CN107345066A - Amilan polyamide resin composition and the method for improving chemical-resistant - Google Patents
Amilan polyamide resin composition and the method for improving chemical-resistant Download PDFInfo
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- CN107345066A CN107345066A CN201710299793.5A CN201710299793A CN107345066A CN 107345066 A CN107345066 A CN 107345066A CN 201710299793 A CN201710299793 A CN 201710299793A CN 107345066 A CN107345066 A CN 107345066A
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- Prior art keywords
- polyamide
- resin composition
- amilan
- acid
- polyamide resin
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The present invention relates to Amilan polyamide resin composition and the method for improving chemical-resistant.The present invention provides the Amilan polyamide resin composition of good chemical resistance.A kind of Amilan polyamide resin composition, its for containing fusing point be less than 240 DEG C, the polyamide (A) that the ratio between carbon number/nitrogen-atoms numbers (C/N ratios) are more than 7 and fusing point are more than 240 DEG C, the ratio between carbon number/nitrogen-atoms numbers (C/N ratios) are less than the Amilan polyamide resin composition that 7 polyamide (B) is formed, wherein, Amilan polyamide resin composition is in temperature range of the temperature range less than 240 DEG C with least one fusing point and more than 240 DEG C with least one fusing point, and the Crystallization peak temperature of Amilan polyamide resin composition is 1.
Description
Technical field
The present invention relates to the side of the Amilan polyamide resin composition with excellent chemical-resistant and raising chemical-resistant
Method.
Background technology
Polyamide has excellent mechanical property (mechanical strength, rigidity and impact resistance etc.), heat resistance, chemically-resistant
Moral character, therefore it is used for the various industrial fields such as clothes, industry material, automobile, Electrical and Electronic part, other industrial products.
For the raw material for car engine chamber, recently, it is contemplated that in the use of cold district, more highly
Ask suppression as caused by the calcium chloride as antifreezing agent resin deterioration, suppress by base part is cooled down as the long-acting of non-freezing solution
Resin caused by cooling agent (LLC) deteriorates；Deng.When for the part related to car engine chamber, to polyamide
It is required that resistance to calcium chloride as described above and hydrolytic resistance.
For the resistance to calcium chloride and the technology of hydrolytic resistance for improving polyamide, known Long carbon chain was poly- in the past
Acid amides (long chain type polyamide；Methene chain is relative to the high polyamide of the ratio of amido link).
On the other hand, the fusing point of long chain type polyamide is low, therefore, in order to improve heat resistance, discloses itself and polyamide 66
Deng mixture (for example, with reference to patent document 1~3).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Application 60-88066 publications
Patent document 2：Japanese Unexamined Patent Publication 2008-144132 publications
Patent document 3：Japanese Unexamined Patent Application Publication 2013-523930 publications
The content of the invention
Invent problem to be solved
It is an object of the present invention to provide the part for being adapted for use in car engine chamber etc., chemical-resistant it is more excellent
Different Amilan polyamide resin composition, and the method for improving chemical-resistant is provided.
Means for solving the problems
The present inventor has carried out research extensively and profoundly to solve above-mentioned problem, as a result finds, by making containing fusing point
For less than 240 DEG C, the ratio between carbon number/nitrogen-atoms numbers (C/N ratios) be more than 7 polyamide and fusing point be more than 240 DEG C, carbon it is former
The Amilan polyamide resin composition of polyamide of the ratio between the subnumber/nitrogen-atoms numbers (C/N ratios) less than 7 has within the scope of specific temperature
Fusing point, and Crystallization peak temperature is 1, it is possible thereby to the Amilan polyamide resin composition of good chemical resistance is obtained, so as to
Complete the present invention.
That is, it containing fusing point is less than 240 DEG C that Amilan polyamide resin composition of the invention, which is, carbon number/nitrogen-atoms numbers it
The polyamide (A) and fusing point for being more than 7 than (C/N ratios) are more than 240 DEG C, the ratio between carbon number/nitrogen-atoms numbers (C/N ratios) are less than
7 polyamide (B) and the Amilan polyamide resin composition formed, the Amilan polyamide resin composition is in the temperature range less than 240 DEG C
Temperature range with least one fusing point and more than 240 DEG C is with least one fusing point, and Crystallization peak temperature is 1.
The list that aliphatic diamine and aliphatic dicarboxylic acid is made up of of the preferred polyamide (A) containing 50 moles of more than %
Member and/or the unit being made up of ω-aliphatic amines carboxylic acid.
Preferred polyamide (A) is selected from by polyamide 410, polyamide 412, polyamide 610, polyamide 612, polyamide
11st, polyamide 12, polyamide 1010, polyamide 1012 and contain they as constituent copolyamide form groups
In more than a kind.
The list that aliphatic diamine and aliphatic dicarboxylic acid is made up of of the preferred polyamide (B) containing 50 moles of more than %
Member.
Preferred polyamide (B) is selected from by polyamide 46, polyamide 56, polyamide 66 and containing them as forming
More than a kind in the group that the copolyamide of composition is formed.
The Crystallization peak temperature of preferred polyamide resin combination is more than polyamide (A) Crystallization peak temperature and is
Below the Crystallization peak temperature of polyamide (B).
Preferably with respect to the mass % of polyamide 100, containing 30 mass %~70 mass % polyamide (A), 30 mass %
~70 mass % polyamide (B).
The method of the raising chemical-resistant of the present invention is poly- by the way that the Amilan polyamide resin composition of the present invention is added to
The method that the chemical-resistant of polyamide is improved in amide resin.
Invention effect
According to the present invention it is possible to provide the Amilan polyamide resin composition of good chemical resistance.
Embodiment
The present invention is specifically described below.
First, each composition that can be used in the present invention is described in detail.
[polyamide]
The Amilan polyamide resin composition of the present invention contains fusing point for less than 240 DEG C, the ratio between carbon number/nitrogen-atoms numbers (C/N
Than) be more than 7 polyamide (A).By the way that containing such polyamide (A), chemical-resistant tends to excellent.Polyamide (A)
The ratio between carbon number/nitrogen-atoms numbers (C/N ratios) be more than 7, preferably more than 8.In addition, the ratio between carbon number/nitrogen-atoms numbers
The upper limit of (C/N ratios) is not particularly limited, preferably less than 15, more preferably less than 12, more preferably less than 10.Pass through
The ratio between carbon number/nitrogen-atoms numbers within the above range, tend to more excellent by chemical-resistant and heat resistance.Need what is illustrated
It is that the ratio between C/N of copolyamide can be by asking using by the average value that the molar ratio of copolymerization ratios calculates as C/N ratios
Go out.
The content of preferred polyamide (A) is 30 relative to the mass % of polyamide 100 contained in Amilan polyamide resin composition
The mass % of quality %~70.The mass % of more preferably 35 mass %~65 mass %, more preferably 40 mass %~60.It is logical
Cross content within the above range, chemical-resistant tends to more excellent.
Fusing point is that the value that (DSC) measure obtains is determined according to JIS K7121, by means of differential scanning calorimetry.Specifically, it is
Fusing peak temperature when being heated with 20 DEG C/min of firing rate.Fusing point can utilize DSC7 (Perkinelmer Inc.'s systems
Make) etc. be measured.Hereinafter, the implication of fusing point, assay method are in this manual the same.
The fusing point of polyamide (A) is less than 240 DEG C, preferably 150 DEG C~240 DEG C, more preferably 180 DEG C~240 DEG C, is entered
One step is preferably 190~230 DEG C.By fusing point within the above range, chemical-resistant and molding processibility, outward appearance are tended to more
It is excellent.
The Amilan polyamide resin composition of the present invention contains fusing point for more than 240 DEG C, the ratio between carbon number/nitrogen-atoms numbers (C/N
Than) it is less than 7 polyamide (B).By containing such polyamide (B), mechanical strength, it is heated when rigid (Hot Time Gang) incline
To in excellent.The ratio between carbon number/nitrogen-atoms numbers of polyamide (B) (C/N ratios) are preferably greater than or equal to 4 and less than 7, more preferably greatly
In equal to 5 and less than 7.It should be noted that the ratio between C/N of copolyamide and polyamide (A) equally can be by will be by altogether
The average value that the molar ratio of poly- ratio calculates is obtained as C/N ratios.
The content of preferred polyamide (B) is 30 relative to the mass % of polyamide 100 contained in Amilan polyamide resin composition
The mass % of quality %~70.The mass % of more preferably 35 mass %~65 mass %, more preferably 40 mass %~60.It is logical
Cross content within the above range, rigidity when heated is tended to more excellent.
The fusing point of polyamide (B) is more than 240 DEG C, preferably 240 DEG C~320 DEG C, more preferably 240 DEG C~300 DEG C, is entered
One step is preferably 250 DEG C~280 DEG C.By fusing point within the above range, mechanical strength and it is heated when rigidity, molding processibility
Tend to more excellent.
Polyamide refers to the high-molecular compound on main chain with-CO-NH- (acid amides) key.Above-mentioned polyamide (A), gather
Acid amides (B) can be：(a) by the ring-opening polymerisation of lactams and the polyamide obtained, the self shrinking that (b) passes through omega-amino carboxylic acid
The polyamide for closing and obtaining, (c) is by the way that diamine and dicarboxylic acids to be condensed to the polyamide to obtain, and their copolymerization
Thing.
Lactams as the raw material of above-mentioned (a) polyamide is not particularly limited, and can enumerate for example：Pyrrolidones, oneself
Lactams, 11 lactams and lauric lactam etc..
In addition, the omega-amino carboxylic acid as the raw material of above-mentioned (b) polyamide is not particularly limited, can enumerate for example：Make
Omega-amino aliphatic acid of the opened loop compound obtained for above-mentioned lactams using water etc..It should be noted that above-mentioned (a) polyamides
Amine and (b) polyamide, which can be respectively to be applied in combination obtained from lactams or omega-amino carboxylic acid of more than two kinds is condensed, to be gathered
Acid amides.
Diamine (monomer) as the raw material of above-mentioned (c) polyamide is not particularly limited, and can enumerate for example：Six methylenes
The straight-chain aliphatic diamine such as base diamines, five methylene diamine；The branched chain types such as 2 methyl pentamethylenediamine, 2- ethyl hexamethylene diamines
Aliphatic diamine；The aromatic diamines such as p-phenylenediamine, m-phenylene diamine (MPD)；The alicyclic rings such as cyclohexanediamine, ring pentanediamine, ring octamethylenediamine
Formula diamine etc..
On the other hand, the dicarboxylic acids (monomer) as the raw material of above-mentioned (c) polyamide is not particularly limited, and can enumerate
Such as：The aliphatic dicarboxylic acids such as adipic acid, pimelic acid, decanedioic acid；The aromatic dicarboxylic carboxylic such as phthalic acid, M-phthalic acid
Acid；Ester ring type dicarboxylic acids such as cyclohexane cyclohexanedimethanodibasic etc..
Above-mentioned (c) polyamide can be that each independent one kind or two or more be applied in combination is gone forward side by side by diamine and dicarboxylic acids
Polyamide obtained from row condensation.
The list that aliphatic diamine and aliphatic dicarboxylic acid is made up of of the preferred polyamide (A) containing 50 moles of more than %
Member and/or the unit being made up of ω-aliphatic amines carboxylic acid.More preferably 60 moles of more than %, more preferably 80 rub
You are more than %, most preferably particularly preferably 90 moles of more than %, 100 moles of %.By being made up of these aliphatic compounds
Unit within the above range, toughness and molding processibility tend to more excellent.
For polyamide (A), it is not particularly limited, can enumerates for example：Selected from by (the poly- decanedioyl of polyamide 410
Butanediamine), polyamide 412 (the poly- acyl butanediamine of dodecane two), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 it is (poly-
Hexamethylene dodecanoamide), polyamide 11 (poly- 11 lactams), polyamide 12 (nylon 12), polyamide 1010 it is (poly-
Decanedioyl decamethylene diamine), polyamide 1012 (the poly- acyl decamethylene diamine of dodecane two) and contain them and gather as the copolymerization of constituent
More than a kind in the group that acid amides is formed.Wherein, it is preferably selected from by polyamide 410, polyamide 412, polyamide 610, polyamide
612 and contain they as constituent copolyamide form group in more than a kind, be more preferably selected from by polyamides
More than a kind in the group that amine 410, polyamide 412, polyamide 610, polyamide 612 are formed.By in their group
More than a kind, chemical-resistant and molding processibility, outward appearance are tended to more excellent.
The list that aliphatic diamine and aliphatic dicarboxylic acid is made up of of the preferred polyamide (B) containing 50 moles of more than %
Member.More preferably 60 moles of more than %, more preferably 80 moles of more than %, particularly preferably 90 moles of more than %, it is optimal
Elect 100 moles of % as.By the unit that is made up of these aliphatic compounds within the above range, toughness and molding processibility incline
To in more excellent.
For polyamide (B), it is not particularly limited, can enumerates for example：Selected from by (poly- α-the pyrrolidines of polyamide 4
Ketone), it is polyamide 6 (polycaprolactam), polyamide 46 (nylon 46), polyamide 56 (poly hexamethylene adipamide pentanediamine), poly-
Acid amides 66 (polyhexamethylene adipamide) and contain they as constituent copolyamide form group in a kind with
On.Wherein, it is preferably selected from by polyamide 46, polyamide 56, polyamide 66 and contains them and gather as the copolymerization of constituent
More than a kind in the group that acid amides is formed, a kind be more preferably selected from the group that is made up of polyamide 46, polyamide 56, polyamide 66
More than.By for more than a kind in their group, mechanical strength and it is heated when rigidity, molding processibility tends to more
It is excellent.
It can also contain in the Amilan polyamide resin composition of the present invention poly- in addition to above-mentioned polyamide (A), polyamide (B)
Acid amides, the polyamide in addition to polyamide (A), polyamide (B) are not particularly limited, can enumerated for example：(poly- couple of polyamide 6 T
Hexamethylene terephthalamide), polyamide 9T (poly-paraphenylene terephthalamide's nonamethylene diamine) and polyamide 6 I (poly-6I hexamethylene isoterephalamide), with
And contain their copolyamides as constituent etc..
The end group of the polyamide used in the present invention is not particularly limited, and amino or carboxyl generally be present.It is preferred that this hair
Aminoterminal base unit weight in the bright middle polyamide used is relative to the ratio between the total amount of aminoterminal base unit weight and c-terminus base unit weight [amino end group
Amount/(aminoterminal base unit weight+c-terminus base unit weight)] it is more than or equal to 0.3 and less than 1.0, more preferably more than 0.3 and less than 0.8, enter
One step is preferably more than 0.3 and less than 0.6.By the ratio between end group amount within the above range, obtained by Amilan polyamide resin composition
Formed body tone, mechanical strength and vibration resistance fatigue properties tend to it is more excellent.
The aminoterminal base unit weight of polyamide is preferably 10 micromoles/g~100 micromoles/g, and more preferably 15 micromoles/g~
80 micromoles/g, more preferably 30 micromoles/g~80 micromoles/g.By aminoterminal base unit weight within the above range, polyamides
The mechanical strength of polyimide resin composition is tended to more excellent.
Here, as aminoterminal base unit weight and the example of the assay method of c-terminus base unit weight in this specification, can enumerate1H-NMR methods and titration.1In H-NMR methods, it can be obtained according to the integrated value of characteristic signal corresponding with each end group.Dripping
Determine in method, for amino end group, the method that can enumerate the phenol solution using 0.1N HCI polyamides is right
For carboxyl end groups, it can enumerate and utilize method of benzyl alcohol solution of 0.1N sodium hydroxide titration polyamides etc..
In addition, the adjusting method of the concentration of the end group of the polyamide used in the present invention can use known method.Make
For adjusting method, it is not particularly limited, can enumerates for example using the method for terminal regulator., can be with as concrete example
The addition in the polymerization of polyamide is enumerated to be selected from by mono-amine compound, diamine compound, monocarboxylic acid compound and binary
More than a kind of terminal regulator in the group that carboxylic acid compound is formed is to reach the method for defined ends concentration.For to molten
The opportunity of terminal regulator is added in agent, is then not particularly limited as the original function of terminal regulator as long as can play,
For example, can be when the raw material of above-mentioned polyamide is added into solvent.
Above-mentioned mono-amine compound is not particularly limited, and can enumerate for example：It is methylamine, ethamine, propylamine, butylamine, hexylamine, pungent
The aliphatic monos such as amine, decyl amine, stearylamine, dimethylamine, diethylamine, di-n-propylamine and dibutyl amine；Cyclohexylamine and dicyclohexyl amine etc.
Ester ring type monoamine；The aromatic monoamines such as aniline, toluidines, diphenylamines and naphthylamines, and their any mixture etc..Its
In, consider from viewpoints such as reactivity, boiling point, the stability of closed end and prices, preferably butylamine, hexylamine, octylame, decyl amine, hard
Fat amine, cyclohexylamine and aniline.They can be used singly or in combination of two or more.
Above-mentioned diamine compound is not particularly limited, and can enumerate for example：Hexamethylene diamine, five methylene diamine etc.
Straight-chain aliphatic diamine；The branched chain type aliphatic diamines such as 2 methyl pentamethylenediamine, 2- ethyl hexamethylene diamines；To benzene two
The aromatic diamines such as amine, m-phenylene diamine (MPD)；Ester ring type diamines such as cyclohexanediamine, ring pentanediamine, ring octamethylenediamine etc..They can be with
1 kind is used alone, two or more can also be applied in combination.
Above-mentioned monocarboxylic acid compound is not particularly limited, and can enumerate for example：Acetic acid, propionic acid, butyric acid, valeric acid, caproic acid,
The aliphatic unitary such as octanoic acid, laurate, tridecanoic acid, tetradecylic acid, hexadecylic acid, stearic acid, pivalic acid (ピ バ リ ソ acid) and isobutyric acid
Carboxylic acid；The ester ring type monocarboxylic acid such as naphthenic acid；Benzoic acid, methyl benzoic acid, α-naphthoicacid, β-naphthoic acid, methyl naphthalene first
Aromatic series monocarboxylic acid such as acid and phenylacetic acid etc..In the present invention, these carboxylic acid compounds can be used alone, can also
Two or more is applied in combination.
Above-mentioned dicarboxylic acid compound is not particularly limited, and can enumerate for example：By malonic acid, dimethyl malonic acid, amber
Amber acid, glutaric acid, adipic acid, 2- methyl adipic acid, trimethyladipic acid, pimelic acid, 2,2- dimethylated pentanedioic acids, 3,3- diethyls
The aliphatic dicarboxylic acids such as base butanedioic acid, azelaic acid, decanedioic acid and suberic acid；1,3- pentamethylene dioctyl phthalate and Isosorbide-5-Nitrae-hexamethylene two
The ester ring type dicarboxylic acids such as formic acid；M-phthalic acid, NDA, 2,7- naphthalenedicarboxylic acids, Isosorbide-5-Nitrae-naphthalenedicarboxylic acid, Isosorbide-5-Nitrae-Asia
Phenyl dioxy diacetic acid, 1,3- phenylene dioxydiacetic acids, diphenic acid, diphenyl-methane -4,4 '-dioctyl phthalate, diphenyl sulphone (DPS) -4,
Unit (unit) derived from the aromatic binary carboxylic acids such as 4 '-dioctyl phthalate and 4,4 '-biphenyl dicarboxylic acid.They can be used alone 1
Kind, two or more can also be applied in combination.
For the polyamide used in the present invention, from mobility when mechanical strength, injection moulding, the viewpoint of outward appearance
Consider, preferably determined according to ISO 307, using the sulfuric acid of 96% (mass fraction) obtained viscosity number (VN) for 100ml/g~
180ml/g.More preferably 110ml/g~150ml/g.
[Amilan polyamide resin composition]
The Amilan polyamide resin composition of the present invention has at least one fusing point and at 240 DEG C in the temperature range less than 240 DEG C
Temperature range above has at least one fusing point, and Crystallization peak temperature is 1.
Crystallization peak temperature is that (DSC) measure is determined according to JIS K7121, by means of differential scanning calorimetry as fusing point
Obtained value, it is Crystallization peak temperature when being cooled down with 20 DEG C/min of cooling velocity specifically.
For the fusing point of Amilan polyamide resin composition, the temperature range preferably at 150 DEG C~238 DEG C has at least 1
Individual and have at least one in 240 DEG C~320 DEG C of temperature range, the more preferably temperature range at 180 DEG C~235 DEG C has extremely
Lack 1 and there is at least one in 240 DEG C~300 DEG C of temperature range, further preferably in 180 DEG C~235 DEG C of temperature model
Enclose with least one and in 240 DEG C~280 DEG C of temperature range with least one, particularly preferably at 190 DEG C~230 DEG C
Temperature range is with least one and in 240 DEG C~280 DEG C of temperature range with least one.Distinguished by least two fusing point
Within the above range, mechanical strength and it is heated when rigidity, chemical-resistant, molding processibility tend to it is more excellent.
The Crystallization peak temperature of Amilan polyamide resin composition is not particularly limited, preferably 150 DEG C~240 DEG C, more preferably
For 160 DEG C~220 DEG C, more preferably 170 DEG C~200 DEG C.By Crystallization peak temperature within the above range, chemicals-resistant
Property and molding processibility tend to more excellent.In addition, by having 1 Crystallization peak temperature, chemicals-resistant within the above range
Property and hydrolytic resistance are tended to more excellent.
Additionally, it is preferred that the Crystallization peak temperature of Amilan polyamide resin composition for polyamide (A) Crystallization peak temperature more than,
And for polyamide (B) Crystallization peak temperature below because thus chemical-resistant and molding processibility tend to it is more excellent
It is different.
[manufacture method of Amilan polyamide resin composition]
For the manufacture method of Amilan polyamide resin composition, it can use and be existed using single screw rod or multi-screw extruder
The method for making to be mediated in the state of molten polyamide., can be by adjusting processing temperature in the case of using extruder
Or holdup time or the Amilan polyamide resin composition that the present invention is manufactured using phosphorous acid esters or phosphorous acid metallic salt.
For example, by the way that processing temperature is set as into 290 DEG C~350 DEG C, mean residence time is adjusted to 2 minutes~10 minutes and manufactured
Polyamide (A) and polyamide (B), it is intended to obtain that there is at least one fusing point and peak crystallization respectively in the range of set point of temperature
It is worth the Amilan polyamide resin composition that temperature is 1.For the Amilan polyamide resin composition of the present invention, processing temperature gets over Gao Yue
It is readily obtained, in addition, mean residence time is more long more is readily obtained.On the other hand, by using phosphorous acid esters or phosphorous acid
Metallic salt, even if mean residence time is short, the Amilan polyamide resin composition of the present invention is also readily obtained, for example, even if average
Holdup time is less than 2 minutes, can also obtain the Amilan polyamide resin composition of the present invention.
Phosphorous acid esters can be enumerated for example：Phosphorous acetoacetic ester, diethyl phosphite, phosphorous acid dipropyl, phosphorous acid two
Butyl ester, diphenyl phosphite, Trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, phosphorous acid
Three monooctyl esters, the butoxyethyl of phosphorous acid three, phosphorous acid three (2- ethylhexyls) ester, triphenyl phosphite, diphenyl phosphite first
Phenyl ester, tricresyl phosphite, phosphorous acid Biphenyl Ester, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, phosphorous acid three (1,5- bis-
Tert-butyl-phenyl) ester, phosphorous acid three (3,5-dimethylphenyl) ester, phosphorous acid three (isopropyl phenyl) ester, phosphorous acid monooctyl ester diphenyl ester,
Or their mixture.
Phosphorous acid metallic salt can be enumerated for example：Phosphorous acid, the 1 of hypophosphorous acid and the periodic table of elements, 2,3,4,5,6,7,
8th, the metal salt of 11,12,13 race's elements and tin, lead etc..It should be noted that these phosphorous acid metallic salts can individually make
With two or more can also be applied in combination.
The content of these phosphorous acid esters or phosphorous acid metallic salt is gathered relative to contained in Amilan polyamide resin composition
The mass parts of acid amides 100, are preferably set to the mass parts of 0.05 mass parts~10, the mass parts of more preferably 0.1 mass parts~5, enter one
Step is preferably the mass parts of 0.1 mass parts~2.5.
[purposes of Amilan polyamide resin composition]
The Amilan polyamide resin composition of the present invention can be used directly, but preferably for example by polyamide and glass fibers
The compound tenses such as the inorganic filling materials such as dimension are added and used, because it is hereby achieved that chemical-resistant, machinery are strong
The Amilan polyamide resin composition of excellent rigidity when spending, be heated.The polyamide combination of the present invention is added to polyamide resin
Ratio during fat is preferably the mass % of 5 mass %~95 relative to the mass % of polyamide 100, and more preferably 10 mass %~
The mass % of 90 mass %, more preferably 10 mass %~60.
It is exemplified below the example of supplementary element.
The inorganic filling materials such as glass fibre, antioxidant, ultra-violet absorber, heat stabilizer, light deterioration can be added
Inhibitor (light deterioration prevents drug), plasticizer, lubricant, releasing agent, nucleator, fire retardant, colouring agent etc., can also be blended it
Its thermoplastic resin.
For lubricant, it is not particularly limited, can enumerates for example：Fatty acid metal salts, fatty acid ester, aliphatic acid
Acid amides, Tissuemat E etc..From the viewpoint of excellent outward appearance and molding processibility, wherein, be preferably selected from fatty acid metal salts,
More than a kind in fatty acid ester, fatty acid amide, two or more is more preferably applied in combination, further preferably by fatty acid metal salts
It is applied in combination with fatty acid ester.
For colouring agent, it is not particularly limited, can enumerates for example：Carbon black, titanium oxide, azines etc..
The composition obtained in this way can by existing known various methods, be for example injection moulded to be molded
For the formed body of various parts.
These various parts can for example be suitably employed in automobile, mechanical industry, electrically and electronics, industry material, daily
And household supplies.
Hereinafter, embodiment is enumerated to specifically describe the present invention, but the invention is not restricted to these embodiments.
Embodiment
Hereinafter, the present invention is illustrated by embodiment and comparative example in further detail, but the invention is not restricted to the implementation
Content shown in example.
(used raw material)
(1) polyamide
(1-1) polyamide 610 (hereafter abbreviated with PA-1)
Fusing point：220 DEG C, Crystallization peak temperature：180℃
VN (sulfuric acid)：115ml/kg, amino end group：40 mMs/kg,
Carboxylic end group：60 mMs/kg
(1-2) polyamide 66 (hereafter abbreviated with PA-2)
Fusing point：260 DEG C, Crystallization peak temperature：215℃
VN (sulfuric acid)：145ml/kg, amino end group：50 mMs/kg,
Carboxylic end group：80 mMs/kg
(2) glass fibre
The glass fibre that 10 μm of avarage fiber diameter (hereafter abbreviated with GF)
(3) heat stabilizer
Cuprous iodide (and Wako Pure Chemical Industries company manufacture, hereafter abbreviated with CuI) and KI (and Wako Pure Chemical Industries company
Manufacture, hereafter abbreviated with KI) mass ratio 1: 5 mixture (hereafter abbreviated with HS)
(4) lubricant
(4-1) montanic acid calcium (hereafter abbreviated with WAX-1)
(4-2) montanate (hereafter abbreviated with WAX-2)
(evaluation method)
Evaluation method described below.
<Chemical-resistant (formic acid dissolubility)>
Use injection (mo(u)lding) machine [PS-40E：Jing resins Co., Ltd. manufactures], injection+dwell time is set as 10
Second, cool time be set as 15 seconds, mold temperature set be 80 DEG C, molten resin temperature be set as 290 DEG C, will in embodiment and
The Amilan polyamide resin composition grain forming obtained in comparative example is 125mm × 12.5mm × 3mm strip matrix band.By gained
To matrix band impregnated 30 minutes in 90% formic acid, then judge whether surface bleaches.
<Chemical-resistant (resistance to calcium chloride)>
Use injection (mo(u)lding) machine [PS-40E：Jing resins Co., Ltd. manufactures], injection+dwell time is set as 10
Second, cool time be set as 15 seconds, mold temperature set be 80 DEG C, molten resin temperature be set as 290 DEG C, will in Production Example and
Compare the plate matrix band that the Amilan polyamide resin composition grain forming obtained in Production Example is 130mm × 130mm × 3mm.
Then, from the center of flat board along flowing right angle orientation (relative to the axle Cheng Zhi of the cast gate from products formed to flow end direction
The direction at angle) strip for being 130mm × 10mm × 3mm is cut, so as to obtain test film.Make resulting test film at 80 DEG C
Water in absorb water 100 hours.Then, 1) by gauze on test film, 2) penetrate into 40 mass % calcium chloride water
Gauze, 3) apply cantilever bending stress 20MPa load, place 1 hour, 4) exposure 2 hours in 100 DEG C of baking oven, 5) remove
Gauze is removed, at room temperature cooling 1 hour, 6) visually confirm there is flawless.Repeat this 1)~6) circulation until that can test
Piece surface observation untill crackle, evaluated by period during by being initially observed crackle.
[embodiment 1]
Use L/D (the barrel diameter of length/extruder of the barrel of extruder)=48 (barrel number：12) twin-screw squeezes
Go out machine [ZSK-26MC：Ke Beilong companies manufacture (Germany)], 300 DEG C will be set as from upstream side supply mouth to die head, in screw rod
Rotating speed 150rpm, under conditions of discharge rate 10kg/ hours, with the PA-1 of 50 mass parts, the PA-2 of 50 mass parts ratio from upper
The supply of side supply mouth and melt kneading are swum, Amilan polyamide resin composition (a-1) has been obtained within 3 minutes with mean residence time.Gained
The Amilan polyamide resin composition (a-1) arrived has 221 DEG C, 258 DEG C of 2 fusing points, and Crystallization peak temperature is 187 DEG C.Carry out
Chemical-resistant is tested, and is as a result not observed and is bleached, surface is not corroded by formic acid.
[embodiment 2]
Use L/D (the barrel diameter of length/extruder of the barrel of extruder)=48 (barrel number：12) twin-screw squeezes
Go out machine [ZSK-26MC：Ke Beilong companies manufacture (Germany)], 300 DEG C will be set as from upstream side supply mouth to die head, in screw rod
Rotating speed 300rpm, under conditions of discharge rate 25kg/ hours, with the PA-1 of 50 mass parts, the PA-2 of 50 mass parts, 0.2 mass parts
Phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, 0.2 mass parts calcium hypophosphite ratio from upstream side supply mouth supply simultaneously
Melt kneading, Amilan polyamide resin composition (a-2) is obtained within 1 minute with mean residence time.Resulting polyamide group
Compound (a-2) has 221 DEG C, 258 DEG C of 2 fusing points, and Crystallization peak temperature is 185 DEG C.Chemical-resistant experiment has been carried out, has been tied
Fruit, which is not observed, to bleach.
[comparative example 1]
Use L/D (the barrel diameter of length/extruder of the barrel of extruder)=48 (barrel number：12) twin-screw squeezes
Go out machine [ZSK-26MC：Ke Beilong companies manufacture (Germany)], 280 DEG C will be set as from upstream side supply mouth to die head, in screw rod
Rotating speed 300rpm, under conditions of discharge rate 25kg/ hours, with the PA-1 of 50 mass parts, the PA-2 of 50 mass parts ratio from upper
The supply of side supply mouth and melt kneading are swum, Amilan polyamide resin composition (a-3) has been obtained within 1 minute with mean residence time.Gained
The Amilan polyamide resin composition (a-3) arrived has 220 DEG C, 260 DEG C of 2 fusing points, has 215 DEG C, 181 DEG C of 2 peak crystallizations
It is worth temperature.Chemical-resistant experiment has been carried out, has as a result observed and bleaches, surface is corroded by formic acid.
[comparative example 2]
Using internal capacity 5.4L autoclave [manufacture of Dong high pressures company], with the PA-1 of 50 mass parts, 50 mass parts
PA-2 ratio heated 1 hour at 300 DEG C under nitrogen atmosphere, obtained Amilan polyamide resin composition (a-4).Resulting
Amilan polyamide resin composition (a-4) has 194 DEG C of 1 fusing point, has 133 DEG C of 1 Crystallization peak temperature.Carry out resistance toization
Moral character experiment is learned, as a result observes and bleaches.
The composition of embodiment and the Amilan polyamide resin composition of comparative example, manufacturing condition, fusing point etc. are shown in Table 1.Such as
Shown in table 1, the good chemical resistance of Amilan polyamide resin composition of the invention.
Table 1
[Production Example 1~4, comparing Production Example 1~5]
Using from extruder upstream side on the 1st barrel with upstream side supply mouth, on the 9th barrel with
Swim side supply mouth, the L/D (barrels of length/extruder of the barrel of extruder with vacuum volatilization mouth on the 11st barrel
Diameter)=48 (barrel number：12) double screw extruder [ZSK-26MC：Ke Beilong companies manufacture (Germany)], will be from upstream side
Supply mouth is set as 290 DEG C to die head, under conditions of screw speed 300rpm, discharge rate 25kg/ hours, is remembered with obtaining table 2
The mode of the ratio of load, from upstream side supply mouth supply polyamide, the polyamide combination of embodiment 1 or 2, comparative example 1 or 2
Thing, heat stabilizer, lubricant, fiberglas chopped strand is supplied from downstream supply mouth, is depressurized, entered from vacuum volatilization mouth
Row melt kneading, so as to make resin composition pellet.By resulting resin combination in 290 DEG C of resin temperature, mould
It is molded at 80 DEG C of temperature, and have rated chemical-resistant.Physics value and composition are recorded in table 2 in the lump.
As shown in table 2, the polyamide combination of the Production Example 1~4 of the Amilan polyamide resin composition of the present invention has been used
The chemical-resistant of thing is tremendously excellent.Therefore, even if Amilan polyamide resin composition of the invention is added to other polyamide
The chemical-resistant of polyamide can also be improved in resin.
Industrial applicability
The Amilan polyamide resin composition of the present invention has excellent chemical-resistant, therefore, can be suitably used as automobile
Enging cabin inner part etc. requires the products formed of mechanical strength and chemical-resistant.
Claims (8)
1. a kind of Amilan polyamide resin composition, its be containing
Fusing point is less than 240 DEG C, the ratio between carbon number/nitrogen-atoms numbers (C/N ratios) are more than 7 polyamide (A) and
Fusing point is more than 240 DEG C, the polyamide (B) of the ratio between carbon number/nitrogen-atoms numbers (C/N ratios) less than 7
And the Amilan polyamide resin composition formed, wherein,
The Amilan polyamide resin composition has at least one fusing point and the temperature more than 240 DEG C in the temperature range less than 240 DEG C
Scope has at least one fusing point, and Crystallization peak temperature is 1.
2. Amilan polyamide resin composition as claimed in claim 1, wherein, the polyamide (A) is containing 50 moles of more than %
The unit being made up of aliphatic diamine and aliphatic dicarboxylic acid and/or the unit being made up of ω-aliphatic amines carboxylic acid.
3. Amilan polyamide resin composition as claimed in claim 1 or 2, wherein, the polyamide (A) is selected from by polyamide
410th, polyamide 412, polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 1010, polyamide 1012, with
And contain them as more than a kind in the group of the copolyamide composition of constituent.
4. such as Amilan polyamide resin composition according to any one of claims 1 to 3, wherein, the polyamide (B) is rubbed containing 50
Your more than the % unit being made up of aliphatic diamine and aliphatic dicarboxylic acid.
5. such as Amilan polyamide resin composition according to any one of claims 1 to 4, wherein, the polyamide (B) be selected from by
Polyamide 46, polyamide 56, polyamide 66 and contain they as constituent copolyamide form group in 1
More than kind.
6. such as Amilan polyamide resin composition according to any one of claims 1 to 5, wherein, the Crystallization peak temperature is institute
State more than polyamide (A) Crystallization peak temperature and for the Crystallization peak temperature of the polyamide (B) below.
7. such as Amilan polyamide resin composition according to any one of claims 1 to 6, wherein, relative to the matter of polyamide 100
Measure %, the Amilan polyamide resin composition contains the matter of the mass % of 30 mass %~70 polyamide (A), 30 mass %~70
Measure the % polyamide (B).
8. a kind of method, it by Amilan polyamide resin composition according to any one of claims 1 to 7 by being added to polyamide
The chemical-resistant of the polyamide is improved in resin.
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| CN111087801A (en) * | 2018-10-24 | 2020-05-01 | 上海凯赛生物技术股份有限公司 | Bio-based polyamide 56 material for heat insulation strip, preparation method and heat insulation strip |
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| CN107345066B (en) | 2021-05-14 |
| JP2017200971A (en) | 2017-11-09 |
| JP6712178B2 (en) | 2020-06-17 |
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