CN111978716B - Polyamide composition, method for producing same, and molded article - Google Patents

Polyamide composition, method for producing same, and molded article Download PDF

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CN111978716B
CN111978716B CN202010423271.3A CN202010423271A CN111978716B CN 111978716 B CN111978716 B CN 111978716B CN 202010423271 A CN202010423271 A CN 202010423271A CN 111978716 B CN111978716 B CN 111978716B
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polyamide composition
polyamide
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carbon atoms
mass
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CN111978716A (en
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渡边将史
永濑康一
家田真次
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Asahi Kasei Corp
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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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/329—Phosphorus containing acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • 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
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles

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Abstract

The present invention relates to a polyamide composition, a method for producing the same, and a molded article. The invention provides a polyamide composition which contains halogen-free flame retardant and has excellent flame retardance and long-term heat resistance, and a method for producing the same. A polyamide composition comprising (A) a polyamide, (B) a phosphorus-containing flame retardant and (C) a styrene copolymer, wherein the content of the (C) styrene copolymer is 0.1 mass% or more and 7.0 mass% or less relative to the total mass of the (A) polyamide, the (B) phosphorus-containing flame retardant and the (C) styrene copolymer. The method for producing the polyamide composition is a method for producing the polyamide composition, wherein raw material components comprising the (A) polyamide, the (B) phosphorus-containing flame retardant and the (C) styrene copolymer are melt kneaded.

Description

Polyamide composition, method for producing same, and molded article
Technical Field
The present invention relates to a polyamide composition, a method for producing the same, and a molded article
Background
The aliphatic polyamide-based composition has excellent characteristic properties and is therefore used for manufacturing molded articles in a very large number of applications. In particular, polyamide compositions having flame retardant properties are necessary for the components in the electrical and electronic industry in order to ensure adequate fire resistance.
Polyamides are often flame retardant treated by the addition of halogen compounds. However, recently, various regulations have been made such that products containing halogen compounds are not used in electric and electronic parts according to regulations of harmful substances such as RoHS (restriction of harmful substances) and PoHS (disabling of specific harmful substances in consumer products). Accordingly, various halogen-free flame retardants for polyamides have been developed.
Examples of the halogen-free flame retardant include phosphorus compounds. Patent document 1 discloses the use of calcium and aluminum salts of phosphinic acid or diphosphinic acid as flame retardants for polyamides. Test pieces having a sample thickness of 1.2mm, which were produced from a polyamide composition containing these halogen-free flame retardants and reinforced with 30 mass% of glass fibers relative to the total mass of the composition, reached a flammability classification V-0 based on UL 94.
In order to achieve the flammability classification V-0 of UL94, patent document 2 discloses: in a glass fiber reinforced polyamide composition containing polyamide 6 as a main component, aluminum phosphinate in an amount of much more than 20 mass% is required with respect to the total mass of the composition; in the glass fiber reinforced polyamide composition having polyamide 66 as a main component, more than 30 mass% of aluminum phosphinate is required. It can be seen that in order to achieve the flammability classification V-0 using the phosphinic flame retardant, a large amount of the phosphinic flame retardant must be added, thereby adversely affecting the mechanical properties, which is problematic.
Accordingly, patent document 3 discloses a polyamide composition containing phosphinate as a flame retardant, which is based on a mixture of aliphatic polyamide and semiaromatic polyamide. It is reported that the addition of the semiaromatic polyamide can reduce the amount of the flame retardant used and improve the tensile elongation.
In addition, patent document 4 discloses a polyamide composition using phosphinate as a flame retardant and based on a mixture of polyamide containing aromatic polyamide and polyphenylene sulfide. It is reported that by adding polyphenylene sulfide excellent in flame retardancy to a polyamide containing an aromatic polyamide, the amount of the flame retardant used can be reduced, and the amount of outgas emissions from the flame retardant can be reduced.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 3947261
Patent document 2: japanese patent No. 4698789
Patent document 3: japanese patent No. 4614959
Patent document 4: japanese patent laid-open No. 2009-270107
Patent document 5: japanese patent laid-open publication No. 2005-179362
Patent document 6: european patent application publication No. 699708 specification
Patent document 7: japanese patent laid-open No. 08-073720
Disclosure of Invention
Problems to be solved by the invention
However, the polyamide composition described in patent document 3 has room for improvement in long-term heat resistance and the like required for automobiles and various electric parts, although the tensile elongation at break is improved by reducing the amount of the flame retardant used.
In addition, although the polyamide composition described in patent document 4 has reduced the amount of flame retardant used and reduced outgas by adding polyphenylene sulfide, there is a concern that it is difficult to maintain the flammability classification V-0 based on UL94 when the proportion of aliphatic polyamide relative to aromatic polyamide is increased.
It can be seen that in the prior art, a polyamide composition using a halogen-free flame retardant and having both flame retardancy and long-term heat resistance is not known.
The present invention has been made in view of the above circumstances, and provides a polyamide composition which contains a halogen-free flame retardant and has excellent flame retardancy and long-term heat resistance, a method for producing the same, and a molded article comprising the polyamide composition. In addition, the invention provides a method for adding the styrene copolymer as a flame retardant auxiliary.
Means for solving the problems
That is, the present invention includes the following modes.
The polyamide composition according to the invention according to the 1 st aspect comprises: the flame retardant composition comprises (A) a polyamide, (B) a phosphorus-containing flame retardant, and (C) a styrene copolymer, wherein the content of the (C) styrene copolymer is 0.1 mass% or more and 7.0 mass% or less relative to the total mass of the (A) polyamide, the (B) phosphorus-containing flame retardant, and the (C) styrene copolymer.
The (a) polyamide may contain (A1) an aliphatic polyamide and (A2) a semiaromatic polyamide, the (A2) semiaromatic polyamide containing diamine units and dicarboxylic acid units.
The (A2) semiaromatic polyamide may contain 50 mol% or more of isophthalic acid units in all dicarboxylic acid units constituting the (A2) semiaromatic polyamide.
The (A2) semiaromatic polyamide may contain 75 mol% or more of isophthalic acid units in all dicarboxylic acid units constituting the (A2) semiaromatic polyamide.
The (A2) semiaromatic polyamide may contain 100 mol% of isophthalic acid units among all dicarboxylic acid units constituting the (A2) semiaromatic polyamide.
The (C) styrene copolymer may contain an acrylonitrile unit and a styrene unit.
The (C) styrene copolymer may contain an acrylonitrile unit and a styrene unit, and the content of the acrylonitrile unit may be 30 mass% or more with respect to the total mass of the constituent units of the (C) styrene copolymer.
The phosphorus-containing flame retardant (B) may contain at least one phosphinate selected from the group consisting of phosphinates represented by the following general formula (1), diphosphinates represented by the following general formula (2) and condensates thereof,
Figure BDA0002497751050000041
(in the general formula (1), R 11 And R is 12 Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; m is M n11+ A metal ion of valence n 11; m is an element belonging to group 2 or group 15 of the periodic Table, a transition element, zinc or aluminum; n11 is 2 or 3; in the case where n11 is 2 or 3, a plurality of R's are present 11 And a plurality of R 12 Each of which may be the same or different;
in the general formula (2), R 21 And R is 22 Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; y is Y 21 An alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms; m's' x m21+ A metal ion having a valence of m 21; m' is a compound belonging to group 2 or 1 of the periodic Table of elements Group 5 elements, transition elements, zinc or aluminum; n21 is an integer of 1 to 3 inclusive; in the case where n21 is 2 or 3, a plurality of R's are present 21 A plurality of R 22 And a plurality of Y 21 Each of which may be the same or different; m21 is 2 or 3; x is 1 or 2; in the case where x is 2, a plurality of M's may be the same or different; n21, x, and m21 are integers satisfying the relationship of 2×n21=m21×x).
The content of the phosphorus-containing flame retardant may be 0.1 mass% or more and 30 mass% or less with respect to the total mass of the (a) polyamide, the (B) phosphorus-containing flame retardant and the (C) styrene copolymer.
The polyamide composition may have a tan delta peak temperature of 90 ℃ or higher.
The weight average molecular weight of the polyamide composition may be 10000 or more and 50000 or less.
The polyamide composition according to the above-mentioned item 1 may further contain at least one filler (D).
The molded article according to claim 2 of the present invention is obtained by molding the polyamide composition according to claim 1.
The method for producing a polyamide composition according to claim 3 of the present invention is the method for producing a polyamide composition according to claim 1, wherein raw material components including the (a) polyamide, the (B) phosphorus-containing flame retardant and the (C) styrene copolymer are melt kneaded.
The method according to the 4 th aspect of the present invention is a method of adding a styrene copolymer as a flame retardant aid to a resin composition containing a polyamide and a phosphorus-containing flame retardant.
Effects of the invention
According to the polyamide composition and the method for producing the same, a molded article containing a halogen-free flame retardant and having excellent flame retardancy and long-term heat resistance can be obtained.
Detailed Description
Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following. The present invention can be implemented by appropriately modifying the scope of the gist thereof.
In the present specification, "polyamide" means a polymer having an amide group (-NHCO-) in the main chain.
Polyamide composition
The polyamide composition of the present embodiment contains the following components (a) to (C).
(A) A polyamide;
(B) A phosphorus-containing flame retardant;
(C) A styrene copolymer.
In the polyamide composition of the present embodiment, the content of the component (C) is 0.1 mass% or more and 7 mass% or less relative to the total mass of the components (a) to (C).
The polyamide composition of the present embodiment can provide a molded article containing a halogen-free flame retardant and having excellent flame retardancy and long-term heat resistance by having the above-described constitution.
< Properties of Polyamide composition >
The molecular weight and tan δ peak temperature of the polyamide composition of the present embodiment may be set to the following structures, and specifically, may be measured by the method described in examples below.
[ weight average molecular weight (Mw) of Polyamide composition ]
As an index of the molecular weight of the polyamide composition, a weight average molecular weight (Mw) can be utilized.
The weight average molecular weight (Mw) of the polyamide composition is preferably 10000 or more and 50000 or less, more preferably 17000 or more and 45000 or less, still more preferably 20000 or more and 45000 or less, still more preferably 25000 or more and 45000 or less, particularly preferably 30000 or more and 42000 or less, and most preferably 34000 or more and 38000 or less.
When the weight average molecular weight (Mw) of the polyamide composition is within the above range, a polyamide composition having more excellent mechanical properties, particularly, water absorption rigidity, thermal rigidity, fluidity and the like can be obtained. Further, molded articles obtained from the polyamide composition containing the component represented by the filler (D) are molded articles having more excellent tensile strength and long-term heat resistance.
Examples of the method for controlling the Mw of the polyamide composition within the above range include using (A) a polyamide and (C) a styrene copolymer having a Mw within the below-described range.
The measurement of Mw (weight average molecular weight) may be performed by GPC (gel permeation chromatography) as described in examples described below.
[ tan delta peak temperature of Polyamide composition ]
The lower limit of the tan delta peak temperature of the polyamide composition is preferably 90 ℃, more preferably 105 ℃, and even more preferably 110 ℃.
On the other hand, the upper limit of the tan δ peak temperature of the polyamide composition is preferably 150 ℃, more preferably 140 ℃, and even more preferably 130 ℃.
That is, the tan δ peak temperature of the polyamide composition is preferably 90 ℃ or higher and 150 ℃ or lower, more preferably 105 ℃ or higher and 140 ℃ or lower, and still more preferably 110 ℃ or higher and 130 ℃ or lower.
When the tan delta peak temperature of the polyamide composition is equal to or higher than the lower limit, a polyamide composition having more excellent water absorption rigidity and thermal rigidity tends to be obtained. On the other hand, when the tan δ peak temperature of the polyamide composition is equal to or lower than the above-mentioned upper limit, a molded article obtained from the polyamide composition containing the component represented by the filler (D) tends to be a molded article having more excellent tensile strength and long-term heat resistance.
Examples of the method for controlling the tan delta peak temperature of the polyamide composition within the above range include: and (A2) a semiaromatic polyamide containing diamine units and dicarboxylic acid units, the content of which is controlled within the range described below.
Hereinafter, each constituent component of the polyamide composition of the present embodiment will be described in detail.
(A) Polyamide ]
From the viewpoint of improving flame retardancy, weld strength and laser welding strength, the polyamide (a) contained in the polyamide composition of the present embodiment preferably contains: (A1) Aliphatic polyamide and (A2) semi-aromatic polyamide, said (A2) semi-aromatic polyamide containing diamine units and dicarboxylic acid units.
[ (A1) aliphatic Polyamide ]
(A1) The constituent unit of the aliphatic polyamide preferably satisfies at least any one of the following conditions (1) and (2).
(1) Contains (A1-a) aliphatic dicarboxylic acid units and (A1-b) aliphatic diamine units.
(2) Comprises (A1-c) at least one member selected from the group consisting of lactam units and aminocarboxylic acid units.
The polyamide composition of the present embodiment may contain, as the aliphatic polyamide (A1), one or two or more kinds of polyamides satisfying at least one of the conditions (1) and (2) described above. Among them, the constituent unit of the (A1) aliphatic polyamide contained in the polyamide composition of the present embodiment particularly preferably satisfies the above (1).
((A1-a) aliphatic dicarboxylic acid units)
Examples of the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit (A1-a) include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms.
The linear saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms is not limited to the following, and examples thereof include: malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, icosanedioic acid, diglycolic acid, and the like.
The branched saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms is not limited to the following, and examples thereof include: dimethyl malonic acid, 2-dimethyl succinic acid, 2, 3-dimethyl glutaric acid, 2-diethyl succinic acid, 2, 3-diethyl glutaric acid, 2-dimethyl glutaric acid, 2-methyl adipic acid, trimethyl adipic acid, and the like.
The aliphatic dicarboxylic acids constituting the aliphatic dicarboxylic acid unit (A1-a) may be used alone or in combination of two or more.
Among them, the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit (A1-a) is preferably a linear saturated aliphatic dicarboxylic acid having 6 or more carbon atoms, because of the tendency of the polyamide composition to be more excellent in heat resistance, flowability, toughness, low water absorption, rigidity, and the like.
Specific examples of the linear saturated aliphatic dicarboxylic acid having 6 or more carbon atoms include: adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and the like.
Among them, adipic acid, sebacic acid, or dodecanedioic acid is preferable as the linear saturated aliphatic dicarboxylic acid having 6 or more carbon atoms from the viewpoint of heat resistance of the polyamide composition.
The aliphatic polyamide (A1) may further contain a unit derived from a polycarboxylic acid having a ternary or higher structure as needed within a range that does not impair the effect of the polyamide composition of the present embodiment. Examples of the polycarboxylic acid having three or more members include: trimellitic acid, trimesic acid, pyromellitic acid, and the like. These three or more polycarboxylic acids may be used alone or in combination of two or more.
(A1-b) aliphatic diamine units
Examples of the aliphatic diamine constituting the aliphatic diamine unit (A1-b) include: a linear saturated aliphatic diamine having 2 to 20 carbon atoms, or a branched saturated aliphatic diamine having 3 to 20 carbon atoms.
The linear saturated aliphatic diamine having 2 to 20 carbon atoms is not limited to the following, and examples thereof include: ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, and the like.
The branched saturated aliphatic diamine having 3 to 20 carbon atoms is not limited to the following, and examples thereof include: 2-methylpentamethylenediamine (also referred to as 2-methyl-1, 5-diaminopentane), 2, 4-trimethylhexamethylenediamine, 2, 4-trimethylhexamethylenediamine, 2-methyl-1, 8-octanediamine (also referred to as 2-methylpentamethylenediamine), 2, 4-dimethyloctamethylenediamine, and the like.
The aliphatic diamine constituting the aliphatic diamine unit (A1-b) may be used alone or in combination of two or more.
Among them, the aliphatic diamine constituting the aliphatic diamine unit (A1-b) has preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aliphatic diamine constituting the aliphatic diamine unit (A1-b) has at least the lower limit of the number of carbon atoms, and the molded article obtained is more excellent in heat resistance. On the other hand, when the number of carbon atoms of the aliphatic diamine constituting the aliphatic diamine unit (A1-b) is not more than the upper limit, the molded article obtained is more excellent in crystallinity and releasability.
Specific examples of the linear or branched saturated aliphatic diamine having 6 to 12 carbon atoms may include: hexamethylenediamine, 2-methylpentamethylenediamine, 2-methyl-1, 8-octanediamine, and the like.
Among them, hexamethylenediamine or 2-methylpentamethylenediamine is preferable as a linear or branched saturated aliphatic diamine having 6 to 12 carbon atoms. By containing such (A1-b) aliphatic diamine units, the molded article obtained from the polyamide composition is more excellent in heat resistance, rigidity, and the like.
The aliphatic polyamide (A1) may further contain a unit derived from an aliphatic polyamine of three or more, as needed, within a range that does not impair the effect of the polyamide composition of the present embodiment. Examples of the aliphatic polyamine having three or more members include bis (hexamethylene) triamine.
((A1-c) at least one constituent unit selected from the group consisting of a lactam unit and an aminocarboxylic acid unit)
(A1) The aliphatic polyamide may contain (A1-c) at least one constituent unit selected from the group consisting of a lactam unit and an aminocarboxylic acid unit. By containing such units, polyamide having excellent toughness tends to be obtained.
Here, "lactam unit" and "aminocarboxylic acid unit" refer to a polymerized (condensed) lactam and aminocarboxylic acid.
The lactam constituting the lactam unit is not limited to the following, and examples thereof include: butyrolactam, valerolactam, epsilon-caprolactam, caprylolactam, enantholactam, undecanolactam, laurolactam (laurolactam) and the like.
Among them, epsilon-caprolactam or laurolactam is preferable as the lactam constituting the lactam unit, and epsilon-caprolactam is more preferable. By containing such a lactam, the molded article obtained from the polyamide composition tends to have more excellent toughness.
The aminocarboxylic acid constituting the aminocarboxylic acid unit is not limited to the following, and examples thereof include: omega-aminocarboxylic acids, alpha, omega-amino acids, and the like, which are compounds obtained by ring opening of lactams.
As the aminocarboxylic acid constituting the aminocarboxylic acid unit, a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms in which ω -position is substituted with an amino group is preferable. Examples of such aminocarboxylic acids include, but are not limited to, the following: 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like. In addition, as the aminocarboxylic acid, p-aminomethylbenzoic acid and the like can be mentioned.
The lactam and the aminocarboxylic acid each having at least one constituent unit selected from the group consisting of a lactam unit and an aminocarboxylic acid unit may be used alone or in combination of two or more.
Among them, the aliphatic polyamide (A1) is preferably a polyamide containing a dicarboxylic acid unit and a diamine unit, and more preferably polyamide 66 (PA 66) from the viewpoints of mechanical properties, heat resistance, moldability and toughness. PA66 is considered to be a material suitable for automobile parts because of its excellent mechanical properties, heat resistance, moldability and toughness.
The content of the aliphatic polyamide (A1) may be, for example, 50 mass% or more and 100 mass% or less, for example, 55 mass% or more and 100 mass% or less, and for example, 57 mass% or more and 100 mass% or less, with respect to the total mass of the polyamide in the polyamide composition.
((A1) weight average molecular weight Mw (A1)) of aliphatic polyamide
As an index of the molecular weight of the aliphatic polyamide (A1), a weight average molecular weight Mw (A1) can be used. The weight average molecular weight Mw (A1) of the aliphatic polyamide is preferably 10000 or more and 50000 or less, more preferably 17000 or more and 45000 or less, still more preferably 20000 or more and 45000 or less, still more preferably 25000 or more and 45000 or less, particularly preferably 30000 or more and 45000 or less, and most preferably 35000 or more and 40000 or less.
In the above range of the weight average molecular weight Mw (A1), a polyamide composition having more excellent mechanical properties, particularly, water absorption rigidity, thermal rigidity, fluidity, tensile strength when molded into a molded article, flexural modulus when water is absorbed, long-term heat resistance, tracking resistance, and the like can be obtained.
The weight average molecular weight Mw (A1) may be measured by GPC as described in examples below.
[ (A2) semi-aromatic Polyamide ]
(A2) The semiaromatic polyamide is a polyamide containing diamine units and dicarboxylic acid units.
The (A2) semiaromatic polyamide preferably contains 20 to 80 mol% of an aromatic constituent unit, more preferably 30 to 70 mol% of an aromatic constituent unit, and still more preferably 40 to 60 mol% of an aromatic constituent unit, based on the total constituent units of the (A2) semiaromatic polyamide. The term "aromatic constituent unit" as used herein means an aromatic diamine unit and an aromatic dicarboxylic acid unit.
The (A2) semiaromatic polyamide preferably comprises (A2-a) dicarboxylic acid units and (A2-b) diamine units, wherein the (A2-a) dicarboxylic acid units comprise 50 mol% or more of isophthalic acid units relative to the total dicarboxylic acid units of the (A2) semiaromatic polyamide, and the (A2-b) diamine units comprise diamine units having 4 to 10 carbon atoms.
In this case, the total content of the isophthalic acid unit and the diamine unit having 4 to 10 carbon atoms in the (A2) semiaromatic polyamide is preferably 50 mol% or more, more preferably 80 mol% or more and 100 mol% or less, still more preferably 90 mol% or more and 100 mol% or less, and particularly preferably 100 mol% based on the total constituent units of the (A2) semiaromatic polyamide.
The ratio of the predetermined monomer units constituting the (A2) semiaromatic polyamide may be measured by nuclear magnetic resonance spectroscopy (NMR) or the like.
((A2-a) dicarboxylic acid units)
The dicarboxylic acid unit (A2-a) is not particularly limited, and examples thereof include: aromatic dicarboxylic acid units, aliphatic dicarboxylic acid units, alicyclic dicarboxylic acid units, and the like.
Among them, the dicarboxylic acid unit (A2-a) preferably contains 50 mol% or more of isophthalic acid units, more preferably 65 mol% or more and 100 mol% or less of isophthalic acid units, still more preferably 75 mol% or more and 100 mol% or less of isophthalic acid units, particularly preferably 80 mol% or more and 100 mol% or less of isophthalic acid units, and most preferably 100 mol% or less of isophthalic acid units, based on the total mole number of the dicarboxylic acid units (A2-a).
When the ratio of the isophthalic acid unit in the dicarboxylic acid unit (A2-a) is not less than the lower limit, a polyamide composition which can satisfy mechanical properties, particularly, water absorption rigidity, thermal rigidity, fluidity and the like, tends to be obtained. Further, molded articles obtained from the polyamide composition tend to be more excellent in tensile strength, flexural modulus upon water absorption, long-term heat resistance and tracking resistance.
(1) Aromatic dicarboxylic acid unit
The aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit other than the isophthalic acid unit is not limited to the following, and examples thereof include dicarboxylic acids having an aromatic group such as a phenyl group and a naphthyl group. The aromatic group of the aromatic dicarboxylic acid may be unsubstituted or substituted.
The substituent is not particularly limited, and examples thereof include: an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an alkylaryl group having 7 to 10 carbon atoms, a halogen group, a silyl group having 1 to 6 carbon atoms, a sulfonic acid group, a salt thereof (sodium salt, etc.), and the like.
Examples of the alkyl group having 1 to 4 carbon atoms include, but are not limited to, the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like.
Examples of the aryl group having 6 to 10 carbon atoms include, but are not limited to, the following groups: phenyl, naphthyl, and the like.
Examples of the aralkyl group having 7 to 10 carbon atoms include, but are not limited to, the following groups: benzyl, and the like.
The alkylaryl group having 7 to 10 carbon atoms is not limited to the following groups, and examples thereof include: tolyl, xylyl, and the like.
The halogen group is not limited to the following groups, and examples thereof include: fluoro, chloro, bromo, iodo, and the like.
The silyl group having 1 to 6 carbon atoms is not limited to the following groups, and examples thereof include: trimethylsilyl, t-butyldimethylsilyl, and the like.
Among them, as the aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit other than the isophthalic acid unit, an unsubstituted aromatic dicarboxylic acid having 8 to 20 carbon atoms or an aromatic dicarboxylic acid having 8 to 20 carbon atoms substituted with a predetermined substituent is preferable.
The unsubstituted aromatic dicarboxylic acid having 8 to 20 carbon atoms or the aromatic dicarboxylic acid having 8 to 20 carbon atoms substituted with a predetermined substituent is not particularly limited, and examples thereof include: terephthalic acid, naphthalene dicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methyltetraphthalic acid, isophthalic acid-5-sodium sulfonate, and the like.
The aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit may be used alone or in combination of two or more.
(2) Aliphatic dicarboxylic acid unit
Examples of the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms.
The linear saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms is not limited to the following, and examples thereof include: malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, icosanedioic acid, diglycolic acid, and the like.
The branched saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms is not limited to the following, and examples thereof include: dimethyl malonic acid, 2-dimethyl succinic acid, 2, 3-dimethyl glutaric acid, 2-diethyl succinic acid, 2, 3-diethyl glutaric acid, 2-dimethyl glutaric acid, 2-methyl adipic acid, trimethyl adipic acid, and the like.
(3) Alicyclic dicarboxylic acid unit
The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit (hereinafter, sometimes referred to as "alicyclic dicarboxylic acid unit") is not limited to the following, and examples thereof include: alicyclic dicarboxylic acids having 3 to 10 carbon atoms in the alicyclic structure, and the like. Among them, preferred as the alicyclic dicarboxylic acid is an alicyclic dicarboxylic acid having an alicyclic structure having 5 to 10 carbon atoms.
Examples of such alicyclic dicarboxylic acids include, but are not limited to, the following: 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid, and the like. Among them, 1, 4-cyclohexanedicarboxylic acid is preferable as the alicyclic dicarboxylic acid.
The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit may be used alone or in combination of two or more.
The alicyclic group of the alicyclic dicarboxylic acid may be unsubstituted or substituted. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include the same groups as those exemplified for the "aromatic dicarboxylic acid unit".
The dicarboxylic acid unit other than the isophthalic acid unit preferably contains an aromatic dicarboxylic acid unit, and more preferably contains an aromatic dicarboxylic acid having 6 or more carbon atoms.
By using such dicarboxylic acid, a polyamide composition which can satisfy mechanical properties, particularly water absorption rigidity, thermal rigidity, fluidity, and the like, tends to be obtained. Further, molded articles obtained from the polyamide composition tend to be more excellent in tensile strength, flexural modulus upon water absorption, long-term heat resistance and tracking resistance.
In the (A2) semiaromatic polyamide, the dicarboxylic acid constituting the dicarboxylic acid unit (A2-a) is not limited to the compounds described as the dicarboxylic acid, and may be compounds equivalent to the dicarboxylic acid.
The term "compound equivalent to a dicarboxylic acid" as used herein means a compound which can give a dicarboxylic acid structure identical to that of a dicarboxylic acid derived from the above dicarboxylic acid. Examples of such a compound include, but are not limited to, the following: anhydrides of dicarboxylic acids, acid halides of dicarboxylic acids, and the like.
The semiaromatic polyamide (A2) may further contain a unit derived from a polycarboxylic acid having a ternary or higher structure as needed within a range that does not impair the effects of the polyamide composition of the present embodiment.
Examples of the polycarboxylic acid having three or more members include: trimellitic acid, trimesic acid, pyromellitic acid, and the like. These three or more polycarboxylic acids may be used alone or in combination of two or more.
((A2-b) diamine units)
The diamine unit (A2-b) constituting the (A2) semiaromatic polyamide is not particularly limited, and examples thereof include: aromatic diamine units, aliphatic diamine units, alicyclic diamine units, and the like. Among them, (A2-b) diamine units constituting (A2) semi-aromatic polyamide preferably contain diamine units having 4 to 10 carbon atoms, more preferably contain diamine units having 6 to 10 carbon atoms.
(1) Aliphatic diamine unit
Examples of the aliphatic diamine constituting the aliphatic diamine unit include: and linear saturated aliphatic diamines having 4 to 20 carbon atoms.
The linear saturated aliphatic diamine having 4 to 20 carbon atoms is not limited to the following, and examples thereof include: ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, and the like.
(2) Alicyclic diamine unit
The alicyclic diamine (hereinafter, sometimes referred to as "alicyclic diamine") constituting the alicyclic diamine unit is not limited to the following, and examples thereof include: 1, 4-cyclohexanediamine, 1, 3-cyclopentanediamine, and the like.
(3) Aromatic diamine unit
The aromatic diamine constituting the aromatic diamine unit is not limited to the following as long as it is a diamine containing an aromatic group. Specific examples of the aromatic diamine include m-xylylenediamine and the like.
These diamines constituting each diamine unit may be used alone or in combination of two or more.
Among them, the diamine unit (A2-b) is preferably an aliphatic diamine unit, more preferably a linear saturated aliphatic diamine unit having 4 to 10 carbon atoms, still more preferably a linear saturated aliphatic diamine unit having 6 to 10 carbon atoms, and particularly preferably a hexamethylenediamine unit.
By using such a diamine, a polyamide composition which can satisfy mechanical properties, particularly water absorption rigidity, thermal rigidity, fluidity, and the like, tends to be obtained. Further, molded articles obtained from the polyamide composition tend to be more excellent in tensile strength, flexural modulus upon water absorption, long-term heat resistance and tracking resistance.
The semiaromatic polyamide (A2) is preferably polyamide 6I (poly (m-xylylene terephthalamide)), polyamide 9I or polyamide 10I, more preferably polyamide 6I. Polyamide 6I is considered to be a material suitable for automobile parts because of its excellent heat resistance, molding processability and flame retardancy.
The content of the (A2) semiaromatic polyamide may be set to 0 mass% or more and 50.0 mass% or less, preferably 10.0 mass% or more and 45.0 mass% or less, more preferably 15.0 mass% or more and 43.0 mass% or less, and still more preferably 20.0 mass% or more and 41.0 mass% or less, relative to the total mass of the polyamide in the polyamide composition.
By setting the content of the (A2) semiaromatic polyamide within the above range, the mechanical properties of a molded article obtained from the polyamide composition are more excellent. Further, the polyamide composition tends to give a molded article having more excellent tensile strength, flexural modulus at the time of water absorption, long-term heat resistance and tracking resistance by containing the component represented by the filler (D).
((A2) weight average molecular weight Mw (A2)) of the semiaromatic polyamide
As an index of the molecular weight of the (A2) semiaromatic polyamide, the weight average molecular weight Mw (A2) can be used. The weight average molecular weight Mw (A2) of the semiaromatic polyamide is preferably 10000 or more and 50000 or less, more preferably 15000 or more and 45000 or less, still more preferably 15000 or more and 40000 or less, still more preferably 17000 or more and 30000 or less, particularly preferably 17000 or more and 25000 or less, and most preferably 18000 or more and 22000 or less.
When the weight average molecular weight Mw (A2) falls within the above range, a polyamide composition having more excellent mechanical properties, particularly, water absorption rigidity, thermal rigidity, fluidity, tensile strength when formed into a molded article, flexural modulus when absorbing water, long-term heat resistance, tracking resistance and the like can be obtained.
The weight average molecular weight Mw (A2) may be measured by GPC as described in examples below.
[ blocking agent ]
The terminal end of the polyamide (a) contained in the polyamide composition of the present embodiment may be blocked with a known blocking agent.
Such a blocking agent may be added as a molecular weight regulator in the case of producing a polyamide from the dicarboxylic acid and the diamine, or in the case of producing a polyamide from at least one selected from the group consisting of the lactam and the aminocarboxylic acid.
Examples of the blocking agent include, but are not limited to, the following: monocarboxylic acids, monoamines, anhydrides (phthalic anhydride, etc.), monoisocyanates, monoesters, monoalcohols, etc. The blocking agent may be used alone or in combination of two or more.
Among them, monocarboxylic acids or monoamines are preferable as the blocking agent. By capping the ends of the polyamide with the capping agent, the molded article obtained from the polyamide composition tends to be more excellent in heat stability.
The monocarboxylic acid that can be used as the blocking agent may be any one that has reactivity with an amino group that may be present at the terminal of the polyamide. Examples of monocarboxylic acids include, but are not limited to, the following: aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, aromatic monocarboxylic acids, and the like.
Examples of the aliphatic monocarboxylic acid include: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid, and the like.
Examples of the alicyclic monocarboxylic acid include: cyclohexane carboxylic acid, and the like.
Examples of the aromatic monocarboxylic acid include: benzoic acid, toluic acid, alpha-naphthoic acid, beta-naphthoic acid, methylnaphthoic acid, phenylacetic acid, and the like.
These monocarboxylic acids may be used alone or in combination of two or more.
In particular, from the viewpoints of fluidity and mechanical strength, the terminal end of the (A2) semiaromatic polyamide is preferably capped with acetic acid.
The monoamine that can be used as the blocking agent may be any one having reactivity with carboxyl groups that may be present at the terminal ends of the polyamide. The monoamine is not limited to the following, and examples thereof include: aliphatic monoamines, alicyclic monoamines, aromatic monoamines, and the like.
Examples of the aliphatic monoamine include: methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, and the like.
Examples of the alicyclic monoamine include: cyclohexylamine, dicyclohexylamine, and the like.
Examples of the aromatic monoamine include: aniline, toluidine, diphenylamine, naphthylamine, and the like.
These monoamines may be used alone or in combination of two or more.
Polyamide compositions containing polyamides end-capped with end-capping agents tend to be more excellent in heat resistance, flowability, toughness, low water absorption and rigidity.
Process for producing polyamide (A)
In the production of the polyamide (a) contained in the polyamide composition of the present embodiment, the amount of the dicarboxylic acid to be added and the amount of the diamine to be added are preferably about the same molar amount as each other. In terms of the molar ratio, the molar amount of the entire diamine is preferably 0.9 to 1.2, more preferably 0.95 to 1.1, still more preferably 0.98 to 1.05, based on the molar amount 1 of the entire diamine, in view of the portion of the diamine escaping to the outside of the reaction system during the polymerization reaction.
The method for producing polyamide is not limited to the following method, and includes, for example, the following polymerization step (1) or (2).
(1) And polymerizing a combination of a dicarboxylic acid constituting a dicarboxylic acid unit and a diamine constituting a diamine unit to obtain a polymer.
(2) And polymerizing at least one selected from the group consisting of lactams constituting the lactam unit and aminocarboxylic acids constituting the aminocarboxylic acid unit to obtain a polymer.
In addition, as the method for producing polyamide, it is preferable that the method further comprises a step of raising the polymerization degree of polyamide after the polymerization step. The polymerization step and the raising step may be followed by a capping step of capping the end of the obtained polymer with a capping agent, if necessary.
Specific methods for producing polyamides include, for example, the various methods described in 1) to 4) below.
1) A method of polymerizing a dicarboxylic acid-diamine salt, a mixture of a dicarboxylic acid and a diamine, and/or a lactam and an aminocarboxylic acid while maintaining the molten state by heating the aqueous solution or suspension (hereinafter, sometimes referred to as "hot melt polymerization").
2) A method of increasing the polymerization degree of a polyamide obtained by a hot melt polymerization method while maintaining the solid state at a temperature of not more than the melting point (hereinafter, sometimes referred to as "hot melt polymerization/solid phase polymerization method").
3) A method of polymerizing one or more selected from the group consisting of a dicarboxylic acid-diamine salt, a mixture of a dicarboxylic acid and a diamine, a lactam and an aminocarboxylic acid while maintaining the solid state (hereinafter, sometimes referred to as "solid-phase polymerization method").
4) A method of polymerizing a dicarboxylic acid halide component and a diamine component equivalent to dicarboxylic acids (hereinafter, sometimes referred to as "solution method") by using them.
Among them, a specific production method of polyamide is preferably a production method including a hot melt polymerization method. In addition, in the production of polyamide by the hot melt polymerization method, it is preferable to keep the molten state until the polymerization is completed. In order to maintain the molten state, it is necessary to carry out the production under polymerization conditions suitable for the polyamide composition. Examples of the polymerization conditions include the following conditions. First, the polymerization pressure in the hot melt polymerization method was controlled to 14kg/cm 2 Above and 25kg/cm 2 Heating was continued as follows (gauge pressure). Then, the pressure was reduced for 30 minutes or longer until the pressure in the tank reached the atmospheric pressure (gauge pressure: 0 kg/cm) 2 )。
In the method for producing polyamide, the polymerization method is not particularly limited, and may be either a batch method or a continuous method.
The polymerization apparatus used for producing polyamide is not particularly limited, and a known apparatus can be used. Specific examples of the polymerization apparatus include: autoclave type reactors, roll type reactors, extruder type reactors (kneaders, etc.), and the like.
Hereinafter, a method for producing polyamide by a batch hot melt polymerization method is specifically described as a method for producing polyamide, but the method for producing polyamide is not limited thereto.
First, an aqueous solution containing about 40 mass% or more and about 60 mass% or less of a raw material component (a combination of a dicarboxylic acid and a diamine, and, if necessary, at least one selected from the group consisting of a lactam and an aminocarboxylic acid) of a polyamide is prepared. Next, the aqueous solution is concentrated to about 65 mass% or more and about 90 mass% or less in a concentration tank operated at a temperature of 110 ℃ or more and 180 ℃ or less and a pressure of about 0.035MPa or more and about 0.6MPa or less (gauge pressure) to obtain a concentrated solution.
The resulting concentrated solution was then transferred to an autoclave and heating was continued until the pressure in the autoclave reached about 1.2MPa or more and about 2.2MPa or less (gauge pressure).
Next, in the autoclave, the pressure was maintained at about 1.2MPa or more and about 2.2MPa or less (gauge pressure) while at least any one of water and gas components was removed. Then, the pressure is reduced to atmospheric pressure (gauge pressure: 0 MPa) at a time when the temperature reaches about 220 ℃ or higher and about 260 ℃ or lower. After the pressure in the autoclave is reduced to atmospheric pressure, the pressure is reduced as needed, whereby water produced as a by-product can be effectively removed.
Next, the autoclave is pressurized with an inert gas such as nitrogen, and the polyamide melt is extruded from the autoclave in the form of strands. The extruded strands were cooled and cut, thereby obtaining pellets of polyamide.
Properties of Polyamide (A)
[ (A) Polymer end of Polyamide ]
The polymer terminals of the polyamide (a) contained in the polyamide composition of the present embodiment are not particularly limited, and can be classified and defined as 1) to 4) below.
I.e., 1) amino-terminal, 2) carboxyl-terminal, 3) terminal formed by the capping agent, 4) other terminal.
1) The amino end is provided with amino (-NH) 2 Radical) and is derived from diamine units.
2) The carboxyl terminus is the polymer terminus with carboxyl (-COOH groups) groups and is derived from dicarboxylic acid units.
3) The terminal end formed by the blocking agent is a terminal end formed in the case where the blocking agent is added at the time of polymerization. The blocking agent may be the blocking agent described above.
4) The other ends are polymer ends which are not classified as 1) to 3) above. As the other end, specifically, there may be mentioned: a terminal produced by deamination of the amino terminus, a terminal produced by decarboxylation of the carboxyl terminus, and the like.
[ (A) weight average molecular weight Mw (A) of the Polyamide ]
As an index of the molecular weight of the polyamide (a), the weight average molecular weight Mw (a) can be used. The weight average molecular weight Mw (a) of the polyamide is preferably 12000 or more and 44000 or less, more preferably 17500 or more and 40000 or less, still more preferably 20000 or more and 40000 or less, still more preferably 24000 or more and 40000 or less, particularly preferably 28000 or more and 37500 or less, and most preferably 32000 or more and 36000 or less.
When the weight average molecular weight Mw (A) is in the above range, a polyamide composition having more excellent flame retardancy, long-term heat resistance, weld strength and laser welding strength can be obtained.
The weight average molecular weight Mw (a) may be measured by GPC as described in examples below.
Phosphorus-containing flame retardant
The phosphorus-containing flame retardant (B) contained in the polyamide composition of the present embodiment is not particularly limited as long as it contains phosphorus element and does not contain halogen. Examples of the phosphorus-containing flame retardant (B) include: phosphate flame retardants, melamine polyphosphate flame retardants, phosphazene flame retardants, phosphinic flame retardants, red phosphorus flame retardants, and the like.
Among them, the phosphorus-containing flame retardant (B) is preferably a phosphate flame retardant, a melamine polyphosphate flame retardant, a phosphazene flame retardant or a phosphinic flame retardant, and particularly preferably a phosphinic flame retardant.
Specifically, the phosphinic flame retardant may include, for example, at least one phosphinate selected from the group consisting of phosphinates represented by the following general formula (1) (hereinafter, abbreviated as "phosphinates (1)"), diphosphinates represented by the following general formula (2) (hereinafter, abbreviated as "diphosphinates (2)") and condensates thereof.
Figure BDA0002497751050000261
(in the general formula (1), R 11 And R is 12 Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. M is M n11+ Is a metal ion of valence n 11. M is an element belonging to group 2 or group 15 of the periodic Table, a transition element, zinc or aluminum. n11 is 2 or 3. In the case where n11 is 2 or 3, a plurality of R's are present 11 And a plurality of R 12 Each of which may be the same or different.
In the general formula (2), R 21 And R is 22 Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Y is Y 21 An alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. M's' m21+ A metal ion having a valence of m 21. M' is an element belonging to group 2 or group 15 of the periodic Table, a transition element, zinc or aluminum. n21 is an integer of 1 to 3. In the case where n21 is 2 or 3, a plurality of R's are present 21 A plurality of R 22 And a plurality of Y 21 Each of which may be the same or different. m21 is 2 or 3.x is 1 or 2. In the case where x is 2, a plurality of M's may be the same or different. n21, x, and m21 are integers satisfying the relationship of 2×n21=m21×x).
[R 11 、R 12 、R 21 And R is 22 ]
R 11 、R 12 、R 21 And R is 22 Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. In the case where n11 is 2 or 3, a plurality of R's are present 11 And a plurality of R 12 The two may be the same or different, but from the viewpoint of easy production, the same is preferable. In addition, when n21 is 2 or 3, a plurality of R's are present 21 And a plurality of R 22 The two may be the same or different, but from the viewpoint of easy production, the same is preferable.
The alkyl group may be chain-shaped or cyclic, but is preferably chain-shaped. The chain alkyl group may be a straight chain alkyl group or a branched alkyl group. Examples of the linear alkyl group include: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and the like. Examples of the branched alkyl group include: 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, 1-methylbutyl, 2-methylbutyl 3-methylbutyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, and the like.
Examples of the aryl group include: phenyl, naphthyl, and the like.
The alkyl group and the aryl group may have a substituent. Examples of the substituent on the alkyl group include aryl groups having 6 to 10 carbon atoms. Examples of the substituent on the aryl group include an alkyl group having 1 to 6 carbon atoms.
Specific examples of the alkyl group having a substituent include: benzyl, and the like.
Specific examples of the aryl group having a substituent include: tolyl, xylyl, and the like.
Wherein R is as R 11 、R 12 、R 21 And R is 22 Alkyl groups having 1 to 6 carbon atoms are preferable, and methyl or ethyl groups are more preferable.
[Y 21 ]
Y 21 An alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. In the case where n21 is 2 or 3, a plurality of Y's are present 21 The two may be the same or different, but from the viewpoint of easy production, the same is preferable.
The alkylene group may be chain-shaped or cyclic, but is preferably chain-shaped. The chain alkylene group may be a straight chain alkylene group or a branched chain alkylene group. Examples of the linear alkylene group include: methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and the like. Examples of the branched alkylene group include: 1-methylethylene, 1-methylpropylene, and the like.
Examples of the arylene group include: phenylene, naphthylene, and the like.
The alkylene group and arylene group may have a substituent. Examples of the substituent on the alkylene group include aryl groups having 6 to 10 carbon atoms. Examples of the substituent on the arylene group include an alkyl group having 1 to 6 carbon atoms.
Specific examples of the alkylene group having a substituent include: phenylmethylene, phenylethylene, phenyltrimethylene, phenyltetramethylene, and the like.
Specific examples of the arylene group having a substituent include: methylphenyl, ethylphenyl, t-butylphenyl, methylnaphthylene, ethylnaphthylene, t-butylnaphthylene, and the like.
Wherein as Y 21 An alkylene group having 1 to 10 carbon atoms is preferable, and a methylene group or an ethylene group is more preferable.
[ M and M' ]
M and M' are each independently an ion of an element belonging to group 2 or group 15 of the periodic table, an ion of a transition element, a zinc ion or an aluminum ion. Examples of the ions of the element belonging to group 2 of the periodic table include calcium ions and magnesium ions. Examples of the ions of the element belonging to group 15 of the periodic table include bismuth ions.
In the case where x is 2, the plurality of M's may be the same or different, but are preferably the same from the viewpoint of ease of production.
Among them, as M and M', calcium, zinc or aluminum is preferable, and calcium or aluminum is more preferable.
[x]
x represents the number of M', and x is 1 or 2.x may be appropriately selected according to the kind of M' and the amount of the diphosphinic acid.
[ n11 and n21]
n11 represents the number of phosphinic acids and the valence of M, and n11 is 2 or 3. n11 may be appropriately selected according to the kind and valence of M.
n21 represents the number of the diphosphinic acids, and n21 is an integer of 1 to 3. n21 may be appropriately selected according to the kind and the number of M'.
[m21]
M21 represents the valence of M', and M21 is 2 or 3.
n21, x, and m21 are integers satisfying a relation of 2×n21=m21×x.
Specific examples of the preferable phosphinate (1) include: calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium methylethylphosphinate, magnesium methylethylphosphinate, aluminum methylethylphosphinate, zinc methylethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methylphosphinate, magnesium methylphosphinate, aluminum methylphosphinate, zinc methylphosphinate, calcium methane bis (methylphosphinate), magnesium methane bis (methylphosphinate), aluminum methane bis (methylphosphinate), zinc methane bis (methylphosphinate), calcium benzene-1, 4- (dimethylphosphinate), magnesium benzene-1, 4- (dimethylphosphinate), aluminum benzene-1, 4- (dimethylphosphinate), zinc methylphosphinate, calcium methylphosphinate, magnesium methylphosphinate, zinc phenylphosphinate, and the like. Among these, calcium dimethylphosphinate or aluminum dimethylphosphinate is particularly preferable as the phosphinate (1) from the viewpoint of excellent flame retardancy.
Specific examples of the preferable bisphosphonate (2) include: calcium methane di (methylphosphinate), magnesium methane di (methylphosphinate), aluminum methane di (methylphosphinate), zinc methane di (methylphosphinate), calcium benzene-1, 4-di (methylphosphinate), magnesium benzene-1, 4-di (methylphosphinate), aluminum benzene-1, 4-di (methylphosphinate), zinc benzene-1, 4-di (methylphosphinate), and the like.
The method for producing the phosphinates is not particularly limited, and examples thereof include the methods described in patent document 5, patent document 6, patent document 7, and the like. Specifically, the production is carried out in an aqueous solution using phosphinic acid and a metal carbonate, metal hydroxide or metal oxide. Although these phosphinates are essentially monomeric compounds, depending on the reaction conditions, polymeric phosphinates may be included as condensates having a degree of condensation of 1 to 3 depending on the circumstances.
The content of the phosphorus-containing flame retardant is preferably 0.1 mass% or more and 30 mass% or less, more preferably 5 mass% or more and 30 mass% or less, still more preferably 10 mass% or more and 29 mass% or less, particularly preferably 15 mass% or more and 29 mass% or less, relative to the total mass of the polyamide (a), the phosphorus-containing flame retardant and the styrene copolymer (C).
By setting the content of the phosphorus-containing flame retardant (B) to the above lower limit or more, a polyamide composition having more excellent flame retardancy can be obtained. On the other hand, by setting the amount of the phosphorus-containing flame retardant (B) to the above upper limit or less, a polyamide composition having more excellent flame retardancy without impairing the properties possessed by the polyamide copolymer can be obtained.
Styrene copolymer (C)
The (C) styrene copolymer contained in the polyamide composition of the present embodiment is a styrene copolymer having a styrene content of 10 mass% or more. The styrene copolymer (C) may be specifically exemplified by: styrene-acrylonitrile copolymer (AS resin), styrene monomer and maleimide monomer such AS maleimide and N-phenylmaleimide; copolymers of acrylamide monomers such as acrylamide, and the like. Further, a copolymer obtained by substituting a part of styrene of the styrene polymer with a monomer such as α -methylstyrene, p-methylstyrene, vinylxylenes, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, p-t-butylstyrene, ethylstyrene, or vinylnaphthalene may be used. Among these, the styrene copolymer (C) is preferably a styrene-acrylonitrile copolymer (AS resin) having a styrene unit and an acrylonitrile unit, and the AS resin having a content of acrylonitrile unit of 30 mass% or more relative to the total mass of the constituent units of the styrene copolymer (C) is preferable, and the AS resin having a content of acrylonitrile unit of 35 mass% or more relative to the total mass of the constituent units of the styrene copolymer (C) is particularly preferable from the viewpoint of excellent flame retardancy and long-term heat resistance.
Since the addition of the styrene copolymer improves the fluidity and improves the dispersibility of the flame retardant, it is presumed that a strong and dense char (carbonized layer formed by combustion) can be formed at the time of combustion, and the flame retardancy is improved. Further, by adding the styrene copolymer, fluidity is improved, and dispersibility of the heat stabilizer is improved, so that it is presumed that radical trapping efficiency of the heat stabilizer is improved and long-term heat resistance is improved.
The content of the (C) styrene copolymer is 0.1 mass% or more and 7 mass% or less, preferably 0.5 mass% or more and 6 mass% or less, more preferably 1 mass% or more and 5 mass% or less, still more preferably 1 mass% or more and 3 mass% or less, relative to the total mass of the (a) polyamide, the (B) phosphorus-containing flame retardant and the (C) styrene copolymer.
By setting the content of the styrene copolymer (C) in the above range, a polyamide composition having excellent flame retardancy and excellent weld strength and long-term heat resistance when formed into a molded article can be obtained.
[ (C) weight average molecular weight Mw (C) of styrene copolymer ]
As an index of the molecular weight of the (C) styrene copolymer, the weight average molecular weight Mw (C) can be used. (C) The weight average molecular weight Mw (C) of the styrene copolymer is preferably 50000 or more and 220000 or less, more preferably 50000 or more and 150000 or less, still more preferably 70000 or more and 150000 or less, and most preferably 70000 or more and 100000 or less.
When the weight average molecular weight Mw (C) is in the above range, a polyamide composition having flame retardancy, weld strength when formed into a molded article, and long-term heat resistance can be obtained.
The weight average molecular weight Mw can be measured by GPC as described in examples below.
Filling material (D)
The polyamide composition of the present embodiment may further contain (D) a filler in addition to the components (a) to (C). By containing the filler (D), a polyamide composition having more excellent mechanical properties such as toughness and rigidity can be obtained.
The filler (D) contained in the polyamide composition of the present embodiment is not particularly limited, and examples thereof include: glass fibers, carbon fibers, calcium silicate fibers, potassium titanate fibers, aluminum borate fibers, flake glass, talc, kaolin, mica, hydrotalcite, zinc carbonate, monocalcium phosphate, wollastonite, zeolite, boehmite, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swellable fluoromica, apatite, and the like.
These (D) fillers may be used alone or in combination of two or more.
Among them, from the viewpoints of rigidity and strength, glass fibers, carbon fibers, scaly glass, talc, kaolin, mica, monocalcium phosphate, wollastonite, carbon nanotubes, graphite, calcium fluoride, montmorillonite, swellable fluoromica, or apatite are preferable as the filler (D). Further, as the filler (D), glass fibers or carbon fibers are more preferable, and glass fibers are further preferable.
When the filler (D) is a glass fiber or a carbon fiber, the number average fiber diameter (D) is preferably 3 μm or more and 30 μm or less. The weight average fiber length (L) is preferably 100 μm or more and 750 μm or less. The aspect ratio ((L)/(D)) of the weight-average fiber length (L) to the number-average fiber diameter (D) is preferably 10 to 100. By using the glass fiber or the carbon fiber having the above-described constitution, higher characteristics can be exhibited.
(D) The number average fiber diameter and the weight average fiber length of the filler can be measured by the following methods.
First, a polyamide-containing solvent such as formic acid is used to dissolve the molded article of the polyamide composition. Then, for example, 100 or more fillers are arbitrarily selected from the obtained insoluble components. Then, the filling material can be obtained by observing the filling material with an optical microscope, a scanning electron microscope, or the like.
The content of the filler (D) in the polyamide composition is preferably 1% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass or less, still more preferably 15% by mass or more and 60% by mass or less, particularly preferably 20% by mass or more and 55% by mass or less, and most preferably 25% by mass or more and 50% by mass or less, relative to the total mass of the polyamide composition.
When the content of the filler (D) is not less than the lower limit, the mechanical properties such as strength and rigidity of the polyamide composition tend to be further improved. On the other hand, when the content of the filler (D) is not more than the upper limit, a polyamide composition having more excellent laser welding strength tends to be obtained.
In particular, (D) the filler is glass fiber, and the content of (D) the filler is in the above range relative to the total mass of the polyamide composition, whereby the mechanical properties such as strength and rigidity of the polyamide composition tend to be further improved.
Other additives (E)
In addition to the components (a) to (C), the polyamide composition of the present embodiment may contain other additives (E) commonly used in polyamides within a range that does not impair the effects of the polyamide composition of the present embodiment. Examples of the other additives (E) include: (E1) A moldability improver, (E2) a deterioration inhibitor, (E3) a nucleating agent, (E4) a heat stabilizer, etc.
The content of the other additive (E) in the polyamide composition of the present embodiment is not particularly limited as long as the effect of the polyamide composition of the present embodiment is not impaired because it varies depending on the kind thereof, the use of the polyamide composition, and the like.
[ (E1) moldability improver ]
The moldability improver (E1) contained in the polyamide composition of the present embodiment is not particularly limited, and examples thereof include: higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amides, and the like. The moldability improver was also used as a "lubricating material".
(higher fatty acid)
Examples of the higher fatty acid include a linear or branched saturated or unsaturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms.
Examples of the linear saturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include: lauric acid, palmitic acid, stearic acid, behenic acid, montanic acid, and the like.
Examples of the branched saturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include: isopalmitic acid, isostearic acid, and the like.
Examples of the linear unsaturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include: oleic acid, erucic acid, and the like.
Examples of the branched unsaturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include: iso-oleic acid, and the like.
Among them, stearic acid or montanic acid is preferable as the higher fatty acid.
(higher fatty acid metal salt)
The higher fatty acid metal salt refers to a metal salt of a higher fatty acid.
Examples of the metal element of the metal salt include: group 1, group 2 and group 3 elements of the periodic table, zinc, aluminum, and the like.
Examples of the group 1 element in the periodic table include: sodium, potassium, and the like.
Examples of the group 2 element in the periodic table include: calcium, magnesium, and the like.
Examples of the group 3 element in the periodic table include: scandium, yttrium, etc.
Among them, group 1 elements and group 2 elements of the periodic table or aluminum are preferable, and sodium, potassium, calcium, magnesium or aluminum is more preferable.
Specific examples of the higher fatty acid metal salt include: calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate, and the like.
Among these, as the higher fatty acid metal salt, montanic acid metal salt or stearic acid metal salt is preferable.
(higher fatty acid ester)
The higher fatty acid ester refers to an ester of a higher fatty acid with an alcohol.
The higher fatty acid ester is preferably an ester of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms.
Examples of the aliphatic alcohol having 8 to 40 carbon atoms include: stearyl alcohol, sorbitol, lauryl alcohol, and the like.
Specific examples of the higher fatty acid ester include: stearyl stearate, behenyl behenate, and the like.
(higher fatty acid amide)
Higher fatty acid amides refer to amide compounds of higher fatty acids.
Examples of the higher fatty acid amide include: stearamide, oleamide, erucamide, ethylene bisstearamide, ethylene bisoleamide, N-stearyl stearamide, N-stearyl erucamide, and the like.
Each of these higher fatty acids, higher fatty acid metal salts, higher fatty acid esters and higher fatty acid amides may be used alone or in combination of two or more.
[ (E2) degradation inhibitor ]
The (E2) deterioration inhibitor contained in the polyamide composition of the present embodiment is used for the purpose of preventing thermal deterioration, thermochromic, and improving thermal aging resistance.
The degradation inhibitor (E2) is not particularly limited, and examples thereof include: copper compounds, phenolic stabilizers, phosphite stabilizers, hindered amine stabilizers, triazine stabilizers, benzotriazole stabilizers, benzophenone stabilizers, cyanoacrylate stabilizers, salicylate stabilizers, sulfur-containing stabilizers, and the like.
Examples of the copper compound include: copper acetate, copper iodide, and the like.
Examples of the phenolic stabilizer include: hindered phenol compounds, and the like.
These (E2) degradation inhibitors may be used singly or in combination of two or more.
[ (E3) nucleating agent ]
(E3) The nucleating agent is a substance which can obtain at least any one of the following effects (1) to (3) by adding the nucleating agent.
(1) Effect of increasing the crystallization peak temperature of the polyamide composition.
(2) The effect of reducing the difference between the extrapolated onset temperature and the extrapolated end temperature of the crystallization peak.
(3) The effect of making the spherulites of the obtained molded article finer or the size thereof uniform.
The nucleating agent (E3) is not limited to the following, and examples thereof include: talc, boron nitride, mica, kaolin, silicon nitride, carbon black, potassium titanate, molybdenum disulfide, and the like.
(E3) The nucleating agent may be used alone or in combination of two or more.
Among them, talc or boron nitride is preferable as the (E3) nucleating agent from the viewpoint of the nucleating agent effect.
The number average particle diameter of the (E3) nucleating agent is preferably 0.01 μm or more and 10 μm or less, because the effect of the nucleating agent is high.
The number average particle diameter of the nucleating agent can be measured by the following method. First, the molded article is dissolved by a solvent such as formic acid in which polyamide is soluble. Then, for example, 100 or more nucleating agents are arbitrarily selected from the insoluble components obtained. Then, the particle diameter can be obtained by observing and measuring the particle diameter by an optical microscope, a scanning electron microscope, or the like.
The content of the nucleating agent in the polyamide composition of the present embodiment is preferably 0.001 parts by mass or more and 1 part by mass or less, more preferably 0.001 parts by mass or more and 0.5 parts by mass or less, still more preferably 0.001 parts by mass or more and 0.09 parts by mass or less, per 100 parts by mass of the polyamide ((A1) aliphatic polyamide and (A2) semiaromatic polyamide).
When the content of the nucleating agent is set to the above lower limit or more relative to 100 parts by mass of the polyamide, the heat resistance of the polyamide composition tends to be further improved, and when the content of the nucleating agent is set to the above upper limit or less relative to 100 parts by mass of the polyamide, a polyamide composition having more excellent toughness can be obtained.
[ (E4) Heat stabilizer ]
The heat stabilizer (E4) is not limited to the following, and examples thereof include: phenolic heat stabilizers, phosphorus-containing heat stabilizers, amine heat stabilizers, metal salts of elements of groups 3, 4 and 11 to 14 of the periodic table, and the like.
(phenolic heat stabilizer)
The phenolic heat stabilizer is not limited to the following, and examples thereof include hindered phenol compounds. The hindered phenol compound has properties of imparting excellent heat resistance and light resistance to resins or fibers such as polyamides.
The hindered phenol compound is not limited to the following, and examples thereof include: n, N '-hexane-1, 6-diylbis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl propionamide), pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide), triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 3, 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1, 1-dimethylethyl } -2,4,8, 10-tetraoxaspiro [5.5] undecane, diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphonate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, and the like.
These hindered phenol compounds may be used alone or in combination of two or more.
When the phenolic heat stabilizer is used, the content of the phenolic heat stabilizer in the polyamide composition is preferably 0.01 mass% or more and 1 mass% or less, more preferably 0.05 mass% or more and 1 mass% or less, relative to the total mass of the polyamide composition.
When the content of the phenolic heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of gas generation can be further reduced.
(phosphorus-containing Heat stabilizer)
Examples of the phosphorus-containing heat stabilizer include, but are not limited to, the following: pentaerythritol phosphite, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, triisodecyl phosphite, diisodecyl phosphite, ditridecyl phosphite, isooctyl phosphite, diphenyl phosphite, isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (butoxyethyl) phosphite, tris (4, 4' -butylidenebis (3-methyl-6-tert-butylphenyl) phosphite-tetra (tridecyl) phosphite, 4' -isopropylidenediphenyl-tetra (C12-C15 mixed alkyl) phosphite, 4' -isopropylidenebis-di (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (1, 4' -di-tert-butylphenyl) diphenyl phosphite, 1, 4' -di-tert-butylphenyl-1-4-di-tert-butylphenyl) 4-di-tert-butylphenyl phosphite, 1-tert-4-butylidene-4-di-tert-butylphenyl phosphite, tris (mono-, di-mixed nonylphenyl) phosphite, 4 '-isopropylidenebis (2-t-butylphenyl) phosphite-bis (nonylphenyl) ester, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3, 5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4, 4' -isopropylidenediphenyl polyphosphite, bis (4, 4 '-butylidenebis (3-methyl-6-t-butylphenyl)) -1, 6-hexanediol bisphosphite bis (octylphenyl) ester, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite hexatridecyl phosphite, tris (4, 4' -isopropylidenebis (2-t-butylphenyl) phosphite, tris (1, 3-stearyloxyisopropyl) phosphite, 2-methylenebis (4, 6-di-t-butylphenyl) octylphosphite, 2-bis (3-methyl-6-t-butylphenyl) phosphite, 2,4 '-di-butylphenyl) biphenyl 4,4' -di-t-butylphenyl) 4,4 '-di-butylphenyl 4,4' -di-t-butylphenyl) phosphite.
These phosphorus-containing heat stabilizers may be used alone or in combination of two or more.
The pentaerythritol-type phosphite compound is not limited to the following, and examples thereof include: pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-phenyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-methyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-2-ethylhexyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-isodecyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-lauryl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-isotridecyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-stearyl ester pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-cyclohexyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-benzyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-ethylcellosolve ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-butylcarbitol ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-octylphenyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-nonylphenyl ester, pentaerythritol diphosphite di (2, 6-di-tert-butyl-4-methylphenyl) ester, pentaerythritol diphosphite bis (2, 6-di-tert-butyl-4-ethylphenyl), pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-2, 6-di-tert-butylphenyl, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-2, 4-di-tert-octylphenyl ester, pentaerythritol diphosphite 2, 6-di-tert-butyl-4-methylphenyl ester-2-cyclohexylphenyl ester, pentaerythritol diphosphite 2, 6-di-tert-amyl-4-methylphenyl ester, pentaerythritol diphosphite bis (2, 6-di-tert-octyl-4-methylphenyl) ester, and the like.
These pentaerythritol-type phosphite compounds may be used alone or in combination of two or more.
When the phosphorus-containing heat stabilizer is used, the content of the phosphorus-containing heat stabilizer in the polyamide composition is preferably 0.01 mass% or more and 1 mass% or less, more preferably 0.05 mass% or more and 1 mass% or less, relative to the total mass of the polyamide composition.
When the content of the phosphorus-containing heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of gas generation can be further reduced.
(amine Heat stabilizer)
Examples of the amine heat stabilizer include, but are not limited to, the following: 4-Acetyloxy-2, 6-tetramethylpiperidine, 4-stearoyloxy-2, 6-tetramethylpiperidine, 4-acryloyloxy-2, 6-tetramethylpiperidine 4- (Phenylacetoxy) -2, 6-tetramethylpiperidine, 4-benzoyloxy-2, 6-tetramethylpiperidine, 4-methoxy-2, 6-tetramethylpiperidine 4- (Phenylacetoxy) -2, 6-tetramethylpiperidine 4-benzoyloxy-2, 6-tetramethylpiperidine, 4-methoxy-2, 6-tetramethylpiperidine 4- (cyclohexylcarbamoyloxy) -2, 6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2, 6-tetramethylpiperidine bis (2, 6-tetramethyl-4-piperidinyl) carbonate, bis (2, 6-tetramethyl-4-piperidinyl) oxalate, bis (2, 6-tetramethyl-4-piperidinyl) malonate bis (2, 6-tetramethyl-4-piperidinyl) carbonate, bis (2, 6-tetramethyl-4-piperidinyl) oxalate malonic acid bis (2, 6-tetramethyl-4-piperidinyl) ester, benzene-1, 3, 4-tricarboxylic acid tris (2, 6-tetramethyl-4-piperidinyl) ester 1- [2- {3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy } butyl ] -4- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] -2, 6-tetramethylpiperidine benzene-1, 3, 4-tricarboxylic acid tris (2, 6-tetramethyl-4-piperidinyl) ester, 1- [2- {3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy } butyl ] -4- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] -2, 6-tetramethylpiperidine 1,2,3, 4-butanetetracarboxylic acid with 1,2, 6-pentamethyl-4-piperidinol and beta, condensate of beta, beta' -tetramethyl-3, 9- [2,4,8, 10-tetraoxaspiro (5.5) undecane ] diethanol, and the like.
These amine heat stabilizers may be used alone or in combination of two or more.
When the amine heat stabilizer is used, the content of the amine heat stabilizer in the polyamide composition is preferably 0.01 mass% or more and 1 mass% or less, more preferably 0.05 mass% or more and 1 mass% or less, relative to the total mass of the polyamide composition.
When the content of the amine heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of gas generation can be further reduced.
(metal salts of elements of groups 3, 4 and 11 to 14 of the periodic Table)
The metal salts of the elements of groups 3, 4 and 11 to 14 of the periodic table are not limited as long as they are salts of metals belonging to these groups.
Among them, copper salts are preferable from the viewpoint of further improving the heat aging resistance of the polyamide composition. The copper salt is not limited to the following, and examples thereof include: copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, copper stearate, copper complex salts obtained by complexing copper with chelating agents.
Examples of the chelating agent include: ethylenediamine, ethylenediamine tetraacetic acid, and the like.
These copper salts may be used singly or in combination of two or more.
Among them, copper acetate is preferable as copper salt. When copper acetate is used, a polyamide composition having more excellent thermal aging resistance and capable of more effectively suppressing metal corrosion of the screw or barrel portion during extrusion (hereinafter, also referred to simply as "metal corrosion") can be obtained.
When a copper salt is used as the heat stabilizer (E4), the content of the copper salt in the polyamide composition is preferably 0.01 mass% or more and 0.60 mass% or less, more preferably 0.02 mass% or more and 0.40 mass% or less, relative to the total mass of the polyamide (a).
When the content of the copper salt is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the precipitation of copper and the corrosion of metal can be more effectively suppressed.
In addition, from the viewpoint of improving the heat aging resistance of the polyamide composition, the heat aging resistance of the polyamide composition is improved relative to (A) polyamide 10 6 The content concentration of the copper element derived from the copper salt is preferably 10 parts by mass or more and 2000 parts by mass or less (100 ten thousand parts by mass), more preferably 30 parts by mass or more and 1500 parts by mass or less, and still more preferably 50 parts by mass or more and 500 parts by mass or less.
The above-described component (E4) may be used alone or in combination of two or more.
Process for producing polyamide composition
The method for producing the polyamide composition of the present embodiment is not particularly limited as long as the polyamide (a) is mixed with the components (B) to (C) and, if necessary, (D) and (E).
Examples of the method for mixing the components (a) to (C) and, if necessary, (D) and (E) include the following methods (1) and (2).
(1) A method in which the components (A) to (C) and, if necessary, (D) and (E) are mixed by using a Henschel mixer or the like, and supplied to a melt kneader and kneaded.
(2) A method in which the components (a) to (C) and, if necessary, the component (E) are mixed in advance using a henschel mixer or the like to prepare a mixture containing the components (a) to (C) and, if necessary, the component (E), the mixture is fed to a melt kneader and kneaded, and then the component (D) is optionally compounded by a side feeder using a single-screw or twin-screw extruder.
In the method of supplying the components constituting the polyamide composition to the melt kneader, all the components may be supplied at once at the same supply port, or the components may be supplied from different supply ports.
When the polyamide (a) contains the aliphatic polyamide (A1), the melt-kneading temperature is preferably a temperature of about 1 ℃ or higher and about 100 ℃ or lower higher than the melting point of the aliphatic polyamide (A1), and more preferably a temperature of about 10 ℃ or higher and about 50 ℃ or lower than the melting point of the aliphatic polyamide (A1).
The shear rate in the mixer is preferably about 100 seconds -1 The above. The average residence time during kneading is preferably about 0.5 minutes to about 5 minutes.
The apparatus for melt kneading may be any known apparatus, and for example, a single screw or twin screw extruder, a Banbury mixer, a melt kneader (mixing roll or the like) or the like is preferably used.
The amount of each component to be blended in the production of the polyamide composition of the present embodiment is the same as the content of each component in the polyamide composition described above.
Molded article
The molded article of the present embodiment is obtained by molding the polyamide composition of the above embodiment.
The molded article of the present embodiment contains a halogen-free flame retardant and is excellent in flame retardancy and long-term heat resistance.
The method for obtaining the molded article is not particularly limited, and a known molding method can be used.
Examples of known molding methods include: extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decoration molding, heterogeneous material molding, gas-assisted injection molding, foaming injection molding, low pressure molding, ultra-thin wall injection molding (ultra-high speed injection molding), in-mold composite molding (insert molding, injection molding on a substrate), and the like.
< use >
The molded article of the present embodiment contains the polyamide composition of the above embodiment, has excellent flame retardancy and long-term heat resistance, and can be used for various applications.
The molded article of the present embodiment can be suitably used in, for example, the fields of automobiles, electric and electronic fields, machinery and industry, office equipment, aviation and aerospace, and the like.
Method of addition
The method of the present embodiment is a method of adding (C) a styrene copolymer as a flame retardant aid to a resin composition containing (a) a polyamide and (B) a phosphorus-containing flame retardant. As described above, by adding (C) the styrene copolymer to the resin composition containing (a) the polyamide and (B) the phosphorus-containing flame retardant, the fluidity of the resin composition is improved, and the dispersibility of (B) the phosphorus-containing flame retardant as the flame retardant becomes good. Therefore, it is presumed that a strong and dense char (carbonized layer formed by combustion) can be formed at the time of combustion, and flame retardancy is improved. Further, by adding (C) a styrene copolymer to a resin composition containing (A) a polyamide and (B) a phosphorus-containing flame retardant, the fluidity of the resin composition is improved, and the dispersibility of the heat stabilizer is improved, so that it is presumed that the radical trapping efficiency of the heat stabilizer is improved and the long-term heat resistance is improved.
The resin composition may contain the component (D) and the component (E) in addition to the component (a) and the component (B). The components (a) to (E) are the same as those exemplified in the polyamide composition.
Examples (example)
Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.
The components of the polyamide compositions used in the present examples and comparative examples will be described below.
< constituent component >
[ (A1) aliphatic Polyamide ]
A1-1: polyamide 66
[ (A2) semi-aromatic Polyamide ]
A2-1: polyamide 6I
A2-2: polyamide 6I/6T (manufactured by EMS Co., ltd., model: G21, content of isophthalic acid unit in all dicarboxylic acid units: 70 mol%, molecular weight: 27000)
[ (B) phosphorus-containing flame retardant ]
B-1: aluminum diethylphosphinate (trade name: "Exolit OP1230", manufactured by Clariant Co., ltd.) as phosphinic acid flame retardant
B-2: calcium diethylphosphinate (manufactured by Taiping chemical industry Co., ltd.) as a phosphinic acid flame retardant
[ (B') flame retardant other than phosphorus-containing flame retardant ]
B' -1: nitrogen-containing flame retardant melamine cyanurate (manufactured by Nissan chemical industry Co., ltd.)
[ (C) styrene copolymer ]
C-1: styrene-Acrylonitrile copolymer (AS) (manufactured by Asahi chemical Co., ltd.) (acrylonitrile content 40% by mass, molecular weight: 80000)
C-2: styrene-Acrylonitrile copolymer (AS) (manufactured by Asahi chemical Co., ltd.) (acrylonitrile content: 25% by mass, molecular weight: 140000)
C-3: styrene-Acrylonitrile copolymer (AS) (manufactured by Asahi chemical Co., ltd.) (acrylonitrile content: 30% by mass, molecular weight: 130000)
[ (D) filler ]
D-1: glass Fiber (GF) (trade name: ECS03T275H, manufactured by Nitro Kogyo Co., ltd., average fiber diameter: 10 μm phi, cut length: 3 mm)
[ (E) other additives ]
E-1: phenolic heat stabilizer (trade name "Irganox 1098", manufactured by Ciba refining Co., ltd.)
< production of Polyamide >
The following describes in detail the production methods of the aliphatic polyamide A1-1 and the semiaromatic polyamide A2-1. The aliphatic polyamide A1-1 and the semiaromatic polyamide A2-1 obtained by the following production methods were dried in a nitrogen gas stream to adjust the water content to about 0.2 mass%, and then used as raw materials for polyamide compositions in examples and comparative examples described below.
Synthesis example 1 Synthesis of aliphatic Polyamide A1-1 (Polyamide 66)
The polymerization of polyamide was carried out by the "hot melt polymerization method" as described below.
First, 1500g of an equimolar salt of adipic acid and hexamethylenediamine was dissolved in 1500g of distilled water to prepare an equimolar 50 mass% homogeneous aqueous solution of the raw material monomers. This aqueous solution was charged into an autoclave having an internal volume of 5.4L, and nitrogen substitution was performed. Then, while stirring at a temperature of about 110 ℃ or higher and about 150 ℃ or lower, the vapor was slowly discharged and concentrated to a solution concentration of 70 mass%. Then, the internal temperature was raised to 220 ℃. At this time, the autoclave was pressurized to 1.8MPa. This state was maintained for 1 hour until the internal temperature reached 245 ℃, and the reaction was carried out for 1 hour while slowly discharging water vapor while maintaining the pressure at 1.8MPa. Then, the pressure was reduced for 1 hour. Then, the inside of the autoclave was kept under reduced pressure of 650 Torr (86.66 kPa) for 10 minutes by means of a vacuum apparatus. At this time, the final internal temperature of the polymerization was 265 ℃. Then, the resultant was pressurized with nitrogen gas, formed into a strand form from a lower spinning nozzle, cooled with water, cut, and discharged in the form of pellets. Next, the pellets were dried at 100℃under a nitrogen atmosphere for 12 hours, whereby aliphatic polyamide A1-1 (polyamide 66) was obtained.
Mw (A1) =40000 of the obtained aliphatic polyamide A1-1 (polyamide 66).
Synthesis example 2 Synthesis of semiaromatic Polyamide A2-1 (Polyamide 6I)
The polymerization of polyamide was carried out by the "hot melt polymerization method" as described below.
First, 1500g of an equimolar salt of isophthalic acid and hexamethylenediamine, adipic acid in an amount of 1.5 mol% exceeding the total equimolar salt content, and acetic acid in an amount of 0.5 mol% were dissolved in 1500g of distilled water to prepare an equimolar 50 mass% homogeneous aqueous solution of the raw material monomers. Then, while stirring at a temperature of about 110 ℃ or higher and about 150 ℃ or lower, the vapor was slowly discharged and concentrated to a solution concentration of 70 mass%. Then, the internal temperature was raised to 220 ℃. At this time, the autoclave was pressurized to 1.8MPa. This state was maintained for 1 hour until the internal temperature reached 245 ℃, and the reaction was carried out for 1 hour while slowly discharging water vapor while maintaining the pressure at 1.8MPa. Then, the pressure was reduced for 30 minutes. Then, the inside of the autoclave was kept under reduced pressure of 650 Torr (86.66 kPa) for 10 minutes by means of a vacuum apparatus. At this time, the final internal temperature of the polymerization was 265 ℃. Then, the resultant was pressurized with nitrogen gas, formed into a strand form from a lower spinning nozzle, cooled with water, cut, and discharged in the form of pellets. Next, the pellets were dried at 100℃under a nitrogen atmosphere for 12 hours to obtain semiaromatic polyamide A2-1 (polyamide 6I).
The content of isophthalic acid unit in the dicarboxylic acid unit of the resulting semiaromatic polyamide A2-1 (polyamide 6I) was 100 mol%. Mw (A2) =20000.
< physical Properties and evaluation >
First, pellets of the polyamide compositions obtained in examples and comparative examples were dried in a nitrogen gas stream, and the water content in the polyamide compositions was adjusted to 500ppm or less. Next, using pellets of each polyamide composition having a water content adjusted, measurement of various physical properties and various evaluations were performed by the following methods.
[ physical Property 1] tan delta Peak temperature
Using a PS40E injection molding machine manufactured by japanese industrial Co., ltd., the cylinder temperature was set to 290 ℃, the mold temperature was set to 100 ℃, and molded into a molded article according to JIS-K7139 under injection molding conditions of an injection time of 10 seconds and a cooling time of 10 seconds. The molded article was measured under the following conditions using a dynamic viscoelasticity evaluation device (EPLEXOR 500N manufactured by GABO corporation).
(measurement conditions)
Measurement mode: stretching
Measuring frequency: 8.00Hz
Heating rate: 3 ℃/min
Temperature range: -100 ℃ to 250 DEG C
The ratio (E2/E1) of the loss elastic modulus E2 to the storage elastic modulus E1 was set to tan delta, and the highest temperature was set to tan delta peak temperature.
Physical Property 2 molecular weight (Mw) of Polyamide composition
The weight average molecular weight (Mw) of the polyamide compositions obtained in examples and comparative examples was measured using GPC under the following measurement conditions.
(measurement conditions)
Measurement device: HLC-8020 manufactured by Tosoh Co., ltd
Solvent: hexafluoroisopropanol solvent
Standard sample: PMMA (polymethyl methacrylate) (manufactured by Polymer laboratories Co., ltd.) conversion
GPC column: TSK-GEL GMHHR-M and G1000HHR
[ evaluation 1] flame retardance
The measurement was performed using the method of UL94 (standard established by underwriters laboratories, usa). Test pieces (length 127mm, width 12.7mm, thickness 1.6 mm) were produced in the following manner: the mold (mold temperature=100℃) for the UL test piece was mounted on an injection molding machine (PS 40E manufactured by japanese industrial Co., ltd.) and each polyamide composition was molded at a cylinder temperature of 290 ℃. Regarding the injection pressure, it was carried out at a total filling pressure +2% at the time of molding the UL test piece. Whether the flame retardant rating corresponds to any of V-0, V-1, V-2 was evaluated according to the UL94 standard (vertical burning test). The smaller the number of the grade, the higher the flame retardancy.
[ evaluation 2] weld Strength
The test piece was obtained by molding with an injection molding machine (PS 40E manufactured by japanese industrial Co., ltd.) equipped with a mold in which molten resin flowed from both ends in the longitudinal direction of a shape having a length of 127mm, a width of 12.7mm, and a thickness of 1.6mm and a weld was to be formed at the center in the longitudinal direction. The specific molding conditions are as follows: the injection+dwell time was set to 25 seconds, the cooling time was set to 15 seconds, the mold temperature was set to 80 ℃, and the molten resin temperature was set to the high temperature side melting peak temperature (Tm 2) +20 ℃ of the polyamide. The tensile strength was determined by performing a tensile test on the test piece obtained by molding according to the method of astm d638, except that the distance between chucks was set to 50mm and the pulling speed was set to 50 mm/min.
[ evaluation 3] Long-term Heat resistance
The multipurpose test piece (type a) of the tensile strength described above was heat aged by heating at 120 ℃ in a hot air circulation oven.
After 1000 hours in the oven, the mixture was taken out of the oven and cooled at 23℃for more than 24 hours. Next, the cooled multipurpose test piece (type A) was subjected to a tensile test according to ISO 527 and at a pulling rate of 5 mm/min by the same method as described above, and each tensile strength was measured. The heat aging retention was determined using the following formula.
Heat aging retention (%) =tensile strength after aging/tensile strength before aging×100
[ evaluation 4] laser welding Strength
A coloring master batch for laser welding (Orient chemical industry: eBIND ACW-9871, hereinafter abbreviated as ACW) was dry-blended in each polyamide resin composition at a dilution ratio of 60 times, to form a flat plate of 60 mm. Times.60 mm. Times.2.0 mm in thickness, and cut into a flat plate of 28 mm. Times.60 mm. Times.2.0 mm in thickness, thereby producing a member A. The specific forming conditions are as follows: the mold temperature was set at 80℃and the molten resin temperature was set at the melting peak temperature (Tm 2) +20deg.C on the high temperature side of the polyamide.
Further, with respect to 100 parts by mass of the polyamide resin composition, 1500ppm of carbon black (primary particle diameter: 27 nm) was dry-blended, a flat plate of 60 mm. Times.60 mm. Times.plate thickness 2.0mm was molded, and a flat plate of 25 mm. Times.60 mm. Times.plate thickness 2.0mm was cut, whereby a member B was produced.
In a state where the members a and B were fixed so as to overlap each other by 20mm in the longitudinal direction of each member, a laser beam was irradiated from one end to the other end of the test piece so as to be parallel to the short side portion of the test piece from the member a side of the laser beam welder at a scanning speed of 50.0 mm/sec and an output power of 150W, and the portion was cooled by air, whereby a test piece was produced.
The maximum point load was measured by a tensile test of a test piece manufactured by Instron, using a 30kN load cell, by sandwiching both ends of the members A and B between chucks, and under test conditions in which the distance between chucks was 30mm and the pulling speed was 5.0 mm/min.
< production of Polyamide composition >
Example 1
A TEM35mm twin-screw extruder (set temperature: 280 ℃ C., screw rotation speed: 300 rpm) manufactured by Toshiba machinery Co., ltd.) was used, and a material obtained by previously mixing (A) polyamide A-1, (C) styrene copolymer C-1 and (E) other additive E-1 was fed from a top feed port provided at the uppermost stream portion of the extruder. In addition, (B) a phosphorus-containing flame retardant B-1 and (D) a filler D-1 are fed from a side feed port on the downstream side of the extruder (in a state where the resin fed from the top feed port is sufficiently melted). Next, the molten kneaded material extruded from the die is cooled in the form of strands, and pelletized, thereby obtaining pellets of the polyamide composition. The blending amounts are shown in Table 1.
Further, using the pellets of the polyamide composition obtained, molded articles were produced by the above-described method, and various physical properties were measured and evaluated. The evaluation results are shown in table 1.
Examples 2 to 12 and comparative examples 1 to 6
The same procedure as in example 1 was used except that the compositions (a) to (E) were set to the compositions shown in table 1. The evaluation results are shown in tables 1 and 2. In table 2, "n.d." is abbreviated as "No Data" (No Data), and indicates that the strength of the test piece produced was low and could not be measured.
Figure BDA0002497751050000521
/>
Figure BDA0002497751050000531
As is clear from table 1, the polyamide compositions (examples 1 to 12) containing the (a) polyamide, the (B) phosphorus-containing flame retardant and the (C) styrene copolymer and having the content of the (C) styrene copolymer in the range of 0.1 mass% or more and 7 mass% or less relative to the total mass of the (a) to (C) components gave molded articles capable of having both flame retardancy and long-term heat resistance.
The polyamide compositions (examples 2 to 12) containing (A1) the aliphatic polyamide A1-1 and (A2) the semiaromatic polyamide A2-1 or A2-2 were excellent in the laser welding strength of the molded articles obtained.
In addition, the polyamide compositions (examples 2, 3, 6 to 10) containing the styrene copolymer C-1 having a high acrylonitrile content gave molded articles having particularly good flame retardancy and long-term heat resistance.
On the other hand, polyamide compositions (comparative examples 1 to 6) which did not contain the (C) styrene copolymer or contained more than 7 mass% of the (C) styrene copolymer based on the total mass of the components (a) to (C) did not give molded articles capable of having both flame retardancy and long-term heat resistance.
As described above, according to the polyamide composition of the present embodiment, a molded article containing a halogen-free flame retardant and having both flame retardancy and long-term heat resistance can be obtained.
[ industrial applicability ]
According to the polyamide composition of the present embodiment, a molded article containing a halogen-free flame retardant and having both flame retardancy and long-term heat resistance can be obtained. The molded article of the present embodiment can be suitably used in the fields of automobiles, electric and electronic fields, machinery and industry, office equipment, aviation and aerospace.

Claims (41)

1. A polyamide composition comprising:
(A) Polyamide(s),
(B) Phosphorus-containing flame retardants
(C) A styrene copolymer, wherein,
the content of the (C) styrene copolymer is 0.1 mass% or more and 7.0 mass% or less relative to the total mass of the (A) polyamide, the (B) phosphorus-containing flame retardant and the (C) styrene copolymer,
the (C) styrene copolymer contains an acrylonitrile unit and a styrene unit.
2. The polyamide composition according to claim 1, wherein the (A) polyamide comprises (A1) an aliphatic polyamide and (A2) a semiaromatic polyamide, and the (A2) semiaromatic polyamide comprises a diamine unit and a dicarboxylic acid unit.
3. The polyamide composition according to claim 2, wherein the (A2) semiaromatic polyamide contains 50 mol% or more of isophthalic acid units in all dicarboxylic acid units constituting the (A2) semiaromatic polyamide.
4. The polyamide composition according to claim 2 or 3, wherein the (A2) semiaromatic polyamide contains 75 mol% or more of isophthalic acid units in all dicarboxylic acid units constituting the (A2) semiaromatic polyamide.
5. A polyamide composition according to claim 2 or 3, wherein the (A2) semiaromatic polyamide contains 100 mol% isophthalic acid units among all dicarboxylic acid units constituting the (A2) semiaromatic polyamide.
6. The polyamide composition as claimed in claim 4, wherein said (A2) semiaromatic polyamide contains 100 mol% of isophthalic acid units among all dicarboxylic acid units constituting said (A2) semiaromatic polyamide.
7. The polyamide composition as claimed in any one of claims 1 to 3 and 6, wherein the (C) styrene copolymer contains an acrylonitrile unit and a styrene unit, and
the content of the acrylonitrile unit is 30 mass% or more relative to the total mass of the constituent units of the (C) styrene copolymer.
8. The polyamide composition as claimed in claim 4, wherein the (C) styrene copolymer contains acrylonitrile units and styrene units, and
the content of the acrylonitrile unit is 30 mass% or more relative to the total mass of the constituent units of the (C) styrene copolymer.
9. The polyamide composition as claimed in claim 5, wherein the (C) styrene copolymer contains acrylonitrile units and styrene units, and
the content of the acrylonitrile unit is 30 mass% or more relative to the total mass of the constituent units of the (C) styrene copolymer.
10. The polyamide composition according to any one of claims 1 to 3, 6, 8 and 9, wherein the phosphorus-containing flame retardant (B) comprises at least one phosphinate selected from the group consisting of phosphinates represented by the following general formula (1), diphosphinates represented by the following general formula (2) and condensates thereof,
Figure FDA0004153132180000021
Figure FDA0004153132180000031
in the general formula (1), R 11 And R is 12 Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; m is M n11+ Is n11 priceMetal ions of (2); m is an element belonging to group IIA or group VA of the periodic Table, a transition element or aluminum; n11 is 2 or 3; in the case where n11 is 2 or 3, a plurality of R's are present 11 And a plurality of R 12 Each of which may be the same or different;
in the general formula (2), R 21 And R is 22 Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; y is Y 21 An alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms; m's' x m21+ A metal ion having a valence of m 21; m' is an element belonging to group IIA or group VA of the periodic Table, a transition element or aluminum; n21 is an integer of 1 to 3 inclusive; in the case where n21 is 2 or 3, a plurality of R's are present 21 A plurality of R 22 And a plurality of Y 21 Each of which may be the same or different; m21 is 2 or 3; x is 1 or 2; in the case where x is 2, a plurality of M's may be the same or different; n21, x, and m21 are integers satisfying a relation of 2×n21=m21×x.
11. The polyamide composition as claimed in claim 4, wherein the phosphorus-containing flame retardant (B) contains at least one phosphinate selected from the group consisting of phosphinates represented by the following general formula (1), diphosphinates represented by the following general formula (2) and condensates thereof,
Figure FDA0004153132180000032
Figure FDA0004153132180000041
in the general formula (1), R 11 And R is 12 Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; m is M n11+ A metal ion of valence n 11; m is an element belonging to group IIA or group VA of the periodic Table, a transition element or aluminum;n11 is 2 or 3; in the case where n11 is 2 or 3, a plurality of R's are present 11 And a plurality of R 12 Each of which may be the same or different;
in the general formula (2), R 21 And R is 22 Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; y is Y 21 An alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms; m's' x m21+ A metal ion having a valence of m 21; m' is an element belonging to group IIA or group VA of the periodic Table, a transition element or aluminum; n21 is an integer of 1 to 3 inclusive; in the case where n21 is 2 or 3, a plurality of R's are present 21 A plurality of R 22 And a plurality of Y 21 Each of which may be the same or different; m21 is 2 or 3; x is 1 or 2; in the case where x is 2, a plurality of M's may be the same or different; n21, x, and m21 are integers satisfying a relation of 2×n21=m21×x.
12. The polyamide composition as claimed in claim 5, wherein the phosphorus-containing flame retardant (B) contains at least one phosphinate selected from the group consisting of phosphinates represented by the following general formula (1), diphosphinates represented by the following general formula (2) and condensates thereof,
Figure FDA0004153132180000042
Figure FDA0004153132180000051
In the general formula (1), R 11 And R is 12 Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; m is M n11+ A metal ion of valence n 11; m is an element belonging to group IIA or group VA of the periodic Table, a transition element or aluminum; n11 is 2 or 3; in the case where n11 is 2 or 3, a plurality of R's are present 11 And a plurality of R 12 Each of which may be the same or different;
in the general formula (2), R 21 And R is 22 Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; y is Y 21 An alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms; m's' x m21+ A metal ion having a valence of m 21; m' is an element belonging to group IIA or group VA of the periodic Table, a transition element or aluminum; n21 is an integer of 1 to 3 inclusive; in the case where n21 is 2 or 3, a plurality of R's are present 21 A plurality of R 22 And a plurality of Y 21 Each of which may be the same or different; m21 is 2 or 3; x is 1 or 2; in the case where x is 2, a plurality of M's may be the same or different; n21, x, and m21 are integers satisfying a relation of 2×n21=m21×x.
13. The polyamide composition as claimed in claim 7, wherein the phosphorus-containing flame retardant (B) contains at least one phosphinate selected from the group consisting of phosphinates represented by the following general formula (1), diphosphinates represented by the following general formula (2) and condensates thereof,
Figure FDA0004153132180000052
Figure FDA0004153132180000061
In the general formula (1), R 11 And R is 12 Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; m is M n11+ A metal ion of valence n 11; m is an element belonging to group IIA or group VA of the periodic Table, a transition element or aluminum; n11 is 2 or 3; in the case where n11 is 2 or 3, a plurality of R's are present 11 And a plurality of R 12 Each of which may be the same or different;
in the general formula (2), R 21 And R is 22 Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; y is Y 21 An alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms; m's' x m21+ A metal ion having a valence of m 21; m' is an element belonging to group IIA or group VA of the periodic Table, a transition element or aluminum; n21 is an integer of 1 to 3 inclusive; in the case where n21 is 2 or 3, a plurality of R's are present 21 A plurality of R 22 And a plurality of Y 21 Each of which may be the same or different; m21 is 2 or 3; x is 1 or 2; in the case where x is 2, a plurality of M's may be the same or different; n21, x, and m21 are integers satisfying a relation of 2×n21=m21×x.
14. The polyamide composition according to any one of claims 1 to 3, 6, 8, 9, 11 to 13, wherein the content of the phosphorus-containing flame retardant is 0.1 mass% or more and 30 mass% or less relative to the total mass of the polyamide (a), the phosphorus-containing flame retardant (B) and the styrene copolymer (C).
15. The polyamide composition according to claim 4, wherein the content of the phosphorus-containing flame retardant is 0.1 mass% or more and 30 mass% or less relative to the total mass of the polyamide (A), the phosphorus-containing flame retardant (B) and the styrene copolymer (C).
16. The polyamide composition according to claim 5, wherein the content of the phosphorus-containing flame retardant is 0.1 mass% or more and 30 mass% or less relative to the total mass of the polyamide (A), the phosphorus-containing flame retardant (B) and the styrene copolymer (C).
17. The polyamide composition according to claim 7, wherein the content of the phosphorus-containing flame retardant is 0.1 mass% or more and 30 mass% or less relative to the total mass of the polyamide (A), the phosphorus-containing flame retardant (B) and the styrene copolymer (C).
18. The polyamide composition according to claim 10, wherein the content of the phosphorus-containing flame retardant is 0.1 mass% or more and 30 mass% or less relative to the total mass of the polyamide (a), the phosphorus-containing flame retardant (B) and the styrene copolymer (C).
19. The polyamide composition according to any one of claims 1 to 3, 6, 8, 9, 11 to 13, and 15 to 18, wherein the polyamide composition has a tan delta peak temperature of 90 ℃ or higher.
20. The polyamide composition as claimed in claim 4, wherein the polyamide composition has a tan delta peak temperature of 90℃or higher.
21. The polyamide composition according to claim 5, wherein the polyamide composition has a tan delta peak temperature of 90℃or higher.
22. The polyamide composition as claimed in claim 7, wherein the polyamide composition has a tan delta peak temperature of 90 ℃ or higher.
23. The polyamide composition according to claim 10, wherein the polyamide composition has a tan delta peak temperature of 90 ℃ or higher.
24. The polyamide composition according to claim 14, wherein the polyamide composition has a tan delta peak temperature of 90 ℃ or higher.
25. The polyamide composition according to any one of claims 1 to 3, 6, 8, 9, 11 to 13, 15 to 18, and 20 to 24, wherein the weight average molecular weight of the polyamide composition is 10000 or more and 50000 or less.
26. The polyamide composition as claimed in claim 4, wherein the weight average molecular weight of the polyamide composition is 10000 or more and 50000 or less.
27. The polyamide composition according to claim 5, wherein the weight average molecular weight of the polyamide composition is 10000 or more and 50000 or less.
28. The polyamide composition as claimed in claim 7, wherein the weight average molecular weight of the polyamide composition is 10000 or more and 50000 or less.
29. The polyamide composition according to claim 10, wherein the weight average molecular weight of the polyamide composition is 10000 or more and 50000 or less.
30. The polyamide composition according to claim 14, wherein the weight average molecular weight of the polyamide composition is 10000 or more and 50000 or less.
31. The polyamide composition as claimed in claim 19, wherein the polyamide composition has a weight average molecular weight of 10000 or more and 50000 or less.
32. The polyamide composition of any one of claims 1-3, 6, 8, 9, 11-13, 15-18, 20-24, 26-31, wherein the polyamide composition further comprises at least one (D) filler material.
33. The polyamide composition of claim 4 wherein said polyamide composition further comprises at least one (D) filler material.
34. The polyamide composition of claim 5 wherein the polyamide composition further comprises at least one (D) filler material.
35. The polyamide composition of claim 7 wherein the polyamide composition further comprises at least one (D) filler material.
36. The polyamide composition of claim 10 wherein the polyamide composition further comprises at least one (D) filler material.
37. The polyamide composition of claim 14 wherein the polyamide composition further comprises at least one (D) filler material.
38. The polyamide composition of claim 19 wherein the polyamide composition further comprises at least one (D) filler material.
39. The polyamide composition of claim 25 wherein the polyamide composition further comprises at least one (D) filler material.
40. A molded article obtained by molding the polyamide composition according to any one of claims 1 to 39.
41. A process for producing a polyamide composition according to any one of claims 1 to 39, wherein,
the raw material components comprising the polyamide (A), the phosphorus-containing flame retardant (B) and the styrene copolymer (C) are melt-kneaded.
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