number average fiber diameter) can be by arbitrarily selecting aforementioned (C) glass fibre of 100 (roots) or more Inorganic filling material in addition is observed with scanning electron microscope (SEM), measures the grain size of these inorganic filling materials (fibre diameter), and arithmetic mean of instantaneous value is calculated to find out.

In aforementioned inorganic packing material, there is the weight average fiber length of the material of needle-like shape about aforementioned wollastonite etc. (hereinafter referred to as " average fiber length "), it is preferably fine by the preferred scope of above-mentioned number average fiber diameter and following weights Tie up the numberical range of length (L) and the preferred scope calculating of the draw ratio (L/D) of number average fiber diameter (D).

The draw ratio of weight average fiber length (L) and number average fiber diameter (D) about the aforementioned material with needle-like shape (L/D), it is examined from the viewpoint of the abrasion for the metallicity component for improving the appearance of formed products, and preventing injection machine etc. Consider, preferably 1.5~10, more preferably 2.0~5, further preferably 2.5~4.

In addition, in inorganic filling material other than (C) glass fibre the material with needle-like shape draw ratio, from reduction From the viewpoint of the generation of warpage in the formed products of the Amilan polyamide resin composition of present embodiment, preferably 10~20, more Preferably 15~20.

Here, the number average fiber diameter (D) in this specification, as set forth above, it is possible to by arbitrarily select 100 (roots) with On the inorganic filling material as raw material, observed with scanning electron microscope (SEM), and measure these and inorganic fill out The fibre diameter of material is filled to find out.In addition, the weight average fiber length (L) of this specification, it can be by with the inorganic of threadiness Packing material is object, arbitrarily selects 100 or more inorganic filling materials, measures fibre length using SEM photograph to ask Go out.

(C) inorganic filling material other than glass fibre can use the progress such as silane coupling agent or titante coupling agent Surface treatment.

As aforementioned silane coupling agent, example not limited to the following can be enumerated for example：Gamma-amino propyl triethoxy Silane, gamma-amino propyl trimethoxy silicane and N- β-(amino-ethyl)-gamma-amino hydroxypropyl methyl dimethoxysilane etc. Hydrosulphonyl silanes class, the rings such as amino silicone alkanes, γ mercaptopropyitrimethoxy silane and γ-Mercaptopropyltriethoxysilane Oxosilane class and vinyl silanes class.

Wherein, from the viewpoint of it can show excellent mechanical strength, more preferable amino silicone alkanes.

One kind can be used only in these substances, can also be used in combination.

Such surface conditioning agent can be in advance on the surface of the inorganic filling material other than (C) glass fibre Reason, can also be in the aliphatic polyamide resin for being 7 or more by the ratio between (A) carbon atom number/nitrogen-atoms numbers (C/N ratios) and (C) glass Inorganic filling material other than glass fiber adds when mixing.

The additive amount of surface conditioning agent is preferably relative to the 100 mass % of inorganic filling material other than (C) glass fibre 0.05~1.5 mass %.

((D) lubricant)

The Amilan polyamide resin composition of present embodiment, relative to the ratio between above-mentioned (A) carbon atom number/nitrogen-atoms numbers (C/N Than) be 7 or more 100 mass parts of aliphatic polyamide resin, contain 0.01~10 mass parts (D) lubricant.

The content of (D) lubricant is 7 or more relative to the ratio between above-mentioned (A) carbon atom number/nitrogen-atoms numbers (C/N ratios) 100 mass parts of aliphatic polyamide resin are preferably 0.03~10 mass parts, more preferably 0.03~5 mass parts, further excellent It is selected as 0.05~3 mass parts.

By the way that the content of (D) lubricant is set in above range, can obtain appearance, release property, mechanical strength and The more excellent Amilan polyamide resin composition of plasticity.

As (D) lubricant, can use selected from by higher fatty acids, higher fatty acid metal salt, high-grade aliphatic ester With at least one of the group of higher fatty acid amides composition.

(D) lubricant can be used alone, and can also be used in combination.

The higher fatty acids refers to the aliphatic monocarboxylic acid of 8 or more carbon atom number.

The carbon atom number of higher fatty acids is preferably 8~40.As the higher fatty acids, example not limited to the following, It can enumerate for example：Saturated or unsaturated, linear chain or branched chain aliphatic monocarboxylic acid.For example, as higher fatty acids, it can To enumerate stearic acid, palmitic acid, behenic acids, sinapic acid, oleic acid, lauric acid and montanic acid etc..

The higher fatty acid metal salt is the metal salt of above-mentioned higher fatty acids.

As the metallic element with higher fatty acids forming salt, can enumerate the 1st race's element (alkali metal) of the periodic table of elements, 2nd race's element (alkaline-earth metal), the 3rd race's element, zinc, aluminium etc..As the metallic element, the preferably alkali metal such as sodium, potassium；Calcium, magnesium Equal alkaline-earth metal；Aluminium.

As the higher fatty acid metal salt, example not limited to the following can be enumerated for example：Calcium stearate, tristearin Sour aluminium, zinc stearate, magnesium stearate, montanic acid calcium, montanic acid sodium, montanic acid aluminium, montanic acid zinc, montanic acid magnesium, behenic acids calcium, Behenic acid sodium, behenic acids zinc, calcium laurate, zinc laurate, calcium palmitate etc..

As the higher fatty acid metal salt, it is preferable to use lignite acid metal salt, behenic acid metal salt and stearic acid gold Belong to salt, wherein preferred calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, montanic acid calcium, montanic acid zinc, montanic acid magnesium, Behenic acid calcium, behenic acid zinc, more preferable aluminum stearate, zinc stearate, magnesium stearate, montanic acid calcium, montanic acid zinc, behenic acids Calcium, behenic acid zinc, further preferred montanic acid calcium, montanic acid zinc, behenic acid zinc.

These higher fatty acid metal salts can be used alone, and can also be used in combination.

Tenor in aforementioned higher fatty acid metal salt relative to 100 mass % of higher fatty acid metal salt, from It is preferably 3.5~11.5 mass % from the viewpoint of the Amilan polyamide resin composition more excellent to appearance and release property.It is more excellent It is selected as 3.5~10.0 mass %, further preferably 4.0~9.0 mass %.

The high-grade aliphatic ester is the carboxylate of above-mentioned higher fatty acids and alcohol.

As aforementioned high-grade aliphatic ester, preferably the aliphatic monocarboxylic acid of carbon atom number 8~40 and carbon atom number 8~40 Aliphatic alcohol carboxylate.

As aliphatic alcohol, example not limited to the following can be enumerated for example：Stearyl alcohol, behenyl alcohols, laruyl alcohol etc..Make For high-grade aliphatic ester, can enumerate for example：Stearyl stearate, behenic acid Shan Yu esters etc..

The higher fatty acid amides are the amidates of above-mentioned higher fatty acids.

As aforementioned higher fatty acid amides, example not limited to the following can be enumerated for example：Stearmide, oleamide, Mustard seed amide, ethylenebisstearamide, ethylenebisoleoamide, N- stearyl stearamides, N- stearyl mustard seed amides etc.. As higher fatty acid amides, preferably stearmide, mustard seed amide, ethylenebisstearamide and N- stearyl mustard seed acyls Amine, more preferable ethylenebisstearamide and N- stearyl mustard seed amides.

As (D) lubricant, from the viewpoint of formability is more good, preferably higher fatty acid metal salt, height Grade fatty acid amide, wherein from the viewpoint of appearance and release property are more good, more preferable higher fatty acid metal salt.

From the viewpoint of appearance and release property are more good, the fusing point of (D) lubricant is preferably 110~150 DEG C, More preferably 115~145 DEG C, further preferably 115~140 DEG C.

In addition, the fusing point of (D) lubricant can utilize differential scanning calorimetry to measure measurement such as (DSC).

((E) copper compound and halogen compounds (wherein, except copper halide))

The Amilan polyamide resin composition of present embodiment can also contain (E) copper compound and halogen compounds (wherein, halogen Except change copper).

It is unlimited as the copper compound used in aforementioned (E) copper compound and halogen compounds (wherein, except copper halide) In example below, can enumerate for example：Copper halide, copper acetate, propionic acid copper, copper benzoate, adipic acid copper, terephthalic acid (TPA) Copper, M-phthalic acid copper, Cupric salicylate, copper nicotinate, copper stearate etc., and with the chelating agents such as ethylenediamine and ethylenediamine tetra-acetic acid The copper complex salt etc. of coordination and formation.

These copper compounds may be used singly or in combination of two or more.

Wherein, from the viewpoint of thermal stability, preferably cupric iodide, cuprous bromide, copper bromide, stannous chloride, copper acetate.

The content of aforementioned copper compound in aforementioned (E) copper compound and halogen compounds (wherein, except copper halide), relatively 100 mass parts of aliphatic polyamide resin preferably 0.001 for being 7 or more in the ratio between (A) carbon atom number/nitrogen-atoms numbers (C/N ratios) ~1.999 mass parts copper compounds, more preferable 0.0025~0.5 mass parts, further preferred 0.01~0.1 mass parts.Pass through Setting in the range, for the Amilan polyamide resin composition of present embodiment and its formed products, may be implemented adequately Heat-resistant aging improves, and copper can be inhibited to be precipitated, corrosion.

As halogen compounds (its used in aforementioned (E) copper compound and halogen compounds (wherein, except copper halide) In, except copper halide), example not limited to the following can be enumerated for example：Potassium iodide, sodium iodide, potassium bromide, potassium chloride, chlorination Sodium etc..

These halogen compounds can be used alone, and can also mix two or more uses.

The content of halogen compounds in aforementioned (E) copper compound and halogen compounds (wherein, except copper halide), relative to (A) the ratio between carbon atom number/nitrogen-atoms numbers (C/N ratios) be 7 or more 100 mass parts of aliphatic polyamide resin preferably 0.001~ 1.999 mass parts halogen compounds, more preferable 0.01~1.999 mass parts, further preferred 0.03~1 mass parts.By setting Determine in the range, for the Amilan polyamide resin composition of present embodiment and its formed products, may be implemented adequately resistance to Heat aging improves, and copper can be inhibited to be precipitated, corrosion.

In order to improve present embodiment Amilan polyamide resin composition performance, preferably comprise aforementioned copper compound and halogen Compound (wherein, except copper halide) both sides.

Total content of aforementioned (E) copper compound and halogen compounds (wherein, except copper halide) is relative to (A) carbon atom 100 mass parts of aliphatic polyamide resin that the ratio between number/nitrogen-atoms numbers (C/N ratios) are 7 or more are preferably 0.002~2 mass parts, More preferably 0.01~2 mass parts, further preferably 0.03~1.5 mass parts are even more preferably 0.03~1 mass Part.By being set as the range, for the Amilan polyamide resin composition of present embodiment and its formed products, can be filled The heat-resistant aging improvement effect divided can inhibit copper to be precipitated, corrosion.

In the Amilan polyamide resin composition of present embodiment, aforementioned (E) copper compound and halogen compounds (wherein, halogenation Except copper) in halogens content x and copper content y the molar ratio (content of the content x/ coppers of halogens Y) be preferably 2/1~50/1, more preferably 3/1~30/1, further preferably 4/1~25/1, even more preferably for 5/1~ 23/1。

When the molar ratio (x/y) of the content x of the halogens and content y of copper is 2 or more, copper can be inhibited to be precipitated, Metal erosion, therefore preferably.In addition, when the molar ratio (x/y) of aforementioned halogen and copper is 50 or less, the mechanical object such as toughness is not damaged Property, the corrosion of screw rod of forming machine etc. can be inhibited.

Aforementioned (E) copper compound and halogen compounds (wherein, except copper halide) are added preferably in the form of masterbatch.

By adding aforementioned (E) copper compound and halogen compounds in the form of masterbatch, the dispersion of (E) ingredient can be improved Property, heat-resistant aging is improved, prevents from corroding, and further suppresses copper precipitation.

As the polyamide used in the polyamide master-batch, example not limited to the following can be enumerated for example：Gather oneself Lactams (polyamide 6), nylon 46 (polyamide 46), polyhexamethylene adipamide (polyamide 66), poly- decanedioyl oneself Diamines (polyamide 610), two formyl hexamethylene diamine (polyamide 612) of poly- 12 carbon, poly hexamethylene adipamide hendecane diamines (polyamide 116), poly- 11 lactams (polyamide 11), nylon 12 (polyamide 12), poly- paraphenylene terephthalamide's trimethylhexane diamine (nylon TMHT), poly-6I hexamethylene isoterephalamide (polyamide 6 I), poly-paraphenylene terephthalamide's nonamethylene diamine (9T), poly- paraphenylene terephthalamide oneself Diamines (6T), poly bis (4- aminocyclohexyls) methane dodecane diamides (nylon PACM12), poly bis (3- methylamino hexamethylenes Base) methane dodecane diamides (nylon dimethyl PACM12), poly-meta-xylylene adipamide (polyamide MXD6) and poly- six 11 carbon diamines of hydrogen paraphenylene terephthalamide (polyamide 11T (H)) etc..

In addition, as the polyamide used in foregoing polyamides masterbatch, can enumerate containing among these at least The mixing of the polyamide copolymer and these polyamide and/or polyamide copolymer of two different polyamide forming components Object etc..

In above-mentioned polyamide, for the Amilan polyamide resin composition of present embodiment and its formed products, from suppression From the viewpoint of mechanical properties decline caused by system is contacted with non-freezing solution for a long time and the mechanical properties under high temperature drying decline, It is preferred that polyhexamethylene sebacamide (polyamide 610), two formyl hexamethylene diamine (polyamide 612) of poly- 12 carbon etc., the particularly preferred poly- last of the ten Heavenly stems Two acyl hexamethylene diamines (polyamide 610).

Contained in Amilan polyamide resin composition about present embodiment, include aforementioned (E) copper compound and halogenated The polyamide master-batch for closing object (wherein, except copper halide), the main component in polyamide contained in the polyamide master-batch Preferably polyamide 610 resin.Here, " main component " refers to the polyamide 610 in the polyamide for constitute the polyamide master-batch The content of resin is 80 mass % or more, preferably 85 mass % or more, more preferable 90 mass % or more.

The content of aforementioned copper compound in foregoing polyamides masterbatch, relative to the polyamide for constituting polyamide master-batch 100 mass parts, preferably 0.1~5 mass parts copper compound, more preferably 0.25~5 mass parts, further preferably 0.40~ 4 mass parts.It, can be with for the Amilan polyamide resin composition of present embodiment and its formed products by being set as the range It realizes sufficient resistance to ag(e)ing, copper can be inhibited to be precipitated, corrosion.

The content of halogen compounds in foregoing polyamides masterbatch, relative to the polyamide for constituting polyamide master-batch 100 mass parts, preferably 1~50 mass parts halogen compounds, more preferably 5~45 mass parts, further preferably 10~40 Mass parts.By being set as the range, for the Amilan polyamide resin composition of present embodiment and its formed products, Ke Yishi Now sufficient resistance to ag(e)ing can inhibit copper to be precipitated, corrosion.

Aforementioned (E) copper compound and halogen compounds are preferably particle shape contained in foregoing polyamides masterbatch.

In addition, contained (E) copper compound and the maximum particle diameter of halogen compounds, i.e. copper compound contained in masterbatch, The grain size of maximum particle in the particle of halogen compounds be both preferably 50 μm hereinafter, more preferably 20 μm hereinafter, further it is excellent It is selected as 10 μm or less.

In polyamide master-batch, particle refers to two axis average diameters, the i.e. average value of minor axis and major diameter.Here, minor axis, major diameter The respectively circumscribed rectangular short side of the area minimum circumscribed with particle, long side.Aforementioned (E) copper compound and halogen compounds The measurement of maximum particle diameter at least 50 particles can be observed by using scanning electron microscope (SEM) to ask Go out.

By the way that the maximum particle diameter of (E) copper compound and halogen compounds is set as 50 μm hereinafter, in polyamide master-batch (E) copper compound and halogen compounds can be made fine to be distributed in polyamide, for the polyamide of present embodiment For composition and its formed products, can further improve metal be precipitated, etching problem, can further improve toughness, heat-resisting Aging, appearance, tone.

In foregoing polyamides masterbatch, in the melting mixing of the polyamide master-batch, it can mix at least one amide The organic compound of base.

The aforementioned organic compound at least one amide groups is the chemical combination at least one amide groups in strand Object.As the organic compound at least one amide groups, example not limited to the following can be enumerated for example：Monoamides Class, substituted amide class, methylol amide class, bisamide class.

Aforementioned monoamides class is by general formula R-CONH₂Indicate that (wherein, R is the representative examples of saturated aliphatic of carbon atom number 8~30, insatiable hunger The group replaced by-OH with a part of aliphatic, aromatic series or their-H).As the monoamides class, it is not limited to following Example, can enumerate for example：Lauramide, palmitamide, stearmide, Shan Yu amide, hydroxystearic etc., oleoyl Amine, mustard seed amide, castor-oil plant amide etc..

Aforementioned substituted amide class is by general formula R₁-CONHR₂Indicate (wherein, R₁And R₂It is each independently carbon atom number 8~30 Representative examples of saturated aliphatic, unsaturated aliphatic, aromatic series or their-H a part by the group of-OH substitutions).It is taken as this For amides, example not limited to the following can be enumerated for example：N- lauryls lauramide, N- palmityls palmitamide, N- are hard Aliphatic radical stearmide, N- oil bases oleamide, N- stearyl oleamides, N- oil bases stearmide, N- stearyl mustard seeds amide, N- oil Base palmitamide, N- stearyl 12- hydroxystearics, N- oil base 12- hydroxystearics etc..

Aforementioned methylol amide class is by general formula R-CONHCH₂OH indicates that (wherein, R is the saturated fat of carbon atom number 8~30 Race, unsaturated aliphatic, aromatic series or their-H a part by the group of-OH substitutions).As the methylol amide Class, example not limited to the following can be enumerated for example：Hydroxymethylstear amide, methylol Shan Yu amides etc..

Aforementioned bisamide class is by general formula (R-CONH)₂(CH₂)_nIndicate that (wherein, R is the saturated fat of carbon atom number 8~30 Race, unsaturated aliphatic, aromatic series or their-H a part by the group of-OH substitutions.In addition, n is 1~8).As The bisamide class, example not limited to the following can be enumerated for example：Di-2-ethylhexylphosphine oxide lauramide, di-2-ethylhexylphosphine oxide hydroxy stearamidopropyl Amine, ethylenebis caprylamide, ethylenebis lauramide, ethylenebisstearamide, ethylenebis isostearoyl amine, ethylidene The double mountain Yu amides of double hydroxystearics, ethylidene, hexa-methylene bis-stearamides, hexamethylene bis mountain Yu amide, six methylenes Base double hydroxystearic, butylidenebis hydroxystearic, N, N '-distearyls adipamide, N, the N '-distearyl last of the ten Heavenly stems two Amide, di-2-ethylhexylphosphine oxide oleamide, ethylenebisoleoamide, ethylenebis mustard seed amide, hexamethylene bis oleamide, N, N '-two Oil base adipamide, N ,-two oil base decanediamides of N ', m-phenylenedimethylim- bis-stearamides, N, N '-distearyl isophthalic diformazans Amide etc..

The above-mentioned organic compound at least one amide groups can be used alone, and two or more can also mix makes With.In the above-mentioned organic compound at least one amide groups, from point for further increasing copper compound, halogen compounds From the viewpoint of dissipating property, bisamide class can be enumerated as preferred substance.

The content of the aforementioned organic compound at least one amide groups, relative to the polyamide for constituting polyamide master-batch 100 mass parts of resin, preferably 0.1~10 mass parts, more preferably 0.5~5.0 mass parts, further preferably 1.0~4.0 Mass parts.

By being set as the range, the copper compound of polyamide master-batch is constituted, halogen compounds is constituting polyamide master-batch Polyamide in dispersibility further increase, the Amilan polyamide resin composition and its formed products for present embodiment come It says, sufficient heat-resistant aging may be implemented and improve, and may be implemented that copper is inhibited to be precipitated and corrode.

(manufacturing method of polyamide master-batch)

The manufacturing method of polyamide master-batch is illustrated.

Polyamide master-batch by above-mentioned copper compound, halogen compounds and as needed aforementioned by having at least one The organic compound of a amide groups is obtained by mixing with polyamide.

Copper compound, halogen compounds, the organic compound at least one amide groups respectively can individually and polyamides Polyimide resin coordinates, and coordinates with polyamide after being pre-mixed at least two compounds in three kinds, can be by three kinds In at least two compounds be pre-mixed and crush after with polyamide coordinate, can also be by least two changes in three kinds It closes object and is pre-mixed crushing and tablet shape is made and then coordinate with polyamide.

The side that aforementioned copper compound, halogen compounds and organic compound at least one amide groups are mixed Method can apply well known method.It is, for example, possible to use roller, Henschel, ploughshare mixing machine, nauta mixer, jet stream are mixed Any one of conjunction machine etc..

Aforementioned breaking method can apply well known method.It is, for example, possible to use beater grinder, blade pulverizer, ball Any one of grinding machine, jaw crusher, conical breaker, tumbling mill, airslide disintegrating mill, mill etc..

It is previously formed the method for tablet shape, well known method can be applied.It is, for example, possible to use compression comminution granulation, pressure Any one of piece forming process, dry type extruding pelletization method, melting extrusion comminution granulation etc..

By the way that as described above by each compound and polyamide with row melting mixing is merged into, polyamide mother can be manufactured Material.

As the device for carrying out melting mixing, it is not particularly limited, well known device can be used.For example, it is preferable to use The melting mixing machines such as single screw rod or double screw extruder, banbury mixers and mixing roller.Wherein, it is preferable to use twin-screw squeezes Go out machine.

In addition, in melting mixing machine, deaerating mechanism (venthole) device and side feeder equipment can be installed.

The temperature of melting mixing preferably passes through the differential scanning calorimetry (DSC) according to JIS K7121 than polyamide Measure and the fusing point or softening point that find out it is about 1 DEG C high~about 100 DEG C of temperature.

The shear velocity of kneading machine was preferably from about for 100 (seconds^-1) more than, mean residence time when mixing is preferably from about 1 point Clock~about 15 minute.

The moisture rate of foregoing polyamides masterbatch is preferably 0.06~1.0 mass %, more preferably 0.10~0.75 mass %, Further preferably 0.15~0.75 mass %.

Moisture in polyamide master-batch can exist as the moisture of the state combined with polyamide molecule, or attached The moisture of polyamide master-batch surface such as masterbatch pellet or masterbatch powder surface.

The range is arrived by adjusting the moisture rate of foregoing polyamides masterbatch, copper compound, halogen compounds can be inhibited Cohesion.Mechanical properties, the heat-resistant aging such as toughness of Amilan polyamide resin composition and its formed products of present embodiment as a result, Improved effect it is high, can more inhibit copper to be precipitated, metal protection.

The moisture rate of foregoing polyamides masterbatch can by the vacuum degree of extruder, it is cooling when strands bath in dipping when Between, the control of steeping length or the control of water spray amount adjusts.

((F) colorant)

The Amilan polyamide resin composition of present embodiment can also contain (F) colorant.

(F) aliphatic poly that the content of colorant is 7 or more relative to the ratio between (A) carbon atom number/nitrogen-atoms numbers (C/N ratios) 100 mass parts of amide resin are preferably 0.01~5.0 mass parts, more preferably 0.02~4.0 mass parts, further preferably 0.03~2.0 mass parts.

(degradation inhibitor)

In the Amilan polyamide resin composition of present embodiment, as needed, in the model for the purpose for not damaging present embodiment In enclosing, change colour when can add for preventing heat deterioration, heating, improve heat-resistant aging and the degradation inhibitor of weatherability.

As degradation inhibitor, example not limited to the following can be enumerated for example：The phenols such as hindered phenol compound are stablized Agent；Phosphite-type stabilisers；Hindered amines stabilizer；Triazine type stabilizer；And sulphur-containing stabilizer etc..

These degradation inhibitors can be used alone, and can also be used in combination.

(other resins)

In the Amilan polyamide resin composition of present embodiment, as needed, in the model for the purpose for not damaging present embodiment In enclosing, other resins can be added.

As such resin, example not limited to the following can enumerate aftermentioned thermoplastic resin, rubber constituent etc..

As aforementioned thermoplastic resin, example not limited to the following can be enumerated for example：It is random isotactic polystyrene, complete With polystyrene resins, poly terephthalic acid second such as vertical structure polystyrene, syndiotactic polystyrene, AS resins, ABS resins Other polyamide such as the polyester resins such as diol ester, polybutylene terephthalate (PBT), nylon 6,66,612 be (present embodiment Polyamide other than polyamide), makrolon, polyphenylene oxide, polysulfones, polyethers resinoid, polyphenylene sulfide, the polyformaldehyde such as polyether sulfone etc. The acrylic resins such as condensed type resin, polyacrylic acid, polyacrylate, polymethyl methacrylate, polyethylene, polypropylene, The vinyl compounds containing halogen such as the polyolefin resins such as polybutene, ethylene-propylene copolymer, polyvinyl chloride, polyvinylidene chloride Resinoid, phenolic resin, epoxy resin etc..

These thermoplastic resins can be used alone, and can also be used in combination.

As the rubber constituent, it is not limited to following substance, can be enumerated for example：Natural rubber, polybutadiene, poly- isoamyl Diene, polyisobutene, neoprene, polysulfide rubber, polysulfide rubber (チオコー Le go system), acrylic rubber, polyurethane Rubber, silicon rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymerization Object (SEB), Styrene-Butadiene-Styrene Block Copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymerization Object (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene isoprene block copolymer (SEP), benzene Ethylene-isoprene-styrene block copolymer (SIS), hydrogenated styrene isoprene-styrene block copolymer (SEPS), styrene butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene ethylene-propylene without Advise copolymer, styrene-ethylene-butadiene random copolymer, ethylene-propylene copolymer (EPR), ethylene-(1- butylene) copolymer, Ethylene-(1- hexenes) copolymer, ethylene-(1- octenes) copolymer, ethylene-propylene-diene copolymer (EPDM), butadiene-the third Alkene nitrile-styrene core shell rubbers (ABS), methyl methacrylate-butadiene-styrene core shell rubbers (MBS), methacrylic acid Methyl esters-butyl acrylate-styrene core shell rubbers (MAS), 2-ethyl hexyl acrylate-butadiene-styrene core shell rubbers (MABS), third Olefin(e) acid Arrcostab-butadiene-acrylonitrile-styrene core shell rubbers (AABS), butadiene-styrene core shell rubbers (SBR), with first Base methyl acrylate-acrylic acid butyl ester siloxanes is nucleocapsid type rubbers materials such as the core shell rubbers of silicone-containing of representative etc..

These rubber constituents can be used alone, and can also be used in combination.

[manufacturing method of Amilan polyamide resin composition]

The Amilan polyamide resin composition of present embodiment, can be by the ratio between (A) carbon atom number/nitrogen-atoms numbers (C/N Than) coordinate inorganic fill other than above-mentioned (B) glass fibre, (C) glass fibre in the aliphatic polyamide resin that is 7 or more Material, (D) lubricant, (E) copper compound as needed and halogen compounds (wherein, except copper halide), (F) colorant, Degradation inhibitor, other resins manufacture.

As fitting method, well known extruding technology can be used.

For example, melting mixing temperature, in terms of resin temperature, preferably from about 250 DEG C~about 350 DEG C.The melting mixing time is excellent It is selected as about 1 minute~about 30 minutes.

In addition, the ingredient for constituting reinforced polyamide is supplied to the method in melting mixing machine, will can all constitute at Divide and disposably supplied to the same supply mouth, constituent can also respectively be supplied from different supply mouths.

Specific mixed method can be enumerated：Using Henschel mixer etc. by the ratio between (A) carbon atom number/nitrogen-atoms numbers Aliphatic polyamide resin that (C/N ratios) is 7 or more, (B) glass fibre, the inorganic filling material other than (C) glass fibre, (D) lubricant, the mixing of other ingredients, and it is supplied to the method being kneaded in melting mixing machine；In the list with decompressor It is 7 or more to be formed as the ratio between (A) carbon atom number/nitrogen-atoms numbers of molten condition (C/N ratios) in screw rod or double screw extruder Inorganic from side feeder cooperation (B) glass fibre, other than (C) glass fibre is filled out in aliphatic polyamide resin, (D) lubricant Fill the method etc. of material, other ingredients.

[physical property of Amilan polyamide resin composition]

About the Amilan polyamide resin composition of present embodiment, according to JIS K7121, by carrying out differential scanning calorimetry survey Fixed (cooling velocity wherein, is set as 20 DEG C/min to cool down) and measure, it is aforementioned in Amilan polyamide resin composition (A) extrapolation for the aliphatic polyamide resin that the ratio between carbon atom number/nitrogen-atoms numbers (C/N ratios) are 7 or more crystallizes start temperature (T_ic) it is 200 DEG C or more, this is excellent from the viewpoint of obtaining appearance and the more excellent Amilan polyamide resin composition of release property Choosing.More preferably 201 DEG C or more and 220 DEG C hereinafter, further preferably 202 DEG C or more and 220 DEG C hereinafter, further more excellent It is selected as 203 DEG C or more and 220 DEG C or less.

In order to be 7 or more by the ratio between (A) carbon atom number/nitrogen-atoms numbers in foregoing polyamides resin combination (C/N ratios) The extrapolation crystallization start temperature of aliphatic polyamide resin is adjusted into preferred range, containing other than (C) glass fibre Inorganic filling material, (D) lubricant, and the fat for being 7 or more relative to the ratio between (A) carbon atom number/nitrogen-atoms numbers (C/N ratios) 100 mass parts of polyamide resin contain inorganic filling material other than 0.1~10 mass parts (C) glass fibre, 0.01~10 Mass parts (D) lubricant is effective.

In addition, by containing (D) lubricant, there is the tendency for the crystallization start temperature that obtains more preferably extrapolating, it can be with Obtain appearance and the more excellent Amilan polyamide resin composition of release property.

[formed products of Amilan polyamide resin composition]

By shaping the Amilan polyamide resin composition of present embodiment, defined formed products are obtained.

It as the method for obtaining formed products, is not particularly limited, well known manufacturing process can be used.

It can enumerate for example：Extrusion molding, vacuum forming, blow molding, ejection compress moulding, is decorated injection moulding Shape, different materials forming (Ta Cai Quality formings), gas-assisted injection molding, expansion injection molding, low pressure forming, ultra-thin be injected into The manufacturing process such as combined shaping (being shaped on insert part forming, inserts) in shape (ultrahigh speed injection moulding) and mold.

The Amilan polyamide resin composition and its formed products of present embodiment, as described above, it is characterised in that use specific quantity (C) glass fibre other than inorganic filling material, (D) lubricant, thus, it is possible to obtain the creep in excellent water under environment Characteristic, appearance, release property and mechanical strength.

[purposes]

The formed products of the Amilan polyamide resin composition of present embodiment, under harsh molding condition outside the surface of formed body The stability of sight, impact resistance characteristic good, can be applied to various uses.

For example, automotive field, electric and electronic field, mechanical industry field, business machine field, aviation can be suitable for Universe field.

Embodiment

Hereinafter, enumerating specific embodiment and comparative example, the present invention is described in detail, still, the present invention is not limited to Under embodiment.

First, the inscape of polyamide, the assay method of physical property and characteristic evaluation method is as follows shown.

Polyamide is dissolved in 98% sulfuric acid, is measured according to JIS K6920.

It is evaluated using the particle of the Amilan polyamide resin composition manufactured in aftermentioned embodiment and comparative example.

Differential scanning calorimetry measures " DSC7 " manufactured using Perkin-Elmer companies.

It is to refer to JIS K7121, high 30 DEG C of the temperature of temperature at the end of being heated to than the melting peak of polyamide, After the temperature is kept for 3 minutes, 100 DEG C are cooled to 20 DEG C of cooling velocity per minute, thus draws DSC curve.

Straight line obtained from the baseline of high temperature side in cooling procedure is extended to low temperature side and the high temperature at crystallization peak The temperature of the intersection point for the tangent line that maximum place of gradient is drawn in the curve of side is as extrapolation crystallization start temperature (T_ic)。

It is evaluated using JIS3 test films.

Barrel temperature is set as 280 DEG C, mold temperature set is 80 DEG C, is injected into injection 17 seconds, cooling 20 seconds Under the conditions of shape, JIS3 test films are obtained.

Test film is impregnated 450 hours in 130 DEG C of environment, in 50% aqueous solution of long-acting liquid coolant (LLC), in water In tensile test is carried out under 23 DEG C of environment, carry out the measurement of the stress of fracture in 40 hours from on-test.

The formed products of evaluation are made using injection machine.

Injection machine uses " FN-3000 " that Jing resins Co., Ltd. manufactures.

Barrel temperature is set as 290 DEG C, mold temperature set is 80 DEG C, in injection and 20 seconds dwell times, cooling Between under 15 seconds injecting conditions, obtain the cylindric matrix band of internal diameter 30mm × long 60mm × thickness 1.5mm.In addition, as mold, Using be provided on the outside of cylindrical portion one end of matrix band cast gate, with one end of cast gate opposite side configured with force take out Undercut portions and the outside of cylindrical shape configured with force taking-up protrusion mold.

Observe the appearance of the root with the protrusion for forcing taking-up of obtained matrix band.

The evaluation of appearance is carried out with following benchmark.

+++：20 matrix bands are observed, the form of the non-pleated shape of all matrix bands but good appearance

++：20 matrix bands are observed, the form of accordion is observed in 1 or more and 5 matrix bands below

+：20 matrix bands are observed, more than the form for observing accordion in 5 matrix bands

It observes by the appearance in the cylindrical center portion of matrix band obtained above.

The evaluation of appearance is carried out with following benchmark.

+++：20 matrix bands are observed, all equal non-fillings of matrix band swell but good appearance

++：20 matrix bands are observed, filler tilting is observed in 1 or more and 5 matrix bands below

+：20 matrix bands are observed, observe that filler tilts in more than 5 matrix bands

It is evaluated using injection machine.

Injection machine uses " FN-3000 " that Jing resins Co., Ltd. manufactures.

Barrel temperature is set as 290 DEG C, mold temperature set is 80 DEG C, in injection and 20 seconds dwell times, cooling Between under 10 seconds injecting conditions, obtain the cylindric matrix band of internal diameter 30mm × long 60mm × thickness 1.5mm.Evaluation is at this time from mold The release property of demoulding.The evaluation of release property is carried out with following benchmark.

+++：Shape 20 matrix bands, all matrix bands there is no problem ground demoulding

++：Shape 20 matrix bands, generated in 1 or more and 5 matrix bands below demould it is bad

+：20 matrix bands are shaped, it is bad to generate demoulding in more than 5 matrix bands

As injection machine, " PS40E " manufactured using Jing resins Co., Ltd. manufactures the test film of evaluation.

Barrel temperature is set as 280 DEG C, mold temperature set is 80 DEG C, in 25 seconds injection+dwell times, cooling 15 seconds Injecting condition under obtain ISO test films.

Using ISO test films, Xia Shi impact strengths are measured according to ISO 179.

Measured value is the average value of n (determination sample number)=6.

[(A) polyamide]

(A1)：The polyamide 610 resin of 98% sulfuric acid viscosity 2.5

By the ratio for the polymerized unit that decanedioic acid and hexamethylene diamine are constituted：100 moles of %

(A2)：The polyamide 610 resin of 98% sulfuric acid viscosity 2.3

(A3)：The polyamide 610 resin of 98% sulfuric acid viscosity 2.5

Cupric iodide：0.03 mass %, potassium iodide：0.5 mass %

The cupric iodide of iodine/copper molar ratio=20 and potassium iodide are added in polymerization.

(A4)：The polyamide 610 resin of 98% sulfuric acid viscosity 2.3

Cupric iodide：0.03 mass %, potassium iodide：0.5 mass %

(A5)：The polyamide 66 resin of 98% sulfuric acid viscosity 2.5

Cupric iodide：0.03 mass %, potassium iodide：0.5 mass %

[(B) glass fibre]

(B1)：Treated glass fibre number average fiber diameter is carried out using the collecting agent containing copolymer-maleic anhydride： 10μm

(B2)：Treated glass fibre number average fiber diameter is carried out using the collecting agent containing polyurethane resin：10μm

[inorganic filling material other than (C) inorfil]

(C1) talcum

Trade name：ミ Network ロエース (registered trademark) L-1 (Japanese talcum company manufacture)

[(D) lubricant]

(D1) 135 DEG C of montanic acid calcium fusing point, tenor：4.8 mass %

(D2 148 DEG C of) behenic acids calcium fusing point, tenor：5.6 mass %

(D3) 155 DEG C of calcium stearate fusing point, tenor：6.7 mass %

(D4) 125 DEG C of magnesium stearate fusing point, tenor：2.5 mass %

(D5) 120 DEG C of montanic acid zinc fusing point, 7.5 mass % of tenor

(D6 126 DEG C of) behenic acids zinc fusing point, tenor：8.8 mass %

(D7) 123 DEG C of zinc stearate melting point, tenor：10.7 quality %

(D8) 134 DEG C of zinc laurate fusing point, tenor：14.0 quality %

(D9) 85 DEG C of zinc oleate fusing point, tenor：10.5 quality %

The fusing point of aforementioned each (D) lubricant measures (DSC) using differential scanning calorimetry and is measured.

[polyamide master-batch for containing (E) copper compound and halogen compounds (wherein, except copper halide)]

(E1) the polyamide 610 resin cupric iodide of 98% sulfuric acid viscosity 2.3：3 mass %, potassium iodide：15 mass %, iodine/ Copper molar ratio=8, ethylenebisstearamide：2 mass %

(E2) the polyamide 610 resin cupric iodide of 98% sulfuric acid viscosity 2.3：3 mass %, potassium iodide：30 mass %, iodine/ Copper molar ratio=20, ethylenebisstearamide：2 mass %

[(F) colorant]

(F1) carbon black

Trade name：Mitsubishi (registered trademark) カーボ Application Block ラッ Network #2600 (Mitsubishi Chemical Ind's manufacture)

[embodiment 1~11]

The TEM35 twin-screws that (A) polyamide above-mentioned is supplied to Toshiba Machine Co. Ltd's manufacture by charging hopper squeeze Go out machine (set temperature：280 DEG C, screw rod revolution 300rpm).

In addition, relative to aforementioned 100 mass parts of (A) polyamide, ratio is supplied by side feed inlet shown in following table 1 Aforementioned (B) glass fibre, and carry out melting mixing.

Relative to aforementioned 100 mass parts of (A) polyamide, ratio shown in following table 1 is supplied aforementioned by charging hopper (C) inorganic filling material, aforementioned (D) lubricant.

Ratio shown in following table 1 is supplied other additives and aforementioned (A) polyamide by charging hopper simultaneously.

The melting mixing object squeezed out from spinning mouth is cooled down with strands shape, and is granulated, to obtain granular polyamide Resin combination.

In addition, using obtained Amilan polyamide resin composition, by the method for above-mentioned record, carries out extrapolation crystallization and melt The measurement of beginning temperature, and formed products are manufactured, carry out evaluation, appearance, release property and the Xia Shi of Some Tensile Creep Characteristics in 23 DEG C of water The measurement of impact strength.

Evaluation result is as shown in table 1 below.

[comparative example 1~13]

In addition, relative to aforementioned 100 mass parts of (A) polyamide, ratio is supplied by side feed inlet shown in following table 2 Aforementioned (B) glass fibre, and carry out melting mixing.

As needed, relative to aforementioned 100 mass parts of (A) polyamide, ratio is by charging hopper shown in following table 2 Supply aforementioned (C) inorganic filling material, aforementioned (D) lubricant.

Ratio shown in following table 2 is supplied other additives and aforementioned (A) polyamide by charging hopper simultaneously.

Evaluation result is as shown in table 2 below.

[embodiment 12~24]

In addition, relative to aforementioned 100 mass parts of (A) polyamide, ratio is supplied by side feed inlet shown in following table 3 Aforementioned (B) glass fibre, and carry out melting mixing.

Relative to aforementioned 100 mass parts of (A) polyamide, ratio shown in following table 3 is supplied aforementioned by charging hopper (C) inorganic filling material, aforementioned (D) lubricant.

Ratio shown in following table 3 is supplied other additives and aforementioned (A) polyamide by charging hopper simultaneously.

Evaluation result is as shown in table 3 below.

As shown in aforementioned table 1, table 3, it was confirmed that the formed products of the Amilan polyamide resin composition of Examples 1 to 22 all have pole Some Tensile Creep Characteristics, appearance, release property, mechanical property in its 23 DEG C of excellent water.

On the other hand, it was confirmed that the 23 of the formed products of the Amilan polyamide resin composition of comparative example 1~11 shown in aforementioned table 2 Some Tensile Creep Characteristics, appearance, release property, mechanical property significantly reduce in DEG C water.

Industrial applicability

The Amilan polyamide resin composition of the present invention and the formed products for using the composition are led in automotive field, electric and electronic Domain, mechanical industry field, office equipment field, aviation, universe field etc. have industrial applicability.

Claims

1. a kind of Amilan polyamide resin composition, contains：

(A) the ratio between carbon atom number/nitrogen-atoms numbers are C/N than 100 mass parts of aliphatic polyamide resin for 7 or more,

(B) 1~200 mass parts of glass fibre,

(C) 0.1~10 mass parts of inorganic filling material other than glass fibre, and

(D) 0.01~10 mass parts of lubricant,

Inorganic filling material other than (C) glass fibre is selected from wollastonite, kaolin, mica, talcum, calcium carbonate, carbonic acid Magnesium, potassium titanate, aluminium borate and clay,

The average grain diameter of inorganic filling material other than (C) glass fibre is 0.01~38 μm,

The lubricant be in montanic acid calcium, behenic acids calcium, montanic acid zinc, behenic acids zinc and zinc stearate it is a kind of with On.

2. Amilan polyamide resin composition as described in claim 1, wherein

As according to the differential scanning calorimetry of JIS K7121 measure obtained from, in the Amilan polyamide resin composition described in (A) the extrapolation crystallization start temperature (T of polyamide_ic) it is 200 DEG C or more, it, will in differential scanning calorimetry measurement Cooling velocity is set as 20 DEG C/min and is cooled down.

3. Amilan polyamide resin composition as claimed in claim 1 or 2, wherein

4. Amilan polyamide resin composition as claimed in claim 1 or 2, wherein

(A) polyamide is selected from by polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 1010 One or more of the group formed with polyamide 1012.

5. Amilan polyamide resin composition as claimed in claim 1 or 2, wherein

(B) glass fibre is to carry out treated glass fibre using collecting agent, and the collecting agent contains copolymer, described Copolymer has the alkenyl monomer of unsaturated ethylene containing carboxylic acid anhydrides and the unsaturation in addition to the alkenyl monomer of unsaturated ethylene containing carboxylic acid anhydrides Vinyl monomer is as polymerized unit.

6. Amilan polyamide resin composition as claimed in claim 1 or 2, wherein

Also contain 0.002~2 mass parts of (E) copper compound and halogen compounds, the halogen compounds does not include copper halide.

7. Amilan polyamide resin composition as claimed in claim 6, wherein

The molar ratio x/y of halogen element content x and copper coin cellulose content y in (E) copper compound and halogen compounds is 2/1 ~50/1, the halogen compounds does not include copper halide.

8. Amilan polyamide resin composition as claimed in claim 6, wherein

(E) copper compound and halogen compounds are added in the form of polyamide master-batch, and the halogen compounds does not include halogen Change copper.

9. Amilan polyamide resin composition as claimed in claim 7, wherein

10. Amilan polyamide resin composition as claimed in claim 1 or 2, wherein

Also contain 0.01~5 mass parts of (F) colorant.

11. a kind of formed products contain the Amilan polyamide resin composition described in any one of claims 1 to 10.