CN110036074A - Amilan polyamide resin composition, its manufacturing method and the formed body being made of the Amilan polyamide resin composition - Google Patents
Amilan polyamide resin composition, its manufacturing method and the formed body being made of the Amilan polyamide resin composition Download PDFInfo
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- CN110036074A CN110036074A CN201780074795.2A CN201780074795A CN110036074A CN 110036074 A CN110036074 A CN 110036074A CN 201780074795 A CN201780074795 A CN 201780074795A CN 110036074 A CN110036074 A CN 110036074A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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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
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Abstract
The present invention provides a kind of Amilan polyamide resin composition, which is characterized in that 10~80 mass parts of 100 mass parts of polyamide (A) and phosphorus flame retardant (B) for being 270~350 DEG C containing fusing point, yellow chromaticity (YI0) it is 3.0 or less.
Description
Technical field
The present invention relates to Amilan polyamide resin composition, its manufacturing method and the moldings being made of the Amilan polyamide resin composition
Body.
Background technique
Heat resistance, the mechanical property of polyamide are excellent, are used as the engine environment of many electrical and electronic parts, automobile
Component constituent material.
In these components, the anti-flammability of height is required the polyamide for constituting electrical and electronic parts.As to resin
The method for assigning anti-flammability, usually using fire retardant.In recent years, it due to the raising of environmental consciousness, usually avoids using halogen system
Fire retardant and use non-halogen fire retardant.
As non-halogen fire retardant, For example, Patent Document 1 discloses the reaction product of melamine and phosphoric acid with
The mixture of zinc compound and phosphinates, disclose in patent document 2 melamine and phosphoric acid reaction product and time
The mixture of phosphonate and metallic compound discloses and meets flame-retardant standard UL94V-0 in 1/16 inch of molded product
Standard.
However, phosphinates is being kneaded when manufacturing resin combination with molten polyamide, decompose sometimes, due to this
When the gas that generates, polyamide can also decompose, and the molecular weight of polyamide reduces, and there are heat-resisting for the resin combination obtained from
Property, reduce the problem of such as mechanical property, anti-flammability, in addition, due to polyamide heat deterioration, oxidative degradation and thermo-color occurs, have
When yellow chromaticity (yellow colour index, YI) rise.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2004-263188 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2007-023206 bulletin
Summary of the invention
The present invention solves the above subject, and its purpose is to provide a kind of heat resistance, mechanical property, excellent in flame retardance, and
And the Amilan polyamide resin composition that the rising of yellow chromaticity is inhibited.
Further investigation has been repeated in the inventors of the present invention in order to solve the above problems, as a result, it has been found that, under given conditions
The Amilan polyamide resin composition of manufacture is able to solve the above subject, completes the present invention.
That is, purport of the invention is as follows.
(1) a kind of Amilan polyamide resin composition, which is characterized in that the polyamide (A) 100 for being 270~350 DEG C containing fusing point
10~80 mass parts of mass parts and phosphorus flame retardant (B), yellow chromaticity (YI0) it is 3.0 or less.
(2) Amilan polyamide resin composition according to (1), which is characterized in that the yellow after reflow treatment at 265 DEG C
Spending changing value (Δ YI) is 12.0 or less.
(3) Amilan polyamide resin composition according to (1) or (2), which is characterized in that phosphorus flame retardant (B) is time phosphine
Hydrochlorate and/or diphosphinic acid salt.
(4) Amilan polyamide resin composition according to (3), which is characterized in that phosphinates is by the following general formula (I) table
The compound shown, diphosphinic acid salt are the compound indicated by the following general formula (II).
(in formula, R1、R2、R4And R5Each independently represent the alkyl or benzene of the carbon atom number 1~16 of linear chain or branched chain
Base.R3Indicate the alkylidene of carbon atom number 1~10 of linear chain or branched chain, the arlydene of carbon atom number 6~10, alkyl alkylene,
Or alkyl arylene.M indicates calcium ion, aluminium ion, magnesium ion or zinc ion.M is 1 or 3.N, a, b be meet 2 × b=n ×
The integer of the relational expression of a)
(5) Amilan polyamide resin composition according to any one of (1)~(4), which is characterized in that further containing fibre
Tie up shape strengthening material (C) 5~140 mass parts.
(6) Amilan polyamide resin composition according to any one of (1)~(5), which is characterized in that further containing cunning
0.1~20 mass parts of stone (F).
(7) a kind of manufacturing method of Amilan polyamide resin composition, which is characterized in that be for manufacturing in above-mentioned (1)~(6)
The method of described in any item Amilan polyamide resin compositions, in the melting mixing of polyamide (A) and phosphorus flame retardant (B),
1 or more side feeder is arranged in melting mixing machine, with the additive amount of the phosphorus flame retardant (B) of side feeder at every 1 relative to
100 mass parts of polyamide (A) add phosphorus flame retardant (B) from side feeder for 20 mode below the mass.
(8) a kind of manufacturing method of Amilan polyamide resin composition, which is characterized in that be for manufacturing described in above-mentioned (5)
The method of Amilan polyamide resin composition adds fibee reinforced material (C) in the melting mixing of resin combination several times.
(9) manufacturing method of the Amilan polyamide resin composition according to (7) or (8), which is characterized in that in melting mixing
It is preceding to polymerize polyamide (A), implement the polymerization under non-active gas atmosphere.
(10) manufacturing method of the Amilan polyamide resin composition according to any one of (7)~(9), which is characterized in that
Implement the melting mixing of polyamide (A) and phosphorus flame retardant (B) under non-active gas atmosphere.
(11) a kind of formed body, which is characterized in that be by polyamide group described in any one of above-mentioned (1)~(6)
Close what object was molded with.
According to the present invention it is possible to provide a kind of Amilan polyamide resin composition, can substantially inhibit because in melting mixing
Thermo-color caused by heat deterioration, oxidative degradation, and be able to suppress the decomposition of polyamide, can highly maintain mechanical property,
Anti-flammability.In addition, it is 260 DEG C that even if the formed body that Amilan polyamide resin composition of the invention is molded with, which carries out maximum temperature,
The reflow treatment of left and right, is also able to suppress the rising of yellow chromaticity.
Specific embodiment
Hereinafter, explaining the present invention in detail.
Amilan polyamide resin composition of the invention contains polyamide (A) and phosphorus flame retardant (B).
It is 270 DEG C~350 DEG C that the polyamide (A) for constituting Amilan polyamide resin composition of the invention, which needs fusing point,.Polyamide
(A) it is 270 DEG C or more by fusing point, there is heat resistance, is resistant to the reflow process that maximum temperature is 260 DEG C or so.It is another
Aspect, polyamide (A) is if fusing point is more than 350 DEG C, since the decomposition temperature of amido bond is about 350 DEG C, sometimes molten
It is carbonized, decomposed when melting processing.
Polyamide (A) can enumerate fatty polyamide, semiaromatic polyamide composition, alicyclic according to the classification of monomer component
The copolymer of polyamide and they.
As the concrete example of fatty polyamide, polyamide 46 etc. can be enumerated.
As semiaromatic polyamide composition, the polyamides being made of aromatic dicarboxylic acid ingredient and aliphatic diamine ingredient can be enumerated
Amine can enumerate polyamide 4I (I: M-phthalic acid), polyamide 6 I, polyamide 7T (T: terephthalic acid (TPA)), gather as concrete example
Amide 8T, polyamide 9T, polyamide 10T, polyamide 11T, polyamide 12T etc..
As the concrete example of alicyclic polyamide, polyamide 6 C (C:1,4- cyclohexane dicarboxylic acid), polyamide can be enumerated
7C, polyamide 8C, polyamide 9C, polyamide 10C, polyamide 11C, polyamide 12C etc..
In turn, as copolymer, such as when the carbon atom number of diamines is 6, PA6T/6, PA6T/12, PA6T/ can be enumerated
66, PA6T/610, PA6T/612, PA6T/6I, PA6T/6I/66, PA6T/M5T (M5: making methylpentamethylenediamine diamine), PA6T/TM6T
(TM6:2,2,4- or 2,4,4- trimethylhexamethylenediamine), PA6T/MMCT (MMC:4,4 '-di-2-ethylhexylphosphine oxide (2- methyl
Cyclohexylamine)) etc..
It as polyamide (A), can be used alone these polyamide, copolymer or polyamides of more than two kinds also can be used
The mixture of amine.
In the present invention, it can enumerate polyamide 46 from the aspect of industrial versatility height as polyamide (A), gather
Amide 6T, polyamide 9T, polyamide 10T and their copolymer are as preference.In turn, polyamide 6 T, polyamide 9T, polyamides
Amine 10T and their copolymer are resistance to reflow especially excellent from the viewpoint of high-fire resistance, low water absorption, therefore further
It is preferred that, wherein particularly preferred polyamide 10T and its copolymer.
In the present invention, polyamide (A) is preferably using monocarboxylic acid ingredient as constituent.By containing monocarboxylic acid, polyamide
(A) the free ammonia base unit weight of end can be kept as to lower, point of the polyamide caused by heat deterioration, oxidative degradation when because being heated
Solution, discoloration are inhibited.As a result, having the effect of that height maintains mechanical property, anti-flammability.
The content of monocarboxylic acid ingredient is preferably 0.3~4.0 to rub relative to the whole monomer components for constituting polyamide (A)
You are %, and further preferably 0.3~3.0 mole of %, more preferably 0.3~2.5 mole of %, particularly preferably 0.8~2.5 rubs
You are %.By containing monocarboxylic acid ingredient within the above range, the heat deterioration, oxidation when polyamide (A) is able to suppress because being heated are bad
Decomposition, discoloration caused by changing, and reduce molecular weight distribution when polymerization, or release property raising when discovery processing and forming,
Or inhibit the yield of gas in processing and forming.On the other hand, polyamide (A) is if the content of monocarboxylic acid ingredient is more than upper
Range is stated, then mechanical property reduces sometimes.It should be noted that the content of monocarboxylic acid refers to single carboxylic in polyamide (A) in the present invention
The residue of acid, that is, the hydroxyl of end is from ratio shared by group obtained by monocarboxylic acid disengaging.
In the present invention, the molecular weight of monocarboxylic acid ingredient is preferably 140 or more, and further preferably 170 or more.Polyamide
(A) if the molecular weight of monocarboxylic acid is 140 or more, heat deterioration when being able to suppress because being heated, the decomposition caused by oxidative degradation,
Discoloration, and release property improves, and can inhibit the yield of gas at the temperature at which processing and forming, and also can be improved into
Type mobility.
As monocarboxylic acid ingredient, aliphatic monocarboxylic acid, cycloaliphatic monocarboxylic, aromatic monocarboxylate can be enumerated, wherein preferably
Aliphatic monocarboxylic acid.
The aliphatic monocarboxylic acid for being 140 or more as molecular weight, such as octanoic acid, n-nonanoic acid, capric acid, lauric acid, meat can be enumerated
Myristic acid, palmitinic acid, stearic acid, behenic acid.Wherein, from the aspect of versatility height, preferred stearic acid.
The cycloaliphatic monocarboxylic for being 140 or more as molecular weight, such as 4- ethyl cyclohexane carboxylic acid, 4- hexyl can be enumerated
Cyclohexane-carboxylic acid, 4- lauryl cyclohexane-carboxylic acid.
The aromatic monocarboxylate for being 140 or more as molecular weight, such as 4- ethyl benzoate, 4- hexyl benzene first can be enumerated
Acid, 4- laurel yl benzoic acid, 1- naphthoic acid, 2- naphthoic acid and their derivative.
Monocarboxylic acid ingredient can be used alone, and also can be used together.Alternatively, it is also possible to and with molecular weight be 140 or more list
The monocarboxylic acid of carboxylic acid and molecular weight less than 140.
It should be noted that the molecular weight of monocarboxylic acid refers to the molecular weight of the monocarboxylic acid of raw material in the present invention.
In general, known polymer, there are crystal phase and amorphous phase, the crystallization properties such as fusing point are mainly determined by the state of crystal phase
It is fixed.Since the end group in polymer is present in amorphous phase, the fusing point of polyamide will not because the presence or absence of end group,
Type and change.Moreover, the monocarboxylic acid for being bonded to the end of polyamide chains exists in amorphous phase, therefore the fusing point of polyamide is not
It can decline because containing monocarboxylic acid.
In the present invention, melt flow rate (MFR) (MFR) of the polyamide (A) under 340 DEG C, 1.2kg load be preferably 1~
200g/10 minutes, more preferably 10~150g/10 minutes, further preferably 20~100g/10 minutes.MFR can be used as into
The value of the index of type mobility, MFR is higher, indicates that mobility is higher.If the MFR of polyamide (A) is more than 200g/10 minutes,
The mechanical property of the resin combination then obtained sometimes reduces, if the MFR of polyamide (A) is less than 1g/10 minutes, mobility
It significantly reduces, it sometimes can not melt-processed.
Previously known heating polymerization, the manufacture of the method for solution polymerization process can be used in polyamide (A).Wherein, from industry
, it is preferable to use heating polymerization from the perspective of going up favorably.The polymerization of polyamide (A) is preferably non-live by nitrogen, carbon dioxide, argon etc.
Property gas enclose polymeric kettle in, implement under non-active gas atmosphere.There is the oxidative degradation because of the polyamide in polymerization as a result,
Caused discoloration is inhibited, while polymerizeing the effect that the discoloration in later process is also inhibited.
In the manufacture of polyamide (A), in order to improve the efficiency of polymerization, polymerization catalyst can be used.As polymerization catalyzed
Agent, such as phosphoric acid, phosphorous acid, hypophosphorous acid or their salt can be enumerated, the additive amount of polymerization catalyst is usually relative to dicarboxylic acids
Total moles with diamines are preferably 2 moles of % or less.
As the phosphorus flame retardant (B) for constituting Amilan polyamide resin composition of the invention, phosphate compound, secondary can be enumerated
Phosphonate, diphosphinic acid salt, phosphazene compound etc..
As phosphate compound, such as can to enumerate trimethyl phosphate, triethyl phosphate, tributyl phosphate, tricresyl phosphate pungent
Ester, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate base diphenyl ester, octyl diphenyl phosphate,
Tri-2-ethylhexyl phosphate, phosphoric acid 6-diisopropyl benzene ester, tricresyl phosphate (xylyl) ester, tricresyl phosphate (isopropyl phenyl)
Ester, tri naphthyl phosphate, bisphenol-A biphosphonate, quinhydrones biphosphonate, resorcinol biphosphonate, resorcinol-phosphoric acid hexichol
Ester, trihydroxy benzene triguaiacyl phosphate or their substituent, condensation product.Wherein, from being not easy to be attached to mold, formed body it is heat-resisting
From the aspect of property, moisture-proof are excellent, preferred phosphate compound.Phosphate compound can be monomer, oligomer, polymer
Or their mixture.As the specific trade name of phosphate compound, such as Daihachi Chemical Industry Co., Ltd. can be enumerated
" TPP " (triphenyl phosphate) of system, " TXP " (tricresyl phosphate (xylyl) ester), " CR-733S " (bis- (di(2-ethylhexyl)phosphates of resorcinol
Phenyl ester)), " PX200 " (1,3- phenylene-four (2,6- 3,5-dimethylphenyl) phosphate), " PX201 " (1,4- phenylene-
Four (2,6- 3,5-dimethylphenyl) phosphates), " PX202 " (4,4 '-biphenylene-four (2,6- 3,5-dimethylphenyl) phosphoric acid
Ester).They can be used alone, and also can be used together.
As phosphinates and diphosphinic acid salt, the chemical combination indicated respectively by the following general formula (I) and logical formula (II) can be enumerated
Object.
In formula, R1、R2、R4And R5Need to be each independently the alkyl or benzene of the carbon atom number 1~16 of linear chain or branched chain
Base, the preferably alkyl or phenyl of carbon atom number 1~8, more preferably methyl, ethyl, n-propyl, isopropyl, normal-butyl, tertiary fourth
Base, n-pentyl, n-octyl, phenyl, further preferably ethyl.R1With R2And R4With R5Ring can be formed each other.
R3Need the alkylidene of carbon atom number 1~10, the arlydene of carbon atom number 6~10, alkyl for linear chain or branched chain
Alkylidene or alkyl arylene.The alkylidene of carbon atom number 1~10 as linear chain or branched chain, for example, can enumerate methylene,
Ethylidene, n-propylene, isopropylidene, isopropylidene, positive butylidene, tertiary butylidene, positive pentylidene, positive octamethylene, positive Asia ten
Dialkyl group.As the arlydene of carbon atom number 6~10, such as phenylene, naphthylene can be enumerated.As alkyl arylene, such as
Methylphenylene, ethylphenylene, tert-butylphenylene, methyinaphthylene, ethyl naphthylene, tert-butyl naphthylene can be enumerated.
As aryl alkylene, such as phenylmethylene, phenyl-ethylene, phenylpropylene, phenyl butylidene can be enumerated.
M indicates metal ion.As metal ion, such as calcium ion, aluminium ion, magnesium ion, zinc ion can be enumerated, preferably
Aluminium ion, zinc ion, more preferable aluminium ion.
M, n indicates the valence mumber of metal ion.M is 2 or 3.A indicates the number of metal ion, and b indicates diphosphinic acid ion
Number.N, a, b are the integer for meeting " 2 × b=n × a ".
Phosphinates, diphosphinic acid salt respectively use corresponding phosphinic acids or diphosphinic acid and metal carbonate, metallic hydrogen
Oxide or metal oxide manufacture in aqueous solution, exist usually in the form of monomer, but also rely on reaction condition sometimes
And exist in the form of condensation degree is 1~3 polymer phosphinates.
Phosphinic acids used in manufacture as phosphinates, such as dimethylphosphinic acid, ethyl-methyl time phosphine can be enumerated
Acid, diethyl phosphinic acids, methyl-n-propyl phosphinic acids, isobutyl methyl phosphinic acids, octyl methyl phosphinic acids, aminomethyl phenyl time
Phosphonic acids, diphenyl phosphonic acid, wherein preferred diethyl phosphinic acids.
As the concrete example of the phosphinates indicated by above-mentioned logical formula (I), such as dimethylphosphinic acid calcium, diformazan can be enumerated
Base phosphinic acids magnesium, dimethylphosphinic acid aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid calcium, ethylimethyphosphinic acid magnesium, second
Ylmethyl phosphinic acids aluminium, ethylimethyphosphinic acid zinc, diethyl phosphinic acids calcium, diethyl phosphinic acids magnesium, aluminum diethylphosphinate,
Diethyl phosphinic acids zinc, methyl-n-propylphosphinic acid calcium, methyl-n-propylphosphinic acid magnesium, methyl-n-propylphosphinic acid aluminium, methyl
N-propyl phosphinic acids zinc, methylphenylphosphinic acid calcium, methylphenylphosphinic acid magnesium, methylphenylphosphinic acid aluminium, aminomethyl phenyl time
Zinc phosphonate, diphenyl phosphonic acid calcium, diphenyl phosphonic acid magnesium, diphenyl phosphonic acid aluminium, diphenyl phosphonic acid zinc.Wherein, from resistance
Combustion property, electrical characteristics balancing good from the aspect of, preferably aluminum diethylphosphinate, diethyl phosphinic acids zinc, more preferable diethyl
Base phosphinic acids aluminium.
In addition, diphosphinic acid used in manufacture as diphosphinic acid salt, such as (the methyl time phosphine of methane two can be enumerated
Acid), benzene -1,4- two (methyl-phosphinic acid).
As the concrete example of the diphosphinic acid salt indicated by above-mentioned logical formula (II), for example, (the methyl time phosphine of methane two can be enumerated
Acid) calcium, methane two (methyl-phosphinic acid) magnesium, methane two (methyl-phosphinic acid) aluminium, methane two (methyl-phosphinic acid) zinc, benzene -1,
4- bis- (methyl-phosphinic acid) calcium, benzene -1,4- two (methyl-phosphinic acid) magnesium, benzene -1,4- two (methyl-phosphinic acid) aluminium, benzene -
1,4- bis- (methyl-phosphinic acid) zinc.Wherein, from anti-flammability, electrical characteristics balancing good from the aspect of, two (first of optimization methane
Base phosphinic acids) aluminium, methane two (methyl-phosphinic acid) zinc.
As phosphorus flame retardant (B), from excellent with the Combination of polyamide (A), and a small amount of addition can be assigned effectively
Show off consideration, preferably phosphinates or diphosphinic acid salt in the side for giving anti-flammability.In turn, particularly preferred phosphinates or diphosphinic acid
The mixture of salt.As the combination of phosphinates and diphosphinic acid salt, such as aluminum diethylphosphinate, diethyl time phosphine can be enumerated
The diphosphinic acid salt such as the phosphinates such as sour zinc and methane two (methyl-phosphinic acid) aluminium, methane two (methyl-phosphinic acid) zinc.As secondary
The specific trade name of phosphonate, diphosphinic acid salt and their mixture, such as Clariant corporation can be enumerated
“Exolit OP1230”、“Exolit OP1240”、“Exolit OP1312”、“Exolit OP1314”、“Exolit
OP1400”。
As phosphazene compound, such as the cyclic phosphazene compound indicated by the following general formula (III) can be enumerated.
In formula, R6、R7The alkyl of carbon atom number 1~10, the aryl of carbon atom number 6~15 are each independently represented, c indicates 3
~15 integer.As the alkyl of carbon atom number 1~10, such as methyl, ethyl, n-propyl, isopropyl, various fourths can be enumerated
Base, various hexyls, various octyls, cyclopenta, cyclohexyl.R6、R7It can be any one of straight-chain, branched, ring-type.Separately
Outside, the aryl as carbon atom number 6~15, such as can enumerate and can import the substituent groups such as alkyl, aryl, alkoxy on ring
Phenyl.As R6、R7, it is preferably to it is aryl, wherein be both preferably phenyl.As the specific trade name of phosphazene compound, example
" the Rabitle FP-100 ", " Rabitle FP-110 ", great Zhong chemical company system of pharmacy institute corporation are seen as volt can be enumerated
" SPS-100 ", " SPB-100 ".
Phosphorus flame retardant (B) can be used in combination with flame retardant (D).As flame retardant (D), such as can to enumerate nitrogen system fire-retardant
Agent, inorganic flame retardant, wherein preferred nitrogenated flame retardant.
As nitrogenated flame retardant, such as melamine cyanurate, melamine polyphosphate, pyrophosphoric acid melamine can be enumerated
Amine, melamine phosphate, pyrophosphoric acid double melamine, polyphosphoric acid melam, polyphosphoric acid melems, wherein from phosphinates,
From the aspect of the combined effect of diphosphinic acid salt is high, preferred melamine polyphosphate.The quantity of phosphorus is preferably 2 or more, more excellent
It is selected as 10.The content ratio of phosphinates, diphosphinic acid salt and melamine polyphosphate is preferably 1:1~8:1 by quality ratio,
More preferably 2:1~4:1.
As inorganic flame retardant, such as the metal hydroxides such as magnesium hydroxide, calcium hydroxide, calcium aluminate, boron can be enumerated
Other zinc salts such as sour zinc, trbasic zinc phosphate etc..Wherein, the mixture of more than two kinds of preferred boric acid zinc and other zinc salts, further preferably
The mixture of magnesium hydroxide and zinc borate and trbasic zinc phosphate.
As zinc borate, such as 2ZnO3B can be enumerated2O3、4ZnO·B2O3·H2O、2ZnO·3B2O3·3.5H2O。
As other zinc salts, such as Zn can be enumerated3(PO4)2The trbasic zinc phosphates such as ZnO, ZnSn (OH)6、ZnSnO3Etc. zinc stannates
And calcium molybdate zinc, wherein preferred trbasic zinc phosphate.
And when with zinc borate and trbasic zinc phosphate, the content ratio of zinc borate and trbasic zinc phosphate by quality ratio be preferably 1:0.1~
1:5, more preferably 1:2~1:4, further preferably 1:2.5~1:3.5.
Metal hydroxides can be any one of granular, plate, needle-shaped.Use granular or plate metal hydroxide
When object, average grain diameter is preferably 0.05~10 μm, and more preferably 0.1~5 μm.When using acicular metal hydroxides,
Average diameter is preferably 0.01~10 μm, and more preferably 0.1~5 μm, average length is preferably 5~2000 μm, more preferably 10
~1000 μm.From the viewpoint of heat resistance, the impurity such as the preferably other metals of metal hydroxides, chlorine, sulphur it is poor
Metal hydroxides.In addition, being examined in terms of it can be improved the dispersibility in Amilan polyamide resin composition, improve thermal stability
Consider, the surface of metal hydroxides is preferably surface-treated with surface treating agent, solid solution etc..As surface treating agent, example
Silane coupling agent, titanium coupling agent, fatty acid or derivatives thereof can such as be enumerated.As solid solution, such as the metals such as nickel can be enumerated.
In Amilan polyamide resin composition of the invention, flame retardant (D) be can be used alone, and also can be used together.
The content of phosphorus flame retardant (B) in Amilan polyamide resin composition is needed relative to 100 mass parts of polyamide (A)
10~80 mass parts, preferably 20~40 mass parts.If the content of phosphorus flame retardant (B) is difficult to assign less than 10 mass parts
Give anti-flammability.On the other hand, if the content of phosphorus flame retardant (B) is more than 80 mass parts, it is difficult to melting mixing resin combination
Object, the excellent in flame retardance of obtained resin combination, but mechanical property becomes inadequate instead.
Amilan polyamide resin composition of the invention can substantially inhibit because in melting mixing heat deterioration, caused by oxidative degradation
Thermo-color, and yellow chromaticity (YI0) need for 3.0 hereinafter, preferably -10.0~-1.0, more preferably -10.0~-
5.0.Thermo-color in melting mixing is substantially inhibited and yellow chromaticity (YI0) it is 3.0 Amilan polyamide resin compositions below as after
The phosphorus system resistance that polyamide (A) can be made an addition to by limiting in the melting mixing of polyamide (A) and phosphorus flame retardant (B)
It fires the amount of agent (B) and manufactures.
In addition, formed body obtained from Amilan polyamide resin composition of the invention is formed has excellent resistance to thermo-color
Property, the decomposition of polyamide is able to suppress heating to formed body, therefore xanthochromia is inhibited, the reflux at 265 DEG C
Treated, and yellow chromaticity changing value (Δ YI) is preferably 12.0 or less.Huang of the resin combination after the reflow treatment at 265 DEG C
When coloration changing value (Δ YI) is 12.0 or less, the discoloration that is able to suppress in the installation procedure of electrical and electronic parts.
Amilan polyamide resin composition of the invention preferably further contains fibee reinforced material (C).Fibee reinforced material
Material (C) is not particularly limited, such as can enumerate glass fibre, carbon fiber, boron fibre, asbestos fibre, vinal, polyester
Fiber, acrylic fiber, fully aromatic polyamide fiber, polyphenyl are simultaneouslyAzoles fiber, polytetrafluoroethylene fibre, kenaf, bamboo
Fiber, flaxen fiber, sugarcane fiber, high-strength polyethylene fiber, alumina fibre, silicon carbide fibre, potassium titanate fibre, brass are fine
Dimension, stainless steel fibre, steel fibre, ceramic fibre, basalt fibre etc..Wherein, from the improvement effect height of mechanical property, with energy
The heat resistance of enough tolerance and heating temperature when polyamide melting mixing, from the aspect of being easy to get, preferred glass fibers
Dimension, carbon fiber, metallic fiber.Fibee reinforced material (C) can be used alone, and also can be used together.
Glass fibre, carbon fiber are preferably surface-treated with silane coupling agent.Silane coupling agent can be dispersed in boundling
Agent.As silane coupling agent, such as vinyl silanes system, silicon Acrylote methane series, epoxy silane system, amino silicone methane series can be enumerated,
Wherein, from the sealing property of polyamide and glass fibre or carbon fiber it is high from the aspect of, preferred amino silicone methane series coupling agent.
Fibre length, the fibre diameter of fibee reinforced material are not particularly limited, and fibre length is preferably 0.1~7mm,
More preferably 0.5~6mm.It is 0.1~7mm by the fibre length of fibee reinforced material, mouldability can not be caused not
Good influence ground reinforced resin composition.In addition, fibre diameter is preferably 3~20 μm, more preferably 5~13 μm.Pass through threadiness
The fibre diameter of strengthening material is 3~20 μm, and ground reinforced resin composition can not be lost in melting mixing.As threadiness
The cross sectional shape of strengthening material can enumerate circle, rectangle, ellipse, odd-shaped cross section other than it etc., wherein preferably circular.
The content of fibee reinforced material (C) in Amilan polyamide resin composition is excellent relative to polyamide (A) 100 mass parts
It is selected as 5~140 mass parts, more preferably 40~80 mass parts.If the content of fibee reinforced material less than 10 mass parts,
Sometimes the improvement effect of mechanical property is small.On the other hand, if the content of fibee reinforced material is more than 140 mass parts, gather
Amide resin composition not only the improvement effect saturation of mechanical property and can not it is expected the improvement effect more than it, but also melt mixed
Operability when refining reduces, and is difficult to obtain particle sometimes.
Amilan polyamide resin composition of the invention by contain phosphorous antioxidant (E), can make stability, mouldability into
One step is excellent.
Phosphorous antioxidant can be any one of inorganic compound, organic compound.As phosphorous antioxidant, example
Sodium dihydrogen phosphate, disodium hydrogen phosphate, tertiary sodium phosphate, sodium phosphite, Arizona bacilli, phosphorous acid magnesium, phosphorous acid manganese can such as be enumerated
Inorganic phosphate, triphenyl phosphite, phosphorous acid three (octadecyl) ester, tridecyl phosphite, trisnonyl phenyl phosphite, Asia
Diphenyl phosphate isodecyl ester, bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphites
(" Adekastab PEP-36 "), bis- (2,4- di-t-butyl phenyl) pentaerythritol diphosphites (" Adekastab
PEP-24G "), three (2,4- di-t-butyl phenyl) phosphite esters, distearyl pentaerythrityl diphosphite
(" Adekastab PEP-8 "), bis- (nonyl phenyl) pentaerythritol diphosphites (" Adekastab PEP-4C "), 1,
1 '--4,4 '-diyl of biphenyl bis- [bis- (the 2,4- di-t-butyl phenyl) esters of phosphonous acid], four (2,4- di-t-butyl benzene
Base)-two phosphinate (" HOSTANOX P-EPQ ") of 4,4 '-biphenylene, four (tridecyls -4,4 '-different sub- fork base
The organic phosphorus chemical combination such as diphenyl diphosphites, 2,2- di-2-ethylhexylphosphine oxide (4,6- di-t-butyl phenyl) octyl phosphite ester
Object.Phosphorous antioxidant can be used alone, and also can be used together.
Phosphorous antioxidant (E) uniformly mixes with phosphorus flame retardant (B), prevents the decomposition of fire retardant due to being easy,
It can be improved anti-flammability.In addition, can prevent the molecular weight of polyamide (A) reduces, improves operability when squeezing out processing, forms
Property, mechanical property.The reduction of discoloration degree when especially can be to reflow treatment plays significant effect.
The content of phosphorous antioxidant (E) is preferably 0.1~3 mass parts relative to 100 mass parts of polyamide (A), into one
Step is preferably 0.1~1 mass parts.By making 0.1~3 mass parts of content of phosphorous antioxidant (E), can not reduce it is crowded
In the case where stability, mouldability, mechanical property when processing out, release property when forming from mold is improved, mould gas is inhibited
The blocking of body ventilation opening improves continuous injection moldability.
Even if it is 260 DEG C or so that the formed body that Amilan polyamide resin composition of the invention is molded with, which carries out maximum temperature,
Reflow treatment, be also able to suppress the rising of yellow chromaticity, talcum (F) further contained by Amilan polyamide resin composition, can
Inhibit to generate blistering in reflow treatment.Talcum (F) is not particularly limited, and average grain diameter is preferably 10~30 μm.In addition, talcum
(F) it can be surface-treated with organic compounds such as silane coupling agents, by being surface-treated, can be improved and polyamide
(A) adaptation to raising intensity, inhibits blistering effective.The average grain diameter of talcum (F) in the present invention refers to is spread out by laser
The median particle diameter (D50) that the method for penetrating obtains.
Amilan polyamide resin composition of the invention, which can according to need, further to be added containing other packing materials, stabilizer etc.
Add agent.As additive, such as the filling material such as can enumerate bloating tendency clay mineral, silica, aluminium oxide, bead, graphite
The pigment such as material, titanium oxide, carbon black, hindered phenolic antioxidant, sulfur antioxidant, light stabilizer, antistatic agent.
Polyamide (A) and phosphorus flame retardant (B) are mixed and further cooperate fibee reinforced material (C), other additions
Agent etc. and the method for manufacturing Amilan polyamide resin composition of the invention is not particularly limited as long as long as damaging its effect, it is preferably molten
Melt mixing method.As melting mixing method, can enumerate using Brabender (to the batch-types such as Brabender Brabender kneader,
The method of Banbury mixer, Henschel mixer, helical rotor, roller, single axle extruding machine, biaxial extruder etc..Melting mixing
Temperature is melted from polyamide, is selected in Undec region.If melting temperature is excessively high, not only polyamide (A) is decomposed,
And phosphorus flame retardant (B) is also possible to decompose, therefore relative to the fusing point of polyamide (A) (Tm), preferably (Tm-20 DEG C)
~(Tm+50 DEG C).
When manufacturing resin combination of the invention by melting mixing, need to limit the phosphorus system resistance for making an addition to polyamide (A)
Fire the amount of agent (B).In the melting mixing of polyamide (A) and phosphorus flame retardant (B), if by a large amount of phosphorus flame retardant (B)
Make an addition to polyamide (A), then since temperature temporarily drastically reduces, the viscosity of resin combination steeply rises, and
Apply big shearing.As a result, the actual temperature of resin combination becomes temperature more higher than the set temperature of device, the resistance of phosphorus system
The organic principles such as combustion agent (B) are likely to occur decomposition or thermo-color.
The method that the amount of the phosphorus flame retardant (B) of polyamide (A) is supplied to as limitation, for example, using continuous molten
When melting kneading machine, it can enumerate and 1 or more side feeder is set in melting mixing machine, the phosphorus system resistance of side feeder at limitation every 1
Fire the method for the additive amount of agent (B).In present invention, it is desirable to opposite with the additive amount of the phosphorus flame retardant (B) of side feeder at every 1
Phosphorus flame retardant (B) is added from side feeder in 100 mass parts of polyamide (A) for 20 mode below the mass.
In addition, the method for being supplied to the amount of the phosphorus flame retardant (B) of polyamide (A) as limitation, uses the mixed of batch-type
When conjunction machine is as melting mixing machine, the method supplied several times can be enumerated, the additive amount of every 1 phosphorus flame retardant (B) is opposite
In 100 mass parts of polyamide (A) be preferably 20 below the mass.
In the manufacture of the resin combination containing fibee reinforced material (C), in the melting mixing of resin combination
It is preferred that adding fibee reinforced material (C) several times, the additive amount of every 1 time fibee reinforced material (C) is relative to polyamide
(A) 100 mass parts are preferably 30 below the mass.
Polyamide (A), energy are supplied to by the additive amount of limitation phosphorus flame retardant (B) or fibee reinforced material (C)
Enough the actual temperature of resin combination is inhibited excessively to rise, inhibited because of the heat deterioration in melting mixing, the change caused by oxidative degradation
Color, and the discoloration in the formed body obtained by resin combination, caused by being also able to suppress because of heat deterioration, oxidative degradation.
It is preferably enclosed to the entirety until the raw material supply unit to heating part of board in the melting mixing of resin combination
The non-active gas such as nitrogen, carbon dioxide, argon carry out melting mixing under non-active gas atmosphere.Have as a result, because of melting mixing
In polyamide (A) and the oxidative degradation of organic principles such as various surface treating agents caused by discoloration be inhibited, melt simultaneously
The effect that the discoloration being kneaded in later process is also inhibited.
It is processed into method of various shapes as by resin combination, can enumerate and squeeze out molten mixture simultaneously in harness shape
The method of made into particulate form, the method that molten mixture is subjected to thermal cutting, imderwater cutting and made into particulate form, in the form of sheets
The method for squeezing out and cutting, in it is blocky squeeze out and crush and method that powder shape is made.
Formed body of the invention is to be molded with Amilan polyamide resin composition of the invention.
As the forming method of Amilan polyamide resin composition of the invention, such as injection moulding, extrusion molding can be enumerated
Method, blow molding method, sinter molding method, from mechanical property, the improvement effect of mouldability it is big from the aspect of, be preferably injection moulded
Method.
It as injection (mo(u)lding) machine, is not particularly limited, such as coaxial reciprocating screw type injection (mo(u)lding) machine or plunger can be enumerated
Formula injection (mo(u)lding) machine.The Amilan polyamide resin composition that melting is heated in the barrel of injection (mo(u)lding) machine is measured by per injection,
It is injected into mold with molten condition, after, solidification cooling with defined shape, is taken out as formed body from mold.Injection moulding
When resin temperature be preferably the fusing point (Tm) of polyamide (A) more than and less than (Tm+50 DEG C).
When Amilan polyamide resin composition is formed, it is also preferred that the entirety until the raw material supply unit to heating part of board
The non-active gas such as enclosed nitrogen, carbon dioxide, argon, form under non-active gas atmosphere.Thus, it is possible to inhibit because in molding
Discoloration caused by the oxidative degradation of organic principles such as polyamide (A) and various surface treating agents, while after molding procedure
Also discoloration is able to suppress in process.
It should be noted that in the heating melting of Amilan polyamide resin composition, used Amilan polyamide resin composition particle
It is preferable to use particles fully dried.If the amount of moisture contained is more, resin is sent out in the barrel of injection (mo(u)lding) machine sometimes
Bubble, it is difficult to obtain optimal formed body.The moisture rate of Amilan polyamide resin composition particle used in injection moulding is relative to poly-
100 mass parts of amide resin composition are preferably smaller than 0.3 mass parts, more preferably less than 0.1 mass parts.
For Amilan polyamide resin composition of the invention other than mechanical property, heat resistance, anti-flammability, resistance to thermochromism is also excellent
It is different, therefore its formed body can be used in the extensive purposes such as automobile component, electrical and electronic parts, groceries, civil construction articles.
Wherein, Amilan polyamide resin composition of the invention due to anti-flammability it is especially excellent, electrical and electronic parts can be suitable for.
As electrical and electronic parts, such as connector, LED reflection device, switch, sensor, socket, capacitor, jack, guarantor can be enumerated
Dangerous silk seat, relay, coil spool, breaker, electromagnetic switch, electrode holder, plug.In addition, can also be suitable for portable
The OA equipment such as personal computer is housing parts, resistor, the shell of IC, LED of electrical equipment etc. of representative.
Embodiment
Hereinafter, specifically describing the present invention by embodiment, but the present invention is not limited to these embodiments.
1. measuring method
The physical property measurement of Amilan polyamide resin composition is carried out by the following method.
(1) fusing point
It, will be 20 DEG C/min with heating rate using differential scanning calorimetry (DSC) (the DSC-7 type of PerkinElmer corporation)
It after being warming up to 350 DEG C, is kept for 5 minutes at 350 DEG C, is cooled to 25 DEG C with 20 DEG C/min of cooling rate, further kept at 25 DEG C
After five minutes, the summit of endothermic peak when using 20 DEG C/min of heating rate carrying out heating measurement again is as fusing point (Tm).
(2) melt flow rate (MFR) (MFR)
According to JIS K7210, it is measured under 340 DEG C, the load of 1.2kg using Amilan polyamide resin composition particle.
MFR can be used as the index of molding mobility, and the value of MFR is higher, indicate that mobility is higher.
(3) mechanical property
Using injection (mo(u)lding) machine (the S2000i-100B type of FANUC corporation) in barrel temperature (+25 DEG C of fusing point), mold
Amilan polyamide resin composition is injection moulded under conditions of temperature (- 185 DEG C of fusing point), is made test film (dumbbell shaped piece).
Using obtained test film, bending strength, bending elastic modulus are measured according to ISO178.
Bending strength, the numerical value of bending elastic modulus are bigger, indicate that mechanical property is more excellent.
(4) anti-flammability
Using injection (mo(u)lding) machine (CND15 of Niigata Machine Techno corporation), barrel temperature (fusing point+
25 DEG C), 5 inches (127mm) × 1/2 inch (12.7mm) × 1/32 inch is made under conditions of mold temperature (- 185 DEG C of fusing point)
The test film of (0.79mm).
Using obtained test film, according to (the U.S. Under Writers Laboratories of UL94 shown in table 1
Inc. standard specified in) benchmark evaluated.When being unsatisfactory for any benchmark, it is set as " not V-2 ".
Total residual flame time is shorter, indicates that anti-flammability is more excellent.
[table 1]
| Evaluation | V-0 | V-1 | V-2 |
| 1 residual flame time | 10 seconds or less | 30 seconds or less | 30 seconds or less |
| 5 test films totally 10 total residual flame time | 50 seconds or less | 250 seconds or less | 250 seconds or less |
| Whether there is or not because of the cotton kindling caused by dripping | Nothing | Nothing | Have |
| Sample is burnt | Nothing | Nothing | Nothing |
(5) yellow chromaticity (yellow colour index, YI), yellow chromaticity changing value (Δ YI)
It will be carried out at moisture absorption in 168 hours by the test film that method identical with above-mentioned (4) obtains with 85 DEG C × 85%RH
After reason, in the reflow ovens of infrared heating type, is heated 1 minute at 150 DEG C, is warming up to 265 DEG C with 100 DEG C/min of speed,
Protection 10 seconds.
By the yellow chromaticity (YI of the formed body after heat treatment1) and heat treatment before formed body yellow chromaticity (YI0) utilize light splitting
Colour difference meter (SE6000 of Japan's electricity color corporation) finds out the value of illuminant-C, tristimulus values XYZ in 2 degree of visuals field, according to JIS
K7313 is calculated by following formula.
YI=100 (1.2769X-1.0592Z)/Y
In addition, calculating yellow chromaticity changing value (Δ YI) by following formula.
Δ YI=YI1- YI0
(6) resistance to reflow
To the test film observation after reflow treatment obtained in above-mentioned (5) whether there is or not blistering (bubble), melting etc. is generated, pass through
Benchmark below is evaluated.
Zero: not generating blistering and the melting of test film.
△: blistering is generated, but its area is the area of test film 50% hereinafter, test film does not melt.
×: generate the blistering or test film melting of the area of the benchmark 50% more than test film.
2. raw material
Raw material used in embodiment described below and comparative example.
(1) polyamide (A)
Polyamide (A-1)
By as dicarboxylic acid component powdered terephthalic acid (TPA) (TPA) 4.70kg, as the tristearin of monocarboxylic acid ingredient
Acid (STA) 0.32kg and sodium hypophosphite monohydrate 9.3g as polymerization catalyst are put into the hybrid-type reaction unit of ribbon,
In the case where nitrogen is closed, 170 DEG C are heated to while with revolving speed 30rpm stirring.Thereafter, 170 DEG C are being kept the temperature at and will turned
Speed is maintained in the state of 30rpm, uses priming device will be as 1, the 10- decamethylene diamine for being heated to 100 DEG C of diamine component
(DDA) 4.98kg obtains reaction product with addition in 2.5 hours continuous (continuous fluid injection mode).It should be noted that starting monomer
Molar ratio be that (the equivalent ratio of the functional group of starting monomer is TPA:DDA:STA to TPA:DDA:STA=48.5:49.6:1.9
=49.0:50.0:1.0).
Next, by obtained reaction product with identical reaction unit under nitrogen flowing with 250 DEG C, revolving speed 30rpm
It heats 8 hours and polymerize, make the powder of polyamide.
Thereafter, harness shape is made in the powder of obtained polyamide using twin shaft kneading machine, harness is carried out by sink
It is obtained polyamide (A-1) particle with pelletizer cutting by cooling and solidifying.
Polyamide (A-2)~(A-4)
Resin composition is changed as shown in table 2, in addition to this, gets similarly polyamide with polyamide (A-1)
(A-2)~(A-4).
Above-mentioned polyamide (A-1)~(A-4) resin composition and characteristic value are shown in table 2.
[table 2]
TPA: terephthalic acid (TPA), AA: adipic acid
DDA:1,10- decamethylene diamine, NDA:1,9- nonamethylene diamine, HDA:1,6- hexamethylene diamine, BDA:1,4- butanediamine
STA: stearic acid
(2) phosphorus flame retardant (B)
B-1: phosphinates (the Exolit OP1230 of Clariant corporation)
B-2: hexaphenoxycyclotriphosphazene (the Rabitle FP-100 that volt is shown in pharmacy institute corporation)
(3) fibee reinforced material (C)
C-1: glass fibre (03JAFT692 of Asahi Fiber Glass corporation), 10 μm of avarage fiber diameter,
Average fiber length 3mm
(4) flame retardant (D)
D-1: melamine polyphosphate (Melapur 200/70 of BASF AG)
D-2: zinc borate 4ZnOB2O3·H2O (Firebrake415 of Borax corporation)
(5) phosphorous antioxidant (E)
- two phosphinate of E-1: four (2,4- di-t-butyl phenyl) 4,4 '-biphenylenes be (Clariant corporation
HOSTANOX P-EPQ)
(6) talcum (F)
F-1: talcum (MSZ-C of Japanese talcum corporation, is surface-treated product by 11 μm of average grain diameter)
Embodiment 1
By 100 mass parts of polyamide (A-1), 3 mass parts of melamine polyphosphate (D-1), 3 mass parts of zinc borate (D-2),
The progress of 0.4 mass parts of phosphorous antioxidant (E-1) is dry-mixed, uses weightless (Loss-in-weight) formula continuous and quantitative feedway
(the CE-W-1 type of KUBOTA corporation) is measured, to the equidirectional biaxial extruder (Toshiba of screw diameter 26mm, L/C50
The TEM26SS type of Mechanology Inc.) main supply mouth (base portion) supplied, carry out melting mixing.Then, from side feeder 1
Phosphorus flame retardant (B-1) 17.0 mass parts, 30 mass parts of glass fibre (C-1) are supplied, further progress is kneaded, thereafter, into one
It walks from the side feeder 2 for being set to side farther downstream than side feeder 1 and supplies phosphorus flame retardant (B-1) 17.0 mass parts, glass
30 mass parts of fiber (C-1).It should be noted that either side feeder is arranged at than making polyamide in equidirectional biaxial extruder
(A-1) the first kneading portion side farther downstream melted.In addition, being fed from weight feed device, the main supply mouth of extruder and side
Nitrogen is connected in device, and is to maintain in a manner of 1% below by oxygen concentration.It is drawn from die head by Amilan polyamide resin composition in harness shape
It after out, is cooled and solidified by sink, it is cut with pelletizer, obtains the particle of Amilan polyamide resin composition.Extruder
Barrel temperatures set be (- 5 DEG C of fusing point)~(+15 DEG C of fusing point), screw speed 250rpm, spray volume 25kg/h.
Embodiment 2~11, comparative example 1~6
By phosphorus flame retardant (B), the fibee reinforced material at the composition of resin combination, the setting number of side feeder, every 1
The additive amount of material (C) changes as shown in Table 3, 4, in addition to this, carries out operation similarly to Example 1 and obtains polyamide
Resin composition pellet.
Various evaluation tests are carried out using obtained Amilan polyamide resin composition particle.It the results are shown in table 3,4.
[table 3]
[table 4]
The resin combination of embodiment is low yellow chromaticity, heat resistance, mechanical property, excellent in flame retardance, and resistance to thermo-color
Property is also excellent, the low resin combination of the yellow chromaticity changing value after reflow treatment.
The resin combination of embodiment 1,2 is compared with embodiment 3, comparative example 1, and the fusing point of polyamide (A) is high, therefore resistance to time
Fluidity is excellent, will not generate blistering, formed bodies are also kept after reflow process.
Contain the resin combination of embodiment 3 in the embodiment 4 of talcum (F), the generation of blistering is inhibited, and flow back work
Also formed bodies is kept after sequence
The phosphorus flame retardant (B) of the resin combination of embodiment 1 is phosphinates, with embodiment 8 (phosphazene compound) phase
Than excellent in flame retardance.
Since the resin combination of comparative example 2 is free of phosphorus flame retardant (B), poor fire.
Since the resin combination of comparative example 3~6 is opposite with the additive amount of the phosphorus flame retardant (B) of side feeder at every 1
It is more than 20 mass parts in 100 mass parts of polyamide (A) and manufactures, therefore cause the deterioration of polyamide, becomes the high tree of yellow chromaticity
Oil/fat composition, and resistance to thermochromism is poor, and the yellow chromaticity changing value after reflow treatment is big.
Claims (11)
1. a kind of Amilan polyamide resin composition, which is characterized in that 100 mass of polyamide (A) for being 270~350 DEG C containing fusing point
Part and phosphorus flame retardant (B) 10~80 mass parts, yellow chromaticity (YI0) it is 3.0 or less.
2. Amilan polyamide resin composition according to claim 1, which is characterized in that the Huang after reflow treatment at 265 DEG C
Coloration changing value (Δ YI) is 12.0 or less.
3. Amilan polyamide resin composition according to claim 1 or 2, which is characterized in that phosphorus flame retardant (B) is phosphinic acids
Salt and/or diphosphinic acid salt.
4. Amilan polyamide resin composition according to claim 3, which is characterized in that phosphinates is by the following general formula (I)
The compound of expression, diphosphinic acid salt are the compound indicated by the following general formula (II),
In formula, R1、R2、R4And R5Each independently represent the alkyl or phenyl of the carbon atom number 1~16 of linear chain or branched chain, R3Table
Show the alkylidene of carbon atom number 1~10, the arlydene of carbon atom number 6~10, alkyl alkylene or the alkyl of linear chain or branched chain
Arlydene, M indicate that calcium ion, aluminium ion, magnesium ion or zinc ion, m are 1 or 3, and n, a, b are to meet 2 × b=n × a relationship
The integer of formula.
5. Amilan polyamide resin composition according to any one of claims 1 to 4, which is characterized in that further containing fibre
Tie up shape strengthening material (C) 5~140 mass parts.
6. Amilan polyamide resin composition according to any one of claims 1 to 5, which is characterized in that further containing cunning
0.1~20 mass parts of stone (F).
7. a kind of manufacturing method of Amilan polyamide resin composition, which is characterized in that be for any in manufacturing claims 1~6
The method of Amilan polyamide resin composition described in is melting in the melting mixing of polyamide (A) and phosphorus flame retardant (B)
1 or more side feeder is arranged in kneading machine, with the additive amount of the phosphorus flame retardant (B) of side feeder at every 1 relative to polyamides
100 mass parts of amine (A) add phosphorus flame retardant (B) from side feeder for 20 mode below the mass.
8. a kind of manufacturing method of Amilan polyamide resin composition, which is characterized in that be for polyamides described in manufacturing claims 5
The method of polyimide resin composition adds fibee reinforced material (C) in the melting mixing of resin combination several times.
9. the manufacturing method of Amilan polyamide resin composition according to claim 7 or 8, which is characterized in that in melting mixing
It is preceding to polymerize polyamide (A), implement the polymerization under non-active gas atmosphere.
10. the manufacturing method of the Amilan polyamide resin composition according to any one of claim 7~9, which is characterized in that
Implement the melting mixing of polyamide (A) and phosphorus flame retardant (B) under non-active gas atmosphere.
11. a kind of formed body, which is characterized in that be by Amilan polyamide resin composition according to any one of claims 1 to 6 at
Made of type.
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| CN111073269A (en) * | 2019-12-03 | 2020-04-28 | 天津金发新材料有限公司 | Flame-retardant polyamide composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111073269A (en) * | 2019-12-03 | 2020-04-28 | 天津金发新材料有限公司 | Flame-retardant polyamide composition and preparation method thereof |
| CN111073269B (en) * | 2019-12-03 | 2022-06-07 | 天津金发新材料有限公司 | Flame-retardant polyamide composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2018123563A1 (en) | 2019-10-31 |
| TW201835219A (en) | 2018-10-01 |
| WO2018123563A1 (en) | 2018-07-05 |
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