CN108003610A - Amilan polyamide resin composition and its formed body - Google Patents
Amilan polyamide resin composition and its formed body Download PDFInfo
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- CN108003610A CN108003610A CN201711042996.2A CN201711042996A CN108003610A CN 108003610 A CN108003610 A CN 108003610A CN 201711042996 A CN201711042996 A CN 201711042996A CN 108003610 A CN108003610 A CN 108003610A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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Abstract
The present invention relates to Amilan polyamide resin composition and its formed body.The present invention provides a kind of well balanced Amilan polyamide resin composition and formed body with high shaping mobility and with toughness and anti-flammability.A kind of Amilan polyamide resin composition, it is the resin combination containing (a) polyamide He (b) melamine cyanurate, wherein, (a) ratio of component of the molecular weight obtained in polyamide by gel permeation chromatography (GPC) below 15000 is the mass % of 15.0 mass %~30.0 of whole (a) polyamide, the mass % of and 4.0 mass % that the ratio of the component of molecular weight more than 100000 is whole (a) polyamide~8.0.
Description
Technical field
Formed body obtained from being molded the present invention relates to Amilan polyamide resin composition and by said composition.
Background technology
The molding processibility of polyamide including comprising mechanical property etc. has excellent characteristic, therefore always
Since be widely used in the various parts such as automobile component, electronic and electric components, industrial machinery part.Especially because toughness is excellent
It is different, it thus be accordingly used in the product with articulated sections such as connector, clips.Under many circumstances, to these product requirement anti-flammabilitys.It is special
It is not from the viewpoint of environment, it is expected to use halogen-free flame retardants.
As the typical example of such fire-resistant polyamide resin, the resistance for having used melamine cyanurate can be enumerated
Combustion property polyamide material, such as connector for electric and electronic field, clip etc. (referenced patent document 1 and 2).Patent document
The Amilan polyamide resin composition for having used specific phosphotriester, higher fatty acid metal salt and polyalcohol is proposed in 3.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Application 53-125459 publications
Patent document 2：Japanese Unexamined Patent Application 53-031759 publications
Patent document 3：Japanese Unexamined Patent Publication 11-106645 publications
The content of the invention
Problem to be solved by the invention
For the above-mentioned fire-resistant polyamide resin for having used melamine cyanurate, melamine cyanurate
It is not compatible in polyamide fully, but is filled in as inorganic filler with scattered shape in composition.Therefore,
It is filled with the tendency that there is the Amilan polyamide resin composition of melamine cyanurate its toughness to reduce.
The present invention completes in view of the foregoing, improves anti-flammability, toughness its purpose is to provide one kind and reduces
The Amilan polyamide resin composition of the inequality (バ ラ つ I) of toughness.
The means used to solve the problem
The present inventor has made intensive studies to solve the above-mentioned problems, it turns out that, by will contain polyamide and
The molecular weight constituent amount of polyamide in the resin combination of melamine cyanurate is adjusted to particular range, can improve resistance
Combustion property, toughness and the inequality for reducing toughness, so as to complete the present invention.
That is, Amilan polyamide resin composition of the invention is the resin containing (a) polyamide He (b) melamine cyanurate
Composition, the ratio of component of the molecular weight obtained by gel permeation chromatography (GPC) in (a) polyamide below 15000 is whole
(a) ratio of the mass % of 15.0 mass % of polyamide~30.0 and the component of molecular weight more than 100000 is whole (a) polyamides
The mass % of 4.0 mass % of amine~8.0.
(a) molecular weight distribution (weight average molecular weight (Mw)/number-average molecular weight (Mn)) of polyamide is preferably 1.90~2.00.
The Amilan polyamide resin composition of the present invention can also contain (c) polyalcohol and/or its ester derivant.
In addition, the Amilan polyamide resin composition of the present invention can also contain (d) higher fatty acid metal salt.
Relative to 100 mass parts (a) polyamide, (b) melamine cyanurate of the mass parts of 2 mass parts~20 is preferably comprised
Salt.
The Amilan polyamide resin composition of the present invention preferably comprises the mass of (a) polyamide of 100 mass parts, 2 mass parts~20
Part (b) melamine cyanurate and the mass parts of 0.1 mass parts~1.0 (c) polyalcohol and/or its ester derivant.
Additionally, it is preferred that (a) polyamide, 2 mass parts containing 100 mass parts~20 mass parts (b) melamine cyanogen urea
(d) higher fatty acid metal salt of the mass parts of hydrochlorate and 0.05 mass parts~2.0.
Additionally, it is preferred that (a) polyamide, 2 mass parts containing 100 mass parts~20 mass parts (b) melamine cyanogen urea
The mass parts of (c) polyalcohol and/or its ester derivant of the mass parts of hydrochlorate, 0.1 mass parts~1.0 and 0.05 mass parts~2.0
(d) higher fatty acid metal salt.
It is preferred that more than 80 mass % it is polyamide 66 among (a) polyamide.
(a) polyamide is more preferably polyamide 66.
(a) the relative sulfuric acid viscosity η r of polyamide 66 are preferably 2.65~2.88.
(a) the relative sulfuric acid viscosity η r of polyamide 66 are more preferably 2.73~2.88.
The formed body of the present invention is obtained by the way that the Amilan polyamide resin composition of the present invention is molded.
Invention effect
The Amilan polyamide resin composition of the present invention is the polyamide containing (a) polyamide He (b) melamine cyanurate
Resin combination, the ratio of component of the molecular weight obtained by gel permeation chromatography (GPC) in (a) polyamide below 15000
Example is whole for the mass % of 15.0 mass %~30.0 of whole (a) polyamide and the ratio of the component of molecular weight more than 100000
The mass % of 4.0 mass % of a (a) polyamide~8.0, therefore can be had originally not damaging Amilan polyamide resin composition
Mechanical property, chemical-resistant, good mouldability, improve anti-flammability, toughness in the case of electrical characteristics etc. and reduce toughness
Inequality, and the purposes such as appliances parts, electronic unit, automobile component can be suitably employed in.
Brief description of the drawings
Fig. 1 is the approximate vertical view of the hinged formed body (ヒ Application ジ formed bodies) used in the evaluation of embodiment.
Fig. 2 is the summary side elevation of the hinged formed body used in the evaluation of embodiment.
Reference numeral
10 hinged formed bodys
12 articulated sections
Embodiment
Hereinafter, the present invention is described in detail.
[Amilan polyamide resin composition]
The Amilan polyamide resin composition of the present invention is the resin group containing (a) polyamide He (b) melamine cyanurate
Compound, the ratio of component of the molecular weight obtained by gel permeation chromatography (GPC) in (a) polyamide below 15000 is whole
The mass % of 15.0 mass % of a (a) polyamide~30.0, and the ratio of the component of molecular weight more than 100000 is whole (a) poly-
The mass % of 4.0 mass % of acid amides~8.0.
Hereinafter, each component is described in detail.
[(a) component：Polyamide]
The polyamide used in the present invention is the polymer for having in main chain amido link (- NHCO-), can be enumerated for example：
Polycaprolactam (polyamide 6), nylon 46 (polyamide 46), polyhexamethylene adipamide (polyamide 66), polycyclic oneself
Two acyl hexamethylene diamine (polyamide 6 C) of alkane, polyhexamethylene sebacamide (polyamide 610), nylon 612 (polyamide
612), poly- 11 lactams (polyamide 11), nylon 12 (polyamide 12), poly-6I hexamethylene isoterephalamide (polyamide
6I), poly- hexamethylene terephthalamide (polyamide 6 T), poly-paraphenylene terephthalamide's nonamethylene diamine (polyamide 9T), poly- paraphenylene terephthalamide ten
Dioxane diamines (polyamide 12T), poly-meta-xylylene adipamide (polyamide MXD6) and containing at least two among them not
Polyamide copolymer and their mixture of same polyamide forming component etc..
Among above-mentioned various polyamide, particularly polyamide 66 be suitable as be used for obtain mouldability and fusing point it is higher,
And require the material of the component of more high-fire resistance.In the case of using two or more polyamide, the machine under mouldability, high temperature
From the viewpoint of tool characteristic, the polyamide of the polyamide 66 component further preferably more than 50 mass %, further preferably
The polyamide of the polyamide of the polyamide 66 component of more than 80 mass %, most preferably the polyamide 66 component of 100 mass %.
The molecular weight ＞ of polyamide in ＜ compositions
For the polyamide that uses in the Amilan polyamide resin composition of the present invention, by by molecular weight below 15000
Component and more than 100000 component be adjusted to specifically measure respectively, anti-flammability, toughness can be improved and reduce toughness not
.Specifically, from the viewpoint of anti-flammability, forming stability, relative to whole polyamide, molecular weight is below 15000
Component is the mass % of 15.0 mass %~30.0, the mass % of more preferably 15.0 mass %~20.0.In addition, from anti-flammability, tough
Property from the viewpoint of, the component of molecular weight more than 100000 is the mass % of 4.0 mass %~8.0, more preferably 4.5 mass %~
8.0 mass %.
From the viewpoint of uneven reduction, forming stability from toughness, molecular weight distribution (weight average molecular weight (Mw)/number
Average molecular weight (Mn)) it is preferably 1.90~2.00.
In order to be specified quantitative by the molecular-weight adjusting of the polyamide in Amilan polyamide resin composition, such as preferably in extruder
Melting mixing when by screw speed, screw rod form be controlled.
The molecular weight of polyamide can be obtained by using the measure of gel permeation chromatography (GPC).Device uses Tosoh
" HLC-8320GPC " of Co., Ltd.'s manufacture, detector use differential refractometer (RI), and solvent uses and is dissolved with 0.1 mole of %
Sodium trifluoroacetate hexafluoroisopropanol (HFIP), chromatographic column use TOSOH Co., Ltd manufacture " TSKgel-GMHHR-M " 2
Root and " G1000HHR " 1.Sample concentration is 1~3 (mg samples)/1 (mL solvents), is filtered with filter, is removed insoluble
Component, so as to obtain measure sample.Based on obtained elution curve, converted and counted by polymethyl methacrylate (PMMA)
Calculate the molecular weight of polyamide.
The viscosity ＞ of ＜ polyamide
For polyamide, the polyamide that 98% relative sulfuric acid viscosity η r are 2.65~2.88 is preferably comprised, more preferably
For 2.73~2.88.By having containing such polyamide, obtained Amilan polyamide resin composition in anti-flammability and toughness
Balance in terms of more excellent tendency.It should be noted that 98% relative sulfuric acid viscosity η r can be by described in embodiment
Method is measured.
[(b) component：Melamine cyanurate]
(b) melamine cyanurate used in the present invention is the reaction with same mole product of melamine and cyanuric acid,
Such as obtain in the following way：At a temperature of about 90 DEG C~about 100 DEG C, by melamine aqueous solution and cyanurate aqueous solution
It is stirred, it is reacted and is obtained product, and precipitation filtering is carried out to the product.Obtained material is consolidated for white
Body, is preferably made micro mist shape to use by crushing.
Can contain in present embodiment, in melamine cyanurate more than 0.001 mass % and 0.30 mass % with
Under unreacted melamine or cyanuric acid.Such melamine cyanurate is commercially on sale, can suitably use
The product that can industrially obtain.
The median particle diameter (D50) of (b) melamine cyanurate before being mixed with (a) component polyamide is without special
Limitation, is preferably 1 μm~20 μm from the viewpoint of the dispersiveness of melamine cyanurate, more preferably 1.5 μm~15 μ
m.Median particle diameter by melamine cyanurate is more than 1 μm, and processing becomes easy, can suppress melamine cyanurate
The coherency of salt is deteriorated.It it is less than 20 μm by the median particle diameter of melamine cyanurate, in Amilan polyamide resin composition
Dispersiveness and the balancing good of treatability.
Here, median particle diameter (D50) as defined in JIS Z8901, is to be more than a certain grain in the particle diameter distribution of plastochondria
The quality of the particle in footpath accounts for particle diameter during the 50% of the quality of whole plastochondrias, such as can be surveyed by laser diffraction scattering method
It is fixed.Specifically, it can be longitudinal axis mapping using particle diameter as transverse axis and with frequency (quality), will set by laser diffraction scattering method
When the summation of the accumulated quality of the frequency is 100%, accumulated quality reaches 50% particle diameter and is measured as median particle diameter.
The use level of melamine cyanurate is the mass parts of 2 mass parts~20 relative to 100 mass parts of polyamide, preferably
For the mass parts of 3 mass parts~15.For the use level of melamine cyanurate, it is preferably from the viewpoint of anti-flammability
More than 2 mass parts, it is preferably 20 below mass part from the viewpoint of mechanical properties.Melamine cyanurate is in polyamide resin
Cooperation in fat can also apply known any means, but the industrial side for preferably carrying out being kneaded cooperation in extruder etc.
Method.
[(c) component：Polyalcohol and/or its ester derivant]
The polyalcohol used in the present invention and/or its ester derivant preferably comprise at least one polyalkylene polyol and its
Fatty acid ester.It can enumerate：The glycol such as polyethylene glycol, polypropylene glycol, ethylene glycol, diethylene glycol, trimethylene, propane diols
The polyalcohol such as glycols, glycerine, pentaerythrite such as class, 1,4-butanediol, 1,5-PD, 1,6- hexylene glycols, as poly- alkylene
For the fatty acid ester of polylol, it can enumerate for example：The polyalkylenes such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol are polynary
Alcohol and capric acid, laurate, myristic acid, palmitic acid, stearic acid, behenic acids, cerinic acid, montanic acid, melissic acid, oleic acid, erucic acid etc.
Ester of aliphatic carboxylic acid or derivatives thereof, they are industrially readily available.It is excellent from the viewpoint of the dispersiveness of (b) component
Select higher fatty acids (carbon number more than 12) ester of the fatty acid ester of polyethylene glycol, polyethylene glycol, more preferably polyethylene glycol
Or derivatives thereof.The additive amount of these polyalcohols and/or its ester derivant is usually relative to (a) polyamide of 100 mass parts
The mass parts of the mass parts of 0.1 mass parts~1.0, more preferably 0.1 mass parts~0.8.Addition for higher fatty acid metal salt
For amount, it is preferably more than 0.1 mass parts from the viewpoint of tensile elongation, is preferably 1.0 from the viewpoint of anti-flammability
It is below mass part.
For high-grade aliphatic ester as preferable polyethylene glycol, polyethylene glycol oxide monolaurate can be enumerated, gathered
Ethylene oxide monostearate, polyethylene glycol oxide distearate, polyethylene glycol oxide monoleate, particularly preferred polyethylene glycol oxide
Monolaurate, polyoxyethylene monostearate ester, polyethylene glycol oxide monoleate.
In addition, for as the higher fatty acids ester derivant of preferable polyethylene glycol, can enumerate：Polyethylene glycol oxide loses
Water D-sorbite monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan
Tristearate, polyoxyethylene sorbitan monoleate, polyoxyethylene sorbitan trioleate.
[(d) component：Higher fatty acid metal salt]
The higher fatty acid metal salt (d) used in the present invention can enumerate capric acid, laurate, myristic acid, palmitic acid,
The sodium of the higher aliphatic carboxylic acid of the carbon numbers more than 9 such as stearic acid, behenic acids, cerinic acid, montanic acid, melissic acid, oleic acid, erucic acid
Salt, lithium salts, calcium salt, magnesium salts, zinc salt, aluminium salt etc., among these higher fatty acid metal salts, particularly preferred metallic stearic
Salt, specifically calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, this is because will not reduce finally obtain it is poly-
The anti-flammability of amide resin composition.In addition, from gas during shaping produce it is few from the aspect of, most preferably calcium stearate, hard
Resin acid aluminium.The additive amount of these higher fatty acid metal salts is usually 0.01 mass parts relative to (a) polyamide of 100 mass parts
~5 mass parts, the particularly preferably mass parts of 0.05 mass parts~2.0.For additive amount, from processing and forming when plasticising make
From the viewpoint of be preferably more than 0.01 mass parts, from processing and forming when gas produce, from the viewpoint of anti-flammability preferably
It is below mass part for 5.In addition, these higher fatty acid metal salts can be used alone, can also and with two or more.
The resin combination of present embodiment is that can improve toughness, anti-flammability and the uneven resin combination for reducing toughness
Thing.The inventors of the present invention estimate, these characteristics are attributed to the molecular weight constituent amount of polyamide and disperseing for melamine cyanurate
The cooperative effect of property.That is, estimate：(a) the low molecular weight scope (below molecular weight 15000) of component polyamide anti-flammability, into
Aspect shows effect to type stability (mainly in low injection pressure), high molecular weight range (molecular weight more than 100000) exists
Effect is shown in terms of toughness, in addition, the dispersiveness by improving melamine cyanurate, can show this at a high level
A little characteristics.
[other components]
, can be as needed in the range of the purpose of the present invention not be damaged in the Amilan polyamide resin composition of the present invention
Usual various elastomers, filler are added, for example, the inorfil such as glass fibre, carbon fiber, mica, talcum, clay pit
The inorganic fillers such as thing, aluminium oxide, silica and apatite, aluminium hydroxide, magnesium hydroxide, zinc borate, zinc stannate, hydroxyl tin
Sour zinc, ammonium polyphosphate, adipoguanamine, melamine polyphosphate, melamine sulfate, melamine phthalate
With the fire retardant such as aluminum phosphate, the pigment such as titanium white and carbon black, the phosphorous acid metal salt such as colouring agent, sodium hypophosphite, with hindered phenol, are obstructed
Amine, trialkylphosphate and phosphite ester be representative heat stabilizer, higher fatty acid metal salt, higher fatty acid amides, height
Lubricant, various plasticizer, and the various additives such as antistatic agent such as level fatty acid ester.
[manufacture method of Amilan polyamide resin composition]
The manufacture method of Amilan polyamide resin composition of the present invention is not particularly limited, can first to (a) component, (b) into
Divide, (c) component and (d) component carry out melting mixing, but examined from the dispersed viewpoint of (b) component melamine cyanurate
Consider, the part of (b) component can be added after melting mixing remaining all the components, and further carry out melting mixing.
(a) shape of component is not particularly limited, and is preferably graininess.In this case, the viewpoint that slave device simplifies
Consider, (c) component can be made to extend (exhibition) in the particle surface of (a) component, then expand further (b) component, (d) component
Open up and obtain blend, then carry out melting mixing.
In the manufacture method of the Amilan polyamide resin composition of the present invention, the method for carrying out melting mixing does not limit especially
System, when mixing (a) component, (b) component, (c) component and (d) component, preferably by using an at least raw material feed device
Supply to extruder and the method that carries out melting mixing.Supply of each component to extruder can use each different raw materials to supply
To device, a raw material feed device can also be used.
For extruder, it is not particularly limited, preferably double screw extruder.For double screw extruder, tool
For body, the ZSK series, the TEM series of Toshiba Machinery Co., Ltd.'s manufacture, Japan's system of the manufacture of COPERION companies can be enumerated
TEX series of Gang Suo Co., Ltd. manufacture etc., the L/D (screw rod effective length/outer screw diameter) of double screw extruder is preferably 20
Above and less than 60 scope, be preferably more than 30 and less than 50.In order to by the molecular weight of (a) polyamide in resin combination
Particular range is adjusted to, the preferably resin temperature when being discharged from extruder front end nozzle is higher than the fusing point of the polyamide of principal component
Extruded under conditions of 25 DEG C~40 DEG C, can by the screw speed of extruder, be kneaded hop count and (refer to multiple be referred to as pinching
Close the section that the high screw element of melting effect of disk continuously forms) it is controlled.
The method for supplying source materials to double screw extruder is not particularly limited.Raw material feed device is not particularly limited,
Single screw rod feeder, twin-screw feeder, desk-top feeder, rotary table feeder, liquid supply pump etc. can be used.It is wherein weightless
The variable error of the raw material supply of compensation screw feeder is few, therefore preferably.In addition, plurality of raw materials is put into an original
In the case of expecting in feedway, at least two raw material mixers among the raw material to be put into, taper can be mixed
Device etc. mix and then put into.
[formed body]
Formed body obtained from the Amilan polyamide resin composition shaping of the present invention had into anti-flammability, toughness, stable molding
Property, therefore be suitable as being used as electrical and electronic parts, automobile interior exterior portion component, the auto electrics such as socket, switch, housing, lid
The injection molded article of component etc., as these injection molded articles moulding material particle.
Embodiment
Illustrate the present invention in further detail using embodiment and comparative example.
(raw material evaluation of physical property method)
First, the evaluation method of the physical property of raw material is illustrated.The physical property of the raw material used in embodiment and comparative example
Evaluation proceeds as follows.
＜ relative sulfuric acid viscosities ＞
According to JIS K6920,98% relative sulfuric acid viscosity η r of polyamide 66 are determined.
＜ molecular weight ＞
Using following GPC, the molecular weight distribution (weight average molecular weight (Mw)/number-average molecular weight of polyamide 66 is determined
(Mn))。
Device：" HLC-8320GPC " of TOSOH Co., Ltd's manufacture
Detector：Differential refractometer (RI)
Solvent：Hexafluoroisopropanol (HFIP) dissolved with 0.1 mole of % sodium trifluoroacetate
Chromatographic column：That TOSOH Co., Ltd is manufactured, " TSKgel-GMHHR-M " 2 and " G1000HHR " 1 series connection make
With based on obtained elution curve, being converted by polymethyl methacrylate (PMMA) to calculate.
＜ median particle diameters ＞
(b) median particle diameter of component melamine cyanurate based flame retardant is filled using laser diffraction type particle size distribution
(trade name " SALD-7000 ", Shimadzu Corporation's manufacture) is put to be determined.Sample is scattered in pure water
Obtained material is determined as measure sample using flow cell.It is that the longitudinal axis is made using particle diameter as transverse axis, with frequency (quality)
Figure, during using the summation for the accumulated quality for setting frequency as 100%, accumulated quality reach 50% particle diameter as median particle diameter (D50).
(preparation of each component)
[(A) component：Polyamide]
(a-1) component：Polyamide 66
It is prepared for containing 50 mass % with monomer mixture of the equimolar each containing hexamethylene diamine and adipic acid
Aqueous solution 15kg.Then, above-mentioned monomer solution is loaded with the 40L volumes of agitating device and lower part with extraction nozzle
Autoclave in, and fully stirred monomer solution at 50 DEG C.With nitrogen to being sufficiently carried out displacement in autoclave,
Then the temperature in autoclave is warming up to about 270 DEG C from 50 DEG C while monomer solution is stirred, so as to be polymerize.
At this time, the pressure in autoclave is calculated as about 1.8MPa with gauge pressure, water is expelled to outside system at any time so that the pressure does not reach
To more than 1.8MPa.In addition, polymerization time is have adjusted so that the η r of polyamide 66 resin are about 2.81.
After polymerization in autoclave, polyamide 66 resin is discharged from lower nozzle with wire, by water cooling and is cut
Cut, obtained granular polyamide 66 (η r：2.81、Mw/Mn：1.98).
(a-2)：It is polymerize in a manner of same with (a-1) component, adjusts polymerization time so that η r are about 2.71, obtain
Granular polyamide 66 (η r are arrived：2.71、Mw/Mn：1.97).
(a-3)：It is polymerize in a manner of same with (a-1) component, adjusts polymerization time so that η r are about 2.75, obtain
Granular polyamide 66 (η r are arrived：2.75、Mw/Mn：1.98).
(a-4)：It is polymerize in a manner of same with (a-1) component, adjusts polymerization time so that η r are about 2.61, obtain
Granular polyamide 66 (η r are arrived：2.61、Mw/Mn：1.98).
(a-5)：Polyamide 6, the SF1013A of the emerging production manufacture in space portion
[(b) component：Melamine cyanurate]
(b-1)：Melamine cyanurate, median particle diameter (D50)：10μm
[(c) component：Polyalcohol and/or its ester derivant]
(c-1)：Polyethylene glycol oxide monolaurate, the EMANON (registration mark) 1112 of Kao Corp's manufacture
(PEM)
(c-2)：Polyethylene glycol, the PEG400 (PEG) of Sanyo Chemical Industries Co., Ltd.'s manufacture
[(d) component：Higher fatty acid metal salt]
(d-1)：Calcium stearate, the calcium stearate of NOF Corp's manufacture
[embodiment 1]
(a-1) polyamide 66, (b-1) melamine cyanurate, (c-1) PEM, (d-1) calcium stearate are mixed, and made
Supplied with loss-in-weight feeder to double screw extruder (ZSK-40MC that COPERION Co., Ltd. manufactures, cylinder number：12)
First supply mouth.Extruded when 270 DEG C of cylinder temperature, discharge rate 100kg/ are small, under conditions of screw speed 250rpm.Squeeze
The screw rod for going out machine is provided with two mixing sections.Its first mixing section is located at extruder the 4th, and consist of has from upstream side
R-KD (the feed types that 3 L (length for forming the screw rod direction of principal axis of the screw rod of mixing section) are 12mm：R types kneading disk), 2 L be
N-KD (no conveying types of 24mm：N-type kneading disk) and L-KD (reverse feed types that 1 L is 12mm：L-type kneading disk).Second is mixed
Refining section is located at the 8th of extruder, consists of the R-KD for being 12mm with 2 L from upstream side, the N-KD that 1 L is 24mm
With the L-KD that 1 L is 12mm." mixing section " said here refers to the high screw rod member of multiple melting effects for being referred to as kneading disk
The section that part continuously forms.
Then, polymer is discharged from extruder front end nozzle with wire, water cooling, cutting is carried out, so as to obtain polyamide
Resin composition pellet.
[embodiment 2~5, comparative example 1]
In addition to the composition of each component is set as described in Table 1, implementation has been made in a manner of similarly to Example 1
The Amilan polyamide resin composition particle of example 2~5 and comparative example 1.
[comparative example 2~5]
Except the screw speed of extruder is changed to 200rpm and is changed to the second mixing section (being located at the 8th) defeated
Send beyond section, be carried out in a manner of similarly to Example 1.It should be noted that transportation section refers to, only by feed type
Screw element forms and the section without mixing section.
(evaluation of Amilan polyamide resin composition)
The Amilan polyamide resin composition particle of each embodiment and comparative example is evaluated.By each assessment item and its knot
Fruit is shown in Table 1.Each assessment item evaluation method is as follows shown.
＜ molecular weight ＞
The quantitative of the component of component and molecular weight more than 100000 of the molecular weight below 15000, molecular weight distribution (are divided equally again
Son amount (Mw)/number-average molecular weight (Mn)) it is determined using following GPC.
Device：" HLC-8320GPC " of TOSOH Co., Ltd's manufacture
Detector：Differential refractometer (RI)
Solvent：The hexafluoroisopropanol (HFIP) of sodium trifluoroacetate dissolved with 0.1 mole of %
Chromatographic column：That TOSOH Co., Ltd is manufactured, " TSKgel-GMHHR-M " 2 and " G1000HHR " 1 series connection make
With based on obtained elution curve, being converted by polymethyl methacrylate (PMMA) to calculate.
The tension test of ＜ minimal thickness (thin meat cited Zhang Try test) ＞
Using injection (mo(u)lding) machine (SE50D that Sumitomo Heavy Industries, Ltd manufactures), barrel temperature is set as 270
DEG C, mold temperature set be 80 DEG C, in injection 10 seconds, cool down under the conditions of the injection moulding of 10 seconds to Amilan polyamide resin composition
Grain is injection moulded, and has obtained the test film of 0.5mm thickness.Using obtained dumbbell shape test film, in collet spacing
55mm, draw speed have carried out the measure of tensile elongation under conditions of 50mm/ minutes.At this time, by the stretching of 10 test films
The value of elongation calculates standard deviation.
＜ is hinged standard deviation ＞
Using injection (mo(u)lding) machine, (day Seiko industry Co., Ltd. manufactures：PS40E), barrel temperature is set as 270 DEG C, mould temperature
Degree is set as 80 DEG C, is the hinged formed body 10 shown in Fig. 1 and Fig. 2 by Amilan polyamide resin composition grain forming.Fig. 1 is hinged
The top view of formed body 10, Fig. 2 are the side view of hinged formed body 10.Hinged formed body 10 has articulated section 12.For made
The hinged formed body 10 for each example made, under 23 DEG C, 50%RH atmosphere, repeats hinged testing machine, with 33 beats/min using automatic
Speed repeat by 12 bending of articulated section to substantially 180 ° then be restored to home position (0 °) position action, determine
Stage after how many times bending fractures and destroys.In hinged experiment, 15 formed bodys are determined, by the mark of 15 formed bodys
Index of the quasi- deviation as uneven (バ ラ つ I).
＜ forming stabilities (Spiral flow length) ＞
Using injection (mo(u)lding) machine (SE50D that Sumitomo Heavy Industries, Ltd manufactures), barrel temperature is set as 270
DEG C, mold temperature set be 80 DEG C, and in injection 10 seconds, cooling 10 seconds, injection speed 200mm/ seconds, injection pressure 40MPa
Under the conditions of Amilan polyamide resin composition particle is injection moulded, width 10mm, thickness 1mm spiral flow mold in into
Type, length of flow is determined after 15 experiment injections (Homes て シ ョ ッ ト).For forming stability, the 1st injection is measured
With the length of flow of the 5th injection, judged according to following determinating reference.
(metewand)
A：The difference of the length of flow of 1st injection and the 5th injection is less than ± 2mm
B：The difference of the length of flow of 1st injection and the 5th injection is ± more than 2mm
＜ anti-flammabilitys ＞
Using injection (mo(u)lding) machine (PS40E that Jing resins Co., Ltd. manufactures), barrel temperature is set as 270 DEG C, mould
Temperature is set as 80 DEG C, and Amilan polyamide resin composition particle is injection molded into UL-94 testing vertical flammability measure test films
(thickness：0.40mm、0.80mm).Using different each 5 test films of molding thickness in this way, hung down based on UL-94
Direct combustion burns test evaluation anti-flammability, and implements the judgement of anti-flammability V-0, V-1, V-2, HB.
As shown in table 1, according to the present invention, while anti-flammability, tenacity excellent, additionally it is possible to reduce the inequality of toughness.
On the other hand, molecular weight is that the ratio of more than 100000 polyamide component is less than 1 He of comparative example of 4.0 mass %
In 2, hinged characteristic is good, but tensile elongation is poor, uneven also larger.In addition, molecular weight is less than 15000 polyamide component
Comparative example 3~5 of the ratio less than 15 mass % in, hinged characteristic and tensile elongation are good, but the inequality of tensile elongation
It is larger, and anti-flammability and forming stability are poor.
Industrial applicability
Since the Amilan polyamide resin composition of the present invention has high flame retardant, as various mechanical industry components, electricity
Pneumoelectric subassembly, the particularly industry such as connector, clip are useful with material.
Claims (11)
1. a kind of Amilan polyamide resin composition, it is the resin combination containing (a) polyamide He (b) melamine cyanurate
Thing, wherein,
The ratio of component of the molecular weight obtained in (a) polyamide by gel permeation chromatography (GPC) below 15000 is whole
The ratio of the mass % of 15.0 mass % of (a) polyamide~30.0 and the component of molecular weight more than 100000 is whole institute
State the mass % of the 4.0 mass % of (a) polyamide~8.0.
2. Amilan polyamide resin composition as claimed in claim 1, wherein, the molecular weight distribution of (a) polyamide is that is, heavy equal
Molecular weight (Mw)/number-average molecular weight (Mn) is 1.90~2.00.
3. Amilan polyamide resin composition as claimed in claim 1 or 2, wherein, the Amilan polyamide resin composition also contains (c)
Polyalcohol and/or its ester derivant.
4. such as Amilan polyamide resin composition according to any one of claims 1 to 3, wherein, the Amilan polyamide resin composition
Also contain (d) higher fatty acid metal salt.
5. such as Amilan polyamide resin composition according to any one of claims 1 to 4, wherein, relative to described in 100 mass parts
(a) polyamide, the Amilan polyamide resin composition contain (b) melamine cyanurate of the mass parts of 2 mass parts~20.
6. the Amilan polyamide resin composition as described in claim 3 or 4, wherein, the Amilan polyamide resin composition contains 100 matter
Measure (b) melamine cyanurate, 0.1 mass parts~1.0 of the mass parts of (a) polyamide of part, 2 mass parts~20
(d) of the mass parts of (c) polyalcohol and/or its ester derivant of mass parts, and/or 0.05 mass parts~2.0 is advanced
Fatty acid metal salts.
7. such as Amilan polyamide resin composition according to any one of claims 1 to 6, wherein, 80 matter among (a) polyamide
Amount more than % is polyamide 66.
8. such as Amilan polyamide resin composition according to any one of claims 1 to 6, wherein, (a) polyamide is polyamide
66。
9. Amilan polyamide resin composition as claimed in claim 7 or 8, wherein, the relative sulfuric acid viscosity of (a) polyamide 66
η r are 2.65~2.88.
10. Amilan polyamide resin composition as claimed in claim 7 or 8, wherein, the sulfuric acid phase of (a) polyamide 66 is to viscous
It is 2.73~2.88 to spend η r.
11. a kind of formed body, Amilan polyamide resin composition according to any one of claims 1 to 10 is is molded to obtain by it
Formed body.
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| CN102363672A (en) * | 2011-06-30 | 2012-02-29 | 深圳市科聚新材料有限公司 | MCA (Melamine Cyanurate) flame-retardant polycaprolactam compound material and preparation method thereof |
| US20130131235A1 (en) * | 2010-04-29 | 2013-05-23 | Clariant Finance (Bvi) Limited | Flame-Proof Agent-Stabiliser Combination for Thermoplastic and Duroplastic Polymers |
| CN103408750A (en) * | 2013-07-12 | 2013-11-27 | 东华大学 | Preparation method of melamine cyanurate flame-retardant polyamide material |
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| JP2003301104A (en) * | 2002-04-10 | 2003-10-21 | Ube Ind Ltd | Flame-retardant polyamide resin composition and manufacturing method therefor |
| EP1431340A1 (en) * | 2002-12-19 | 2004-06-23 | DSM IP Assets B.V. | Flame retardant polyamide compound |
| US20080146704A1 (en) * | 2006-12-15 | 2008-06-19 | General Electric Company | Polyamide compositions, methods of manufacture thereof, and articles comprising the same |
| JP6458452B2 (en) * | 2013-11-05 | 2019-01-30 | 東レ株式会社 | Polyamide resin and polyamide resin composition |
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| US20130131235A1 (en) * | 2010-04-29 | 2013-05-23 | Clariant Finance (Bvi) Limited | Flame-Proof Agent-Stabiliser Combination for Thermoplastic and Duroplastic Polymers |
| CN102363672A (en) * | 2011-06-30 | 2012-02-29 | 深圳市科聚新材料有限公司 | MCA (Melamine Cyanurate) flame-retardant polycaprolactam compound material and preparation method thereof |
| CN103408750A (en) * | 2013-07-12 | 2013-11-27 | 东华大学 | Preparation method of melamine cyanurate flame-retardant polyamide material |
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| CN115707736A (en) * | 2021-08-20 | 2023-02-21 | 旭化成株式会社 | Polyamide resin composition and molded article |
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