CN117396559A - Polyamide composition - Google Patents

Polyamide composition Download PDF

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Publication number
CN117396559A
CN117396559A CN202280038893.1A CN202280038893A CN117396559A CN 117396559 A CN117396559 A CN 117396559A CN 202280038893 A CN202280038893 A CN 202280038893A CN 117396559 A CN117396559 A CN 117396559A
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Prior art keywords
polyamide
polyolefin
polyamide composition
pipe
acid
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Chinese (zh)
Inventor
关口健治
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Kuraray Co Ltd
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Kuraray Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • 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
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • 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

Abstract

The present invention relates to a polyamide composition comprising a polyamide, a polyolefin and a copper-based stabilizer, the polyolefin comprising at least one polyolefin (A) comprising a copolymer of ethylene, an alkyl (meth) acrylate and an unsaturated epoxide and at least one polyolefin (B) comprising an unsaturated dicarboxylic anhydride, and the content [ B ]]Content with the polyolefin (A) [ A ]]Mass ratio [ B ]]/[A]The value Z calculated according to the following formula (1) is 33 to 200, and is 0.1 to 2.9. Z=1000× (| [ ANH)]－[EPO]|+[EPO])/X 2 The [ EPO ] of the formula (1)]Is the concentration per unit mass (mmol/kg) of unsaturated epoxide from the polyolefin in the composition. The [ ANH ]]Concentration of unsaturated dicarboxylic anhydride from the polyolefin per unit mass of the compositionDegree (mmol/kg). The X is the content (mass%) of polyolefin in the composition.

Description

Polyamide composition
Technical Field
The present invention relates to a polyamide composition having excellent heat resistance, flexibility, impact resistance, processing stability and whitening resistance.
Background
Polyamide resins are excellent in strength, heat resistance, chemical resistance, and the like, and have been used in automotive fuel pipes, fuel pipe joints (joints), and other automotive mechanism parts. Polyamide resin compositions are also used, for example, in long-acting coolant for cooling an automobile engine, and in pipes for circulating a refrigerant for cooling an air conditioner. For the above-mentioned pipe, aliphatic polyamides such as polyamide 12, polyamide 11, polyamide 6 and the like are widely used from the viewpoints of ease of extrusion molding and flexibility. On the other hand, these aliphatic polyamides are pointed out to have problems such as insufficient chemical resistance and insufficient heat resistance. In particular, in recent years, in order to improve the energy consumption efficiency of automobiles, the resinification of pipes through which cooling water, high-temperature gas, and oil flow has been actively studied, and materials having heat resistance and impact resistance superior to those of conventional pipes have been desired.
Patent document 1 discloses that a pipe having a specific phase separation structure, which includes a semiaromatic polyamide and a modified elastomer, exhibits excellent surface smoothness and flexibility. In addition, it is considered that the concentration of the functional group of the elastomer used in the above tube is preferably within a specific range.
Patent document 2 discloses a composition comprising a semiaromatic polyamide, a specific polyolefin and a plasticizer, which exhibits excellent flexibility, heat aging resistance and impact resistance.
Prior art literature
Patent literature
Patent document 1: international publication No. 2020/175290
Patent document 2: japanese patent application laid-open No. 2015-501341
Disclosure of Invention
Problems to be solved by the invention
It has been previously known that flexibility and impact resistance are imparted by blending a polyamide with a polyolefin containing a functional group reactive with the polyamide. In this case, the dispersibility can be improved by increasing the concentration of the functional group to increase the affinity of the polyolefin for the polyamide, but there are problems that the viscosity of the composition increases and the molding processability decreases. On the other hand, it is pointed out that when the concentration of the functional group is reduced, the affinity of the polyolefin for the polyamide is reduced, and a reduction in processability such as bleeding out of a part of the polyolefin occurs during melt kneading. It is also pointed out that the surface whitens when a molded body using a composition comprising polyamide and polyolefin is subjected to 2 times of processing, and the quality of the product is reduced.
Accordingly, an object of the present invention is to provide a polyamide composition having excellent heat resistance, flexibility, impact resistance, processing stability, and whitening resistance, a method for producing the same, use of the polyamide composition, and a molded article using the polyamide composition.
Means for solving the problems
The present inventors have conducted intensive studies and as a result, have found that a polyamide composition excellent in heat resistance, flexibility, impact resistance, processing stability and whitening resistance can be obtained by melt-kneading a polyamide, a specific polyolefin and a copper-based stabilizer, and have further conducted intensive studies based on the findings, thereby completing the present invention.
Namely, the present invention is as follows.
[1] A polyamide composition comprising a polyamide, a polyolefin and a copper-based stabilizer,
the polyolefin comprises at least one polyolefin (A) and at least one polyolefin (B), the polyolefin (A) comprises a copolymer of ethylene, an alkyl (meth) acrylate and an unsaturated epoxide, the polyolefin (B) comprises an unsaturated dicarboxylic anhydride, and the mass ratio [ B ]/[ A ] of the content [ B ] of the polyolefin (B) to the content [ A ] of the polyolefin (A) is 0.1 to 2.9,
the value Z calculated according to the following formula (1) is 33 to 200.
Z＝1000×(|[ANH]-[EPO]|+[EPO])/X 2 (1)
The above [ EPO ] is the concentration (mmol/kg) of the unsaturated epoxide derived from the above polyolefin per unit mass of the above composition.
The term [ ANH ] is the concentration (mmol/kg) of the unsaturated dicarboxylic anhydride derived from the polyolefin per unit mass of the composition.
The above X is the content (mass%) of polyolefin in the above composition.
[2] The polyamide composition according to item [1], wherein the polyamide contains 50 mol% or more of at least one selected from terephthalic acid units and naphthalene dicarboxylic acid units, relative to all dicarboxylic acid units.
[3] The polyamide composition according to the item [1] or [2], wherein the polyamide contains 60 mol% or more of an aliphatic diamine unit having 4 to 13 carbon atoms or a m-xylylenediamine unit based on the total diamine units.
[4] The polyamide composition according to the item [3], wherein the aliphatic diamine unit is a unit derived from at least one aliphatic diamine selected from the group consisting of 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 9-nonanediamine, 2-methyl-1, 8-octanediamine and 1, 10-decanediamine.
[5] The polyamide composition according to the item [3] or [4], wherein the aliphatic diamine unit is a unit derived from at least one aliphatic diamine selected from the group consisting of 1, 9-nonanediamine and 2-methyl-1, 8-octanediamine.
[6] The polyamide composition according to any one of the above [1] to [5], wherein the polyamide has a polydispersity index of 3.7 or more as measured by gel permeation chromatography, the content of terminal amino groups in the polyamide is 10 to 70. Mu. Eq/g, and the content of terminal carboxyl groups is 10 to 70. Mu. Eq/g.
[7] The polyamide composition as described in any one of the above [1] to [6], wherein the polyolefin content is 14 to 40% by mass.
[8] The polyamide composition as described in any one of the above [1] to [7], wherein the polyolefin content is 15 to 30% by mass.
[9] The polyamide composition as described in any one of the above [1] to [8], wherein the polyolefin (B) is a copolymer of ethylene, an alkyl (meth) acrylate and an unsaturated dicarboxylic anhydride.
[10] The polyamide composition as described in any one of the above [1] to [9], wherein the content of the copper-based stabilizer is 0.01 to 2% by mass.
[11] The polyamide composition as described in any one of [1] to [10], wherein the copper-based stabilizer comprises at least one copper compound selected from copper iodide, copper bromide and copper acetate and at least one metal halide selected from potassium iodide and potassium bromide.
[12] The polyamide composition as described in any one of [1] to [11], which comprises at least one additive selected from the group consisting of polymers other than the polyamide and the polyolefin, antioxidants, fillers, crystal nucleating agents, colorants, antistatic agents, plasticizers, lubricants, flame retardants and flame retardant aids.
[13] A process for producing a polyamide composition as described in any one of the above [1] to [12],
the polyamide, the polyolefin and the copper stabilizer were fed to a twin-screw extruder at the top and melt kneaded.
[14] The polyamide composition as described in any one of [1] to [12], which is used for producing a single-layer structure or at least 1 layer in a multilayer structure.
[15] A molded article comprising the polyamide composition according to any one of the above [1] to [12 ].
[16] The molded article according to [15] above, which is an extrusion molded article, a co-extrusion molded article or a blow molded article.
[17] The molded article according to item [16] above, which is a fuel pipe, an engine coolant pipe, a battery coolant pipe, an electric motor coolant pipe, a fuel cell coolant pipe, a urea solution transport pipe, an air conditioning refrigerant pipe, a blowby pipe, a brake booster pipe, a brake pipe, an oil cooling pipe, a turbine pipe, an air suspension pipe, or a petroleum transportation pipe.
Effects of the invention
According to the present invention, a polyamide composition having excellent heat resistance, flexibility, impact resistance, processing stability, and whitening resistance, a method for producing the same, use of the polyamide composition, and a molded article using the polyamide composition can be provided.
Detailed Description
Further features, modes, advantages of the present invention will become apparent from the following detailed description and examples.
In addition, preferred embodiments of the present invention are given in the present specification, and a combination of two or more of the preferred embodiments is also preferred. Regarding matters represented in numerical ranges, in the case where there are several numerical ranges, their lower limit values and upper limit values may be selectively combined as a preferable mode. For example, the expression "XX to YY" means "XX or more and YY or less". In addition, "-units" (herein "-" means monomers) means "structural units derived from #". For example, "dicarboxylic acid unit" means "structural unit derived from dicarboxylic acid". "diamine unit" means "structural unit derived from diamine". In addition, "(meth) acrylate" means "acrylate" and "methacrylate" corresponding thereto.
Further, "tube" means a tubular structure such as a tube, a hose, or the like.
Polyamide composition
[ Polyamide ]
The polyamide composition of the present embodiment comprises at least one polyamide.
The polyamide comprises at least one repeating unit formed by polycondensation of dicarboxylic acid units and diamine units.
Examples of the dicarboxylic acid unit include aromatic dicarboxylic acid units such as terephthalic acid units, naphthalene dicarboxylic acid units, isophthalic acid units, 1, 4-phenylene dioxydiacetic acid units, 1, 3-phenylene dioxydiacetic acid units, diphenic acid units, diphenylmethane-4, 4' -dicarboxylic acid units, diphenylsulfone-4, 4' -dicarboxylic acid units, and 4,4' -biphenyl acid units.
Examples of the naphthalene dicarboxylic acid unit include units derived from 2, 6-naphthalene dicarboxylic acid, 2, 7-naphthalene dicarboxylic acid and 1, 4-naphthalene dicarboxylic acid, and preferably 2, 6-naphthalene dicarboxylic acid units.
Examples of the dicarboxylic acid unit include aliphatic dicarboxylic acids derived from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, dimethylmalonic acid, 2-diethylsuccinic acid, 2-dimethylglutaric acid, 2-methyladipic acid, trimethyladipic acid, and dimer acid; units of alicyclic dicarboxylic acids such as 1, 3-cyclopentanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid, cyclooctanedicarboxylic acid, and cyclodecane dicarboxylic acid.
These units derived from dicarboxylic acids may be contained in one kind or two or more kinds.
The polyamide used in the present invention preferably contains 50 mol% or more of at least one selected from terephthalic acid units and naphthalene dicarboxylic acid units, relative to the total dicarboxylic acid units. In addition, from the viewpoint of being a polyamide excellent in chemical resistance and heat resistance, the polyamide used in the present invention preferably contains 75 mol% or more of at least one selected from terephthalic acid units and naphthalene dicarboxylic acid units, and more preferably contains 90 mol% or more, based on the total dicarboxylic acid units.
Examples of the diamine unit include linear aliphatic diamines derived from ethylenediamine, 1, 2-propylenediamine, 1, 3-butylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexamethylenediamine, 1, 7-heptylenediamine, 1, 8-octylenediamine, 1, 9-nonylenediamine, 1, 10-decylenediamine, 1, 11-undecylenediamine, 1, 12-dodecylenediamine, and 1, 13-tetradecylenediamine; branched aliphatic diamines such as 2-methyl-1, 3-butanediamine, 2-methyl-1, 5-pentanediamine, 3-methyl-1, 5-pentanediamine, 2, 4-trimethyl-1, 6-hexanediamine, 2, 4-trimethyl-1, 6-hexanediamine, 2-methyl-1, 8-octanediamine, and 5-methyl-1, 9-nonanediamine; alicyclic diamines such as cyclohexanediamine, methylcyclohexamethylenediamine and isophoronediamine; and aromatic diamines such as p-phenylenediamine, m-phenylenediamine, xylylenediamine, 4' -diaminodiphenylmethane, 4' -diaminodiphenylsulfone, and 4,4' -diaminodiphenylether.
These units derived from diamine may be contained in one kind or two or more kinds.
The polyamide used in the present invention preferably contains 60 mol% or more of an aliphatic diamine unit having 4 to 13 carbon atoms or a m-xylylenediamine unit relative to the total diamine units. When a polyamide containing an aliphatic diamine unit having 4 to 13 carbon atoms in the above-mentioned ratio is used, a polyamide composition excellent in toughness, heat resistance, chemical resistance and lightweight can be obtained. The polyamide used in the present invention preferably contains 75 mol% or more of at least one kind of aliphatic diamine unit selected from the group consisting of 4 to 13 carbon atoms, and more preferably contains 90 mol% or more of the entire diamine units.
The aliphatic diamine unit having 4 to 13 carbon atoms is more preferably a unit derived from at least one aliphatic diamine selected from the group consisting of 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 9-nonanediamine, 2-methyl-1, 8-octanediamine and 1, 10-decanediamine. The aliphatic diamine unit having 4 to 13 carbon atoms is more preferably a unit derived from at least one aliphatic diamine selected from the group consisting of 1, 9-nonanediamine and 2-methyl-1, 8-octanediamine, and further preferably a 1, 9-nonanediamine unit and 2-methyl-1, 8-octanediamine unit, from the viewpoint that a polyamide composition having more excellent heat resistance, low water absorption and chemical resistance can be obtained.
In the case where the aliphatic diamine unit contains units derived from both 1, 9-nonanediamine and 2-methyl-1, 8-octanediamine, the molar ratio of 1, 9-nonanediamine units to 2-methyl-1, 8-octanediamine units is preferably in the range of 1, 9-nonanediamine units/2-methyl-1, 8-octanediamine units=95/5 to 40/60, more preferably in the range of 90/10 to 40/60, and even more preferably in the range of 80/20 to 40/60.
The polyamide used in the present invention may comprise aminocarboxylic acid units and/or lactam units.
Examples of the aminocarboxylic acid unit include units derived from 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like. More than two aminocarboxylic acid units may be included. The content of the aminocarboxylic acid unit in the polyamide is preferably 50 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less, based on 100 mol% of the total monomer units constituting the polyamide.
Examples of the lactam unit include units derived from epsilon-caprolactam, enantholactam, undecanolactam, laurolactam, alpha-pyrrolidone, alpha-piperidone, and the like, and may contain two or more kinds of lactam units. The content of the lactam unit in the polyamide is preferably 50 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less, based on 100 mol% of the total monomer units constituting the polyamide.
In the present embodiment, the polyamide is preferably a semiaromatic polyamide containing a dicarboxylic acid unit mainly composed of an aromatic dicarboxylic acid unit and a diamine unit mainly composed of an aliphatic diamine unit having 4 to 13 carbon atoms.
The term "main component" as used herein means 50 to 100 mol%, preferably 60 to 100 mol%, more preferably 80 to 100 mol% of the total unit.
Typical semiaromatic polyamides include polybutylene terephthalate (polyamide 4T), polybutylene terephthalate (polyamide 5T), polybutylene terephthalate (polyamide 6T), polybutylene terephthalate (polyamide 9T), polybutylene terephthalate (polyamide 2-methyl-octanediamine) (nylon M8T), polybutylene terephthalate/polybutylene terephthalate 2-methyl-octanediamine copolymer (nylon 9T/M8T), polybutylene terephthalate (polyamide 9N), polybutylene terephthalate/polybutylene terephthalate 2-methyl-octanediamine copolymer (nylon 9N/M8N), polybutylene terephthalate (polyamide 10T), polybutylene terephthalate (polyamide 6I), copolymers of polyamide 6I and polyamide 6T (polyamide 6I/6T), copolymers of polyamide 66 and polyamide 6T (polyamide 66/polyamide 6I/6T), copolymers of polyamide 6T and polyamide 11 (polyamide 11/polyamide 11) and the like.
Among them, at least one selected from the group consisting of polyamide 10T/11, polynaphthalenenonanediamine (polyamide 9N), polynaphthalenenonanediamine/polynaphthalene2-methyl octanediamine copolymer (polyamide 9N/M8N), polyparaphenylene terephthalonamine (polyamide 9T), polyparaphenylene terephthalonamine/polyparaphenylene terephthalamide 2-methyl octanediamine copolymer (polyamide 9T/M8T) and polyparaphenylene terephthalamide (polyamide 10T) is preferable, and at least one selected from the group consisting of polynaphthalenenonanediamine/polynaphthalenedicarboxylic acid 2-methyl octanediamine copolymer (polyamide 9N/M8N), polyparaphenylene terephthalamide/polyparaphenylene terephthalamide 2-methyl octanediamine copolymer (polyamide 9T/M8T) and polyamide 10T/11 is more preferable from the viewpoint of securing molding processability and rigidity at high temperature.
In addition, a semiaromatic polyamide containing a dicarboxylic acid unit mainly composed of an aliphatic dicarboxylic acid unit and a diamine unit mainly composed of an aromatic diamine unit may be used as the polyamide. The aliphatic dicarboxylic acid unit may be a unit derived from the aforementioned aliphatic dicarboxylic acid, and may include one or two or more of them. The aromatic diamine unit may be a unit derived from the aforementioned aromatic diamine, and may include one or two or more of them. In addition, other units may be included within a range that does not hinder the effects of the present invention.
Typical semiaromatic polyamides containing dicarboxylic acid units mainly composed of aliphatic dicarboxylic acid units and diamine units mainly composed of aromatic diamine units include poly (m-xylylenediamine-adipamide) (MXD 6), poly (p-xylylenediamine-sebacamide) (PXD 10), and the like.
In addition, aliphatic polyamides may also be used as polyamides.
Examples of the aliphatic polyamide include polycaprolactone (polyamide 6), polyundecamide (polyamide 11), polydodecyl amide (polyamide 12), polytetramethylene adipamide (polyamide 46), polyhexamethylene adipamide (polyamide 66), polyhexamethylene adipamide (polyamide 92), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecanoamide (polyamide 612), polyhexamethylene sebacamide (polyamide 910), polyhexamethylene dodecanoamide (polyamide 912), polyhexamethylene sebacamide (polyamide 1010), polydodecanecanoamide (polyamide 1012), polydodecanecanoamide (polyamide 1210), and polydodecanecanoamide (polyamide 1212).
The polyamide used in the present invention is preferably one in which 10 mol% or more of the polyamide is blocked with a blocking agent with respect to the total terminal groups of the molecular chain. When a polyamide having a blocking ratio of 10 mol% or more is used, a polyamide composition having more excellent properties such as melt stability and hot water resistance can be obtained.
As the capping agent, a monofunctional compound having reactivity with a terminal amino group or a terminal carboxyl group can be used. Specifically, monocarboxylic acids, anhydrides, monoisocyanates, monoacylhalides, monoesters, monoalcohols, monoamines, and the like can be mentioned. From the viewpoints of reactivity, blocking stability, and the like, monocarboxylic acids are preferable as the blocking agent for the terminal amino group, and monoamines are preferable as the blocking agent for the terminal carboxyl group. From the viewpoint of ease of handling, etc., monocarboxylic acids are more preferable as the blocking agent.
The monocarboxylic acid used as the blocking agent is not particularly limited as long as it has reactivity with an amino group. Examples of the monocarboxylic acid include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclopentanecarboxylic acid and cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, α -naphthoic acid, β -naphthoic acid, methylnaphthoic acid and phenylacetic acid; mixtures of any of these, and the like. Among them, at least one selected from acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid and benzoic acid is preferable from the viewpoints of reactivity, stability of end capping, price and the like.
The monoamine used as the blocking agent is not particularly limited as long as it has reactivity with a carboxyl group. Examples of the monoamine include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine, and the like; mixtures of any of these, and the like. Among them, at least one selected from butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline is preferable from the viewpoints of reactivity, boiling point, stability of end capping, price, and the like.
The polyamide used in the present invention has an intrinsic viscosity [ eta ] measured at a concentration of 0.2g/dl and a temperature of 30℃using concentrated sulfuric acid as a solvent inh ]Preferably 0.6dl/g or more, more preferably 0.8dl/g or more, and still more preferably 1.0dl/g or more. The intrinsic viscosity is preferably 2.0dl/g or less, more preferably 1.8dl/g or less, and still more preferably 1.6dl/g or less. If the inherent viscosity [ eta ] of the polyamide inh ]Within the above range, various physical properties such as moldability are further improved. Intrinsic viscosity [ eta ] inh ]Can be based on the flow-down time t of the solvent (concentrated sulfuric acid) 0 (seconds), time t of flow of sample solution 1 (seconds) and the sample concentration c (g/dl) (i.e., 0.2 g/dl) in the sample solution, using eta inh ＝[ln(t 1 /t 0 )]The relation of/c.
The terminal amino group content (hereinafter also referred to as "terminal amino group content") of the polyamide used in the present invention (NH 2 ]) Preferably 10 to 70. Mu. Eq/g, more preferably 10 to 65. Mu. Eq/g, still more preferably 10 to 60. Mu. Eq/g. If the terminal amino content ([ NH) 2 ]) When the amount is 10. Mu. Eq/g or more, the polyamide has good compatibility with polyolefin described later. In addition, when the terminal amino group content is 70. Mu. Eq/g or less, gelation promotion due to excessive reaction between the terminal amino group and a modified portion of polyolefin can be avoided in the case of using a modified polyolefin described later as polyolefin.
The terminal amino content ([ NH ] as referred to in the present specification 2 ]) Refers to the amount of terminal amino groups contained in 1g of polyamide (unit: μeq) can be obtained by a neutralization titration method using an indicator.
The content of terminal carboxyl groups (hereinafter also referred to as "terminal carboxyl groups content") ([ COOH ]) of the polyamide used in the present invention is preferably 10 to 70. Mu. Eq/g, more preferably 12 to 65. Mu. Eq/g, still more preferably 14 to 60. Mu. Eq/g. When the terminal carboxyl group content ([ COOH ]) is 10. Mu. Eq/g or more, the polyamide has good compatibility with polyolefin described later. In addition, when the terminal carboxyl group content is 70. Mu. Eq/g or less, gelation promotion due to excessive reaction between the terminal carboxyl group and a modified portion of polyolefin can be avoided in the case of using a modified polyolefin described later as polyolefin.
The terminal carboxyl group content ([ COOH ]) referred to herein refers to the amount of terminal carboxyl groups (unit/. Mu.eq) contained in 1g of the polyamide, and can be determined by a neutralization titration method using an indicator.
Comprising dicarboxylic acid units and diamine units, and having a terminal amino group content ([ NH ] 2 ]) Terminal carboxyl content ([ COOH)]) Polyamides in the above-described range can be produced, for example, as follows.
First, a dicarboxylic acid, a diamine, and if necessary, an aminocarboxylic acid, a lactam, a catalyst, and a capping agent are mixed to prepare a nylon salt. In this case, if the molar number (X) of all carboxyl groups and the molar number (Y) of all amino groups contained in the above-mentioned reaction raw materials satisfy the following formula (Q) for calculating the excess value, the terminal amino group content ([ NH ] can be easily produced 2 ]) Terminal carboxyl content ([ COOH)]) Polyamides in the range of 10 to 70. Mu. Eq/g are preferred.
-0.5-2.0 [ (Y-X)/Y ]. Times.100 ]
Then, the nylon salt is heated to a temperature of 200-250 ℃ to prepare the intrinsic viscosity [ eta ] of 30 ℃ in concentrated sulfuric acid inh ]A prepolymer having a concentration of 0.10 to 0.60dl/g is further increased in polymerization degree, whereby a polyamide can be obtained. If the intrinsic viscosity [ eta ] of the prepolymer inh ]When the amount is in the range of 0.10 to 0.60dl/g, a polyamide having a small decrease in polymerization rate, a small molecular weight distribution, various properties and more excellent moldability can be obtained due to a small deviation in the molar balance between carboxyl groups and amino groups in the stage of increasing the polymerization degree. In the case of carrying out the stage of increasing the polymerization degree by the solid-phase polymerization method, it is preferable to carry out the polymerization under reduced pressure or under inert gas flow, and if the polymerization temperature is in the range of 200 to 280 ℃, the polymerization rate is high, the productivity is excellent, and coloring and gelation can be effectively suppressed. In the case of a stage of increasing the polymerization degree by using a melt extruder, the polymerization temperature is preferably the same as that of the melt extruder When the polymerization is carried out at 370℃or below, there is substantially no decomposition of the polyamide, and a polyamide with little deterioration can be obtained.
< Polyamide content >
The content of the polyamide contained in the polyamide composition of the present embodiment is preferably 60 to 86 mass%, more preferably 65 to 86 mass%, even more preferably 70 to 86 mass%, and still more preferably 70 to 80 mass%, relative to 100 mass% of the polyamide composition. When the content of the polyamide is within the above range, a polyamide composition having more excellent heat resistance, and further excellent processing stability, flexibility and impact resistance at the time of melt kneading can be obtained.
< polydispersity index >
The polyamide contained in the polyamide composition of the present embodiment preferably has a polydispersity index Mw/Mn (Mw is a weight average molecular weight, mn is a number average molecular weight) of 3.7 or more, or may have a polydispersity index of 4.0 or more. When the polydispersity index is 3.7 or more, a composition excellent in melt tension at the time of extrusion molding can be obtained. In addition, the polydispersity Mw/Mn of the polyamide is preferably 8.0 or less. When the polydispersity index is 8.0 or less, a composition excellent in fluidity at the time of extrusion molding can be obtained.
The polydispersity index of the polyamide may be determined by gel permeation chromatography, more specifically, by the method described in the examples.
Examples of the catalyst that can be used in the production of the polyamide include phosphoric acid, phosphorous acid, hypophosphorous acid, and salts and esters thereof. Examples of the salts or esters include salts of phosphoric acid, phosphorous acid, or hypophosphorous acid with metals such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony; ammonium salts of phosphoric acid, phosphorous acid or hypophosphorous acid; ethyl, isopropyl, butyl, hexyl, isodecyl, octadecyl, decyl, stearyl, phenyl, etc. phosphates, phosphites or phosphinates.
The amount of the catalyst to be used is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, still more preferably 1.0 mass% or less, and still more preferably 0.5 mass% or less, based on 100 mass% of the total mass of the raw materials. If the amount of the catalyst used is not less than the lower limit, polymerization proceeds satisfactorily. If the amount is less than the upper limit, impurities derived from the catalyst are less likely to occur, and for example, in the case of extrusion molding of a polyamide composition, defects due to the impurities can be prevented.
[ polyolefin ]
The polyamide composition of the present embodiment comprises polyamide and polyolefin in the form of a phase dispersed in polyamide as a matrix.
The polyolefin contains: at least one polyolefin (a) comprising a copolymer of ethylene, an alkyl (meth) acrylate and an unsaturated epoxide; and at least one polyolefin (B) comprising an unsaturated dicarboxylic anhydride.
The total content of the polyolefin (a) and the polyolefin (B) in the polyolefin is preferably 80 mass% or more, more preferably 90 mass% or more, still more preferably 95 mass% or more, and may be substantially 100 mass%.
< polyolefin (A) >
The polyolefin (A) contains a copolymer of ethylene, an alkyl (meth) acrylate and an unsaturated epoxide. In addition, from the viewpoint of avoiding gelation due to intramolecular reaction, it is desirable that the polyolefin (a) does not contain an unsaturated dicarboxylic anhydride.
Examples of the unsaturated epoxide include the following epoxides: aliphatic glycidyl ethers and esters such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate, glycidyl itaconate, glycidyl acrylate and glycidyl methacrylate; alicyclic glycidyl ethers and esters such as 2-cyclohexen-1-yl glycidyl ether, cyclohexene-4, 5-dicarboxylic acid diglycidyl ester, cyclohexene-4-carboxylic acid glycidyl ester, 5-norbornene-2-methyl-2-carboxylic acid glycidyl ester and endo-cis-bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxylic acid diglycidyl ester.
The alkyl (meth) acrylate preferably contains 2 to 10 carbon atoms.
Examples of the alkyl (meth) acrylate include methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate.
Particularly preferred examples of the polyolefin (a) include a copolymer of ethylene, methyl acrylate and glycidyl methacrylate, and a copolymer of ethylene, butyl acrylate and glycidyl methacrylate. As the polyolefin (a), commercially available products may be used, and for example, the product names Lotader AX8900, lotader AX8750, lotader AX8390 sold by SK global chemical may be used.
< polyolefin (B) >
The polyolefin (B) is a polymer containing an unsaturated dicarboxylic anhydride. The unsaturated dicarboxylic anhydride is incorporated into the polymer by either grafting or copolymerization. In addition, it is desirable that the polyolefin (B) does not contain an unsaturated epoxide in order to avoid gelation due to intramolecular reaction.
Examples of the unsaturated dicarboxylic anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride.
Further, as the polyolefin (B), for example, a modified polyolefin obtained by modifying an α -olefin copolymer, (ethylene and/or propylene)/(α, β -unsaturated carboxylic acid and/or unsaturated carboxylic acid ester) copolymer, an ionomer, or an aromatic vinyl compound/conjugated diene compound block copolymer (hereinafter, sometimes referred to as "copolymer or the like") with an unsaturated dicarboxylic acid anhydride can be used.
The above copolymers may be used singly or in combination of two or more.
Examples of the α -olefin copolymer include a copolymer of ethylene and an α -olefin having 3 or more carbon atoms and a copolymer of propylene and an α -olefin having 4 or more carbon atoms.
Examples of the α -olefin having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-hexene, 4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. One or two or more kinds of them may be used.
In addition, it is also possible to copolymerize polyenes of non-conjugated dienes such as 1, 4-pentadiene, 1, 4-hexadiene, 1, 5-hexadiene, 1, 4-octadiene, 1, 5-octadiene, 1, 6-octadiene, 1, 7-octadiene, 2-methyl-1, 5-hexadiene, 6-methyl-1, 5-heptadiene, 7-methyl-1, 6-octadiene, 4-ethylidene-8-methyl-1, 7-nonadiene, 4, 8-dimethyl-1, 4, 8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2, 3-diisopropylidene-5-norbornene, 2-propenyl-2, 5-norbornadiene and the like. One or two or more kinds of them may be used.
The above-mentioned (ethylene and/or propylene)/(α, β -unsaturated carboxylic acid and/or unsaturated carboxylic acid ester) copolymer is a polymer obtained by copolymerizing ethylene and/or propylene with an α, β -unsaturated carboxylic acid and/or unsaturated carboxylic acid ester. Examples of the α, β -unsaturated carboxylic acid include acrylic acid and methacrylic acid. Examples of the α, β -unsaturated carboxylic acid esters include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl esters of the unsaturated carboxylic acids. One or two or more kinds of them may be used.
The ionomer is a polymer obtained by ionizing at least a part of carboxyl groups in a copolymer of an olefin and an α, β -unsaturated carboxylic acid by neutralization with metal ions. Ethylene is preferably used as the olefin, and acrylic acid and methacrylic acid are preferably used as the α, β -unsaturated carboxylic acid, but the present invention is not limited to the compounds exemplified herein. For the above copolymer of an olefin and an α, β -unsaturated carboxylic acid, an unsaturated carboxylic acid ester may be further copolymerized as a monomer. The metal ion may be an alkali metal such as Li, na, K, mg, ca, sr, ba or an alkaline earth metal, or Al, sn, sb, ti, mn, fe, ni, cu, zn, cd. One or two or more kinds of them may be used.
The aromatic vinyl compound/conjugated diene compound block copolymer is a block copolymer comprising an aromatic vinyl compound polymer block and a conjugated diene polymer block, and a block copolymer having at least one aromatic vinyl compound polymer block and at least one conjugated diene polymer block can be used. In the block copolymer, the unsaturated bond in the conjugated diene polymer block may be hydrogenated.
The aromatic vinyl compound polymer block is a polymer block mainly composed of structural units derived from an aromatic vinyl compound. Examples of the aromatic vinyl compound in this case include styrene, α -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2, 4-dimethylstyrene, vinylnaphthalene, vinylanthracene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, and 4- (phenylbutyl) styrene, and one or more of them may be used. The aromatic vinyl compound polymer block may have a small amount of structural units formed of other unsaturated monomers, as the case may be. The conjugated diene polymer block is a polymer block formed of one or two or more conjugated diene compounds such as butadiene, chloroprene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, 4-methyl-1, 3-pentadiene, and 1, 3-hexadiene. In the hydrogenated aromatic vinyl compound/conjugated diene compound block copolymer, a part or all of the unsaturated bond portion in the conjugated diene polymer block is hydrogenated.
The molecular structure of the aromatic vinyl compound/conjugated diene compound block copolymer and its hydrogenated product may be linear, branched, radial, or any combination thereof. Among them, as the aromatic vinyl compound/conjugated diene compound block copolymer and/or the hydrogenated product thereof, a diblock copolymer in which one aromatic vinyl compound polymer block and one conjugated diene polymer block are bonded in a linear manner, a triblock copolymer in which 3 polymer blocks are bonded in a linear manner in the order of aromatic vinyl compound polymer block-conjugated diene polymer block-aromatic vinyl compound polymer block, or one or more of the hydrogenated products thereof is preferably used. Examples of the aromatic vinyl compound/conjugated diene compound block copolymer and its hydrogenated product include unhydrogenated or hydrogenated styrene/butadiene block copolymer, unhydrogenated or hydrogenated styrene/isoprene/styrene block copolymer, unhydrogenated or hydrogenated styrene/butadiene/styrene block copolymer, unhydrogenated or hydrogenated styrene/isoprene/butadiene/styrene block copolymer, and the like.
The polyolefin (B) is preferably a copolymer of ethylene, an alkyl (meth) acrylate and an unsaturated dicarboxylic anhydride.
The alkyl (meth) acrylate preferably contains 2 to 10 carbon atoms. Examples of the alkyl (meth) acrylate include methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate.
More preferable examples of the polyolefin (B) include a copolymer of ethylene, ethyl acrylate and maleic anhydride and a copolymer of ethylene, butyl acrylate and maleic anhydride. As the polyolefin (B), commercially available products may be used, and for example, the product names Lotader 4700 and Lotader 3410 sold by SK global chemical may be used.
In addition, in the polyolefin (B), even if a part of the maleic anhydride exemplified as the unsaturated dicarboxylic anhydride is partially hydrolyzed, it does not depart from the scope of the present invention.
< mass ratio [ B ]/[ A ] >
The mass ratio [ B ]/[ A ] of the content [ B ] of the polyolefin (B) to the content [ A ] of the polyolefin (A) is 0.1 to 2.9, preferably 0.2 to 2.9, more preferably 0.4 to 2.9, still more preferably 0.5 to 2.9. If the mass ratio [ B ]/[ A ] is less than 0.1, the melt viscosity tends to increase, and the molding processability tends to decrease. If the mass ratio [ B ]/[ A ] is greater than 2.9, it tends to be difficult to achieve both stability at the time of melt kneading and excellent elongation properties.
< polyolefin content >
The content of the polyolefin contained in the polyamide composition of the present embodiment is preferably 14 to 40 mass%, more preferably 15 to 40 mass%, even more preferably 15 to 35 mass%, and still more preferably 15 to 30 mass% relative to 100 mass% of the polyamide composition. When the content of the polyolefin is within the above range, a polyamide composition excellent in processing stability, flexibility and impact resistance at the time of melt kneading can be obtained.
From the viewpoint of improving the flexibility of the molded article comprising the polyamide composition of the present embodiment, the content of the polyolefin is preferably adjusted so that the flexural modulus of the molded article of the polyamide composition measured in accordance with ISO 178 (4 th edition 2001) at 23 ℃ and 50% rh is 2.0GPa or less, more preferably 1.7GPa or less, and still more preferably 1.5GPa or less.
< concentration of functional group >
The polyamide composition of the present embodiment has a value Z calculated from the following formula (1) of 33 to 200, preferably 33 to 150.Z may have a value of 35 to 130. If the value of Z is less than 33, the affinity between the polyamide and the polyolefin may be insufficient, and the stability during melt kneading may be lowered. If the value of Z exceeds 200, the melt viscosity increases, and molding becomes difficult, and flexibility and impact resistance may be insufficient.
In the present specification, the term "functional group" in "functional group concentration" means an epoxy group of an unsaturated epoxide derived from a polyolefin and a carboxyl group and an acid anhydride group of an unsaturated dicarboxylic acid anhydride derived from a polyolefin. The term "functional group concentration" means [ EPO ] and [ ANH ] described below.
(1)
Z＝1000×(|[ANH]-[EPO]|+[EPO])/X 2
In the above formula (1), each of [ EPO ], [ ANH ], and X is as follows.
[ EPO ]: the concentration of unsaturated epoxide from polyolefin per unit mass (mmol/kg) of the polyamide composition.
[ ANH ]: the concentration (mmol/kg) of unsaturated dicarboxylic anhydride from polyolefin per unit mass of the polyamide composition.
X: the content (mass%) of polyolefin in the polyamide composition.
The concentration [ EPO ] of the unsaturated epoxide and the concentration [ ANH ] of the unsaturated dicarboxylic acid in the above formula (1) are calculated according to the following formula (2).
(2)
[ EPO ] or [ ANH ] =100×N×W/M
In the above formula (2), M, W, N are each shown below.
M: molecular weight of unsaturated epoxide or unsaturated dicarboxylic anhydride.
W: the mass% of the unsaturated epoxide or unsaturated dicarboxylic anhydride contained in the polyolefin (A) or the polyolefin (B). W can be measured by a method common to those skilled in the art, such as NMR.
N: the mass% of the polyolefin (A) or the polyolefin (B) per unit mass of the polyamide composition.
When the polyamide, the polyolefin having an unsaturated epoxide and the polyolefin having an unsaturated dicarboxylic anhydride are melt-kneaded, the above-mentioned value of Z is useful for predicting the melt stability of the polyamide composition and obtaining a polyamide composition excellent in melt stability and excellent in flexibility and impact resistance. Since the unsaturated epoxide and the unsaturated dicarboxylic anhydride each react with the polyamide to exhibit a compatibilizing effect, the functional groups can react with each other, and therefore, it is considered that the residual amount of the functional groups which can be used in the reaction with the polyamide and the difference between them (| [ ANH ] - [ EPO ] |) are related. However, the two are not completely reacted, and the unsaturated epoxide is highly reactive in that it can react with both the terminal amino group and the terminal carboxyl group of the polyamide, and therefore the molecular terms indicating affinity and reactivity with the polyamide are weighted by the concentration of the unsaturated epoxide. In general, since the melt stability of the polyamide composition tends to decrease as the amount of the polyolefin blended increases, the content X of the polyolefin is placed in the denominator.
The concentration of the unsaturated epoxide and the concentration of the unsaturated dicarboxylic acid anhydride in the polyamide composition are difficult to determine because the terminal amino group, carboxyl group, unsaturated epoxide and unsaturated dicarboxylic acid anhydride of the polyamide react with each other during melt kneading. The value of Z is thus calculated based on the amount of each component used in the polyamide composition.
[ copper-based stabilizer ]
In order to improve the heat aging resistance, the polyamide composition of the present embodiment contains at least one copper-based stabilizer.
The content of the copper-based stabilizer is preferably 0.01 to 2% by mass, more preferably 0.1 to 1.5% by mass, and even more preferably 0.5 to 1.2% by mass, relative to 100% by mass of the polyamide composition. When the content of the copper-based stabilizer is within the above range, a polyamide composition excellent in heat aging resistance and having a small amount of gas generated during extrusion molding can be obtained.
The copper-based stabilizer may be used in the form of a mixture of a copper compound and a metal halide. Regarding the ratio of the copper compound to the metal halide in the polyamide composition, the copper compound and the metal halide are preferably contained in the polyamide composition such that the ratio of the total molar amount of halogen atoms to the total molar amount of copper atoms (halogen/copper) is 2/1 to 50/1. The ratio (halogen/copper) is preferably 3/1 or more, more preferably 4/1 or more, and still more preferably 5/1 or more. The ratio (halogen/copper) is preferably 45/1 or less, more preferably 40/1 or less, and still more preferably 30/1 or less. When the ratio (halogen/copper) is not less than the lower limit, copper deposition and metal corrosion during molding can be more effectively suppressed. When the ratio (halogen/copper) is not more than the upper limit, corrosion of the screw or the like of the molding machine can be more effectively suppressed without impairing mechanical properties such as tensile properties of the resulting polyamide composition.
Examples of the copper compound include copper halide, copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, copper stearate, and copper complexes coordinated to chelating agents such as ethylenediamine and ethylenediamine tetraacetic acid. Examples of the copper halide include copper iodide; copper bromide such as cuprous bromide and cupric bromide; copper chloride such as cuprous chloride, etc. Among these copper compounds, at least one selected from copper halides and copper acetate is preferable, at least one selected from copper iodide, copper bromide, copper chloride and copper acetate is more preferable, and at least one selected from copper iodide, copper bromide and copper acetate is still more preferable, from the viewpoint of excellent heat aging resistance and being capable of suppressing metal corrosion of screw and barrel portion at the time of extrusion. The copper compound may be used alone or in combination of two or more.
As the metal halide, a metal halide not corresponding to the copper compound may be used, and a salt of a group 1 or 2 metal element of the periodic table with halogen is preferable. Examples of the metal halide include potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium chloride, and the like. Among them, at least one selected from potassium iodide and potassium bromide is preferable, and potassium iodide is more preferable, from the viewpoint of excellent high-temperature heat resistance such as heat aging resistance and the like of the obtained polyamide composition, and the metal corrosion can be suppressed. The metal halides may be used singly or in combination of two or more.
Among the copper compound and the metal halide, the copper-based stabilizer preferably contains at least one copper compound selected from copper iodide, copper bromide and copper acetate and at least one metal halide selected from potassium iodide and potassium bromide.
In order to improve the dispersibility of the copper compound and the metal halide in the polyamide, a dispersant may be used. Examples of the dispersant include higher fatty acids such as lauric acid, palmitic acid, stearic acid, behenic acid, and montanic acid; higher fatty acid metal salts containing higher fatty acids and metals such as aluminum; higher fatty acid amides such as ethylene bisstearamide; waxes such as polyethylene wax; an organic compound having at least one amide group, and the like.
[ other additives ]
The polyamide composition of the present embodiment may contain other additives as needed in addition to the polyamide, polyolefin and copper-based stabilizer described above.
Examples of the other additives include polymers other than the polyamide and polyolefin, antioxidants, fillers, crystal nucleating agents, colorants, antistatic agents, plasticizers, lubricants, flame retardants, flame retardant aids, and the like. These other additives may be used singly or in combination of two or more.
Examples of the other types of polymers include polyether resins such as polyacetal and polyphenylene ether; polysulfone resins such as polysulfone and polyethersulfone; polythioether resins such as polyphenylene sulfide and polythioether sulfone; polyketone resins such as polyether ether ketone and polyallylether ketone; a polynitrile resin such as polyacrylonitrile, polymethacrylonitrile, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and methacrylonitrile-butadiene-styrene copolymer; a polymethacrylate resin such as polymethyl methacrylate and polyethyl methacrylate; polyvinyl ester resins such as polyvinyl acetate; polyvinyl chloride resins such as polyvinylidene chloride, polyvinyl chloride, vinyl chloride-vinylidene chloride copolymer, and vinylidene chloride-methacrylate copolymer; cellulose resins such as cellulose acetate and cellulose butyrate; fluorine-based resins such as polyvinylidene fluoride, polyvinyl fluoride, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer; a polycarbonate resin; polyimide-based resins such as thermoplastic polyimide, polyamideimide, and polyether imide; a thermoplastic polyurethane resin; etc.
The antioxidant is not particularly limited, and one or two or more antioxidants may be used in combination from among amine antioxidants, hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. Among them, an amine antioxidant is preferable as a combination with the copper stabilizer.
Examples of the filler include fibrous fillers such as glass fibers, and powdery fillers such as calcium carbonate, wollastonite, silica alumina, titania, potassium titanate, magnesium hydroxide, and molybdenum disulfide; hydrotalcite, glass flakes, mica, clay, montmorillonite, kaolin and other platy fillers.
The crystallization nucleating agent is not particularly limited as long as it is a substance generally used as a crystallization nucleating agent for polyamide. Examples of the crystal nucleating agent include talc, calcium stearate, aluminum stearate, barium stearate, zinc stearate, antimony oxide, magnesium oxide, and any mixture thereof. Among them, talc is preferable in view of the large effect of increasing the crystallization rate of polyamide. In order to improve the compatibility with polyamide, the crystallization nucleating agent may be treated with a silane coupling agent, a titanium coupling agent, or the like.
The colorant is not particularly limited, and may be appropriately selected from inorganic or organic pigments and dyes according to the use of the polyamide composition. Examples of the colorant to be incorporated into the polyamide composition used in the medical fluid transfer tube include black inorganic pigments such as carbon black, lamp black, acetylene black, bone black, pyrolytic carbon black, channel black, furnace black, and titanium black, as a preferable colorant.
The antistatic agent is not particularly limited, and may be an organic antistatic agent or an inorganic antistatic agent. Examples of the organic antistatic agent include ionic compounds such as lithium ion salts, quaternary ammonium salts, and ionic liquids; and electron conductive polymer compounds such as polythiophene, polyaniline, polypyrrole, and polyacetylene. Examples of the inorganic antistatic agent include metal oxide-based conductive agents such as ATO, ITO, PTO, GZO, antimony pentoxide, and zinc oxide; carbon-based conductive agents such as carbon nanotubes and fullerenes. From the viewpoint of heat resistance, an inorganic antistatic agent is preferable. Carbon black as a colorant may also have a function as an antistatic agent.
The plasticizer is not particularly limited as long as it is a plasticizer generally used as a plasticizer for polyamide. Examples of the plasticizer include benzenesulfonic acid alkylamide compounds, toluenesulfonic acid alkylamide compounds, hydroxybenzoic acid alkyl ester compounds, hydroxybenzoic acid alkylamide compounds, and the like.
The lubricant is not particularly limited as long as it is a lubricant that is generally used as a lubricant for polyamide. Examples of the lubricant include higher fatty acid compounds, oxy fatty acid compounds, fatty acid amide compounds, alkylene bis fatty acid amide compounds, fatty acid lower alcohol ester compounds, metal soap compounds, and polyolefin waxes. Fatty acid amide compounds, for example, various stearates such as calcium stearate, stearic acid amide, palmitic acid amide, methylene distearate amide, ethylene distearate amide and the like are preferable because they are excellent in external lubricity. These lubricants may be added internally or externally to the composition. In particular, when stearate is externally added, the effect of reducing the motor load of the extruder is obtained.
The content of the other additive in the polyamide composition is preferably 50 mass% or less, more preferably 20 mass% or less, and still more preferably 5 mass% or less, relative to 100 mass% of the polyamide composition.
[ method for producing Polyamide composition ]
The polyamide composition of the present embodiment can be produced, for example, by feeding the polyamide, the polyolefin, and the copper-based stabilizer to a twin-screw extruder at the top and melt-kneading the materials.
The method for producing a polyamide composition according to the present embodiment includes a step of melt-kneading the above-described mixture containing polyamide, polyolefin and copper-based stabilizer, and during the melt-kneading, the terminal groups of the polyamide and the modified portions of the polyolefin react with each other, whereby the resulting composition is excellent in flexibility and impact resistance. In addition, by reacting a part of the modified site of the polyolefin (a) with a part of the modified site of the polyolefin (B), a composition excellent in heat resistance can be obtained. In addition, by properly adjusting the concentration and blending ratio of the modified site of polyolefin, a composition excellent in melt-kneading property can be obtained.
The temperature and time during the melt kneading can be appropriately adjusted according to the melting point or the like of the polyamide to be used, and from the viewpoint of suppressing deterioration of the polyolefin, the melt kneading temperature is preferably 380 ℃ or less, more preferably 370 ℃ or less, and still more preferably 360 ℃ or less. The melt kneading time is preferably about 1 to 5 minutes.
The method of melt kneading is not particularly limited, and a method capable of uniformly mixing the polyamide, the polyolefin, the copper-based stabilizer, and other additives used if necessary can be preferably employed. The melt kneader is preferably a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like, and is more preferably a twin-screw extruder from the viewpoints of good dispersibility of polyolefin and copper-based stabilizer and industrial productivity.
As described above, the polyamide composition of the present embodiment can be obtained by reacting the polyamide, the polyolefin (a), and the polyolefin (B) with each other at the time of melt-kneading, and therefore, it is preferable to secure a constant kneading time at the time of melt-kneading. Specifically, when a twin-screw extruder is used as the melt kneading apparatus, it is preferable to feed the polyamide, the polyolefin, the copper-based stabilizer, and other additives added as needed from the first feed port of the start portion of the twin-screw extruder (top feed).
< shaped body >)
The molded article comprising the polyamide composition of the present embodiment can be obtained by molding the polyamide composition by various molding methods such as injection molding, blow molding, extrusion molding, coextrusion molding, coating molding, compression molding, stretch molding, vacuum molding, foam molding, rotational molding, impregnation, laser sintering, and hot melt lamination. Further, the polyamide composition of the present embodiment may be compounded with other polymers to obtain a molded article.
The polyamide composition of the present embodiment has excellent extrusion moldability, coextrusion moldability, blow moldability and coating moldability due to its characteristics, and a molding method using these moldability effectively can be preferably used to obtain a molded article.
< usage >
The molded article of the present embodiment contains the polyamide composition as a main component, and therefore exhibits excellent mechanical properties. In addition, since the polyamide composition contains a specific polyolefin and a copper stabilizer, the polyamide composition is excellent in heat resistance, flexibility and impact resistance.
Therefore, the present invention can be used for automobile parts, internal combustion engine applications, crude oil excavation, transportation applications, electric and electronic parts, medical treatment, foods, home, office supplies, building material related parts, and the like. In particular, since the heat resistance, flexibility and impact resistance are excellent, examples of the hollow body applications include fuel pipes such as a feed pipe, a return pipe, an evaporator pipe, a fuel supply pipe, an ORVR pipe, a storage pipe and a vent pipe; cooling water pipes such as an engine cooling liquid pipe, a battery cooling liquid pipe, an electric motor cooling liquid pipe, a fuel cell cooling pipe and the like; urea solution transporting pipe, air conditioning refrigerant pipe, blowby pipe, brake booster pipe, brake pipe, oil cooling pipe, turbine pipe, air suspension pipe, petroleum transmission pipe, road heating pipe, floor heating pipe, infrastructure supply pipe, fire extinguisher, fire extinguishing equipment pipe, medical cooler material pipe, ink, paint distribution pipe, and other chemical liquid pipe. The present invention can be suitably used as fuel pipes, engine coolant pipes, battery coolant pipes, electric motor coolant pipes, fuel cell coolant pipes, urea solution transport pipes, air conditioning refrigerant pipes, blowby pipes, brake booster pipes, brake pipes, oil cooling pipes, turbine pipes, air suspension pipes, and oil transmission pipes, and in particular, as cooling water pipes, urea water pipes, fuel pipes, blowby pipes, oil cooling pipes, and brake booster pipes. The coated molded article can be suitably used as a wire coating, a bus bar coating, or a metal wire coating.
The polyamide composition of the present embodiment can be used for producing a single-layer structure or at least 1 layer in a multilayer structure. For example, in a tube having a single-layer structure or a multilayer structure, at least 1 layer among the layers constituted may be suitably used with the polyamide composition of the present embodiment.
When the molded article of the present embodiment is used as a pipe, the pipe may be used after bending, end working, or connection of various joints. The bending process is generally performed by the following procedure.
Preheating step: the tube is preheated to soften it in order that the tube does not collapse at the required bend size.
Bending process: the tube is mounted on a jig or deformed by guide rollers to form the tube into a desired shape.
Heat treatment step: the stress generated in the tube is relaxed to fix the shape. The heat treatment temperature is required to be set to a temperature between the glass transition temperature and the melting point of the material constituting the tube, and the shape can be fixed in a shorter heat treatment time as the temperature is increased. Regarding the heat treatment temperature Tf, when the melting point of the lowest melting point material among the materials constituting the tube is set to Tm, the range of Tm-80 ℃ to Tf to Tm-10 ℃ is preferable, and Tm-60 ℃ to Tf to Tm-15 ℃ is more preferable. By setting the temperature to the above range, bending can be performed in an economical time, and melting of the pipe due to heat treatment can be prevented.
The joint may be connected by various methods such as press-fitting, spin welding, and laser welding. In the case where the use environment is high temperature and high pressure, it is desirable to use a welding method such as spin welding or laser welding from the viewpoint of reliability. When the welding method is used, it is desirable that the chemical affinity between the pipe material and the joint material is high, and when the laser welding method is used, it is desirable that the joint side be made of a laser transmitting material, the pipe side be made of an absorbing material, and laser light be irradiated from the upper part of the joint in the circumferential direction of the pipe in a state where the pipe is arranged inside the joint.
Examples
Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples.
The physical properties of examples, comparative examples and production examples were measured by the following methods.
[ measurement of physical Properties of Polyamide ]
Intrinsic viscosity
The semi-aromatic polyamide (sample) obtained in the production example was subjected to the following relational expression using concentrated sulfuric acid as a solvent to obtain an intrinsic viscosity (dl/g) at a concentration of 0.2g/dl and a temperature of 30 ℃.
η inh ＝[ln(t 1 /t 0 )]/c
In the above relation, eta inh Represents the intrinsic viscosity (dl/g), t 0 The flow-down time (seconds) of the solvent (concentrated sulfuric acid), t 1 The flow down time (seconds) of the sample solution is represented, and c represents the concentration (g/dl) of the sample in the sample solution (i.e., 0.2 g/dl).
Melting Point
The melting point of the semiaromatic polyamide (sample) obtained in the production example was measured using a differential scanning calorimeter "DSC7020" manufactured by Kyowa Kagaku Co., ltd., hitachi High Tech Science.
Melting points were determined in accordance with ISO11357-3 (2011 version 2). Specifically, the sample was heated at a rate of 10℃per minute from 30℃to 340℃under a nitrogen atmosphere, kept at 340℃for 5 minutes to completely melt the sample, and then cooled to 50℃at a rate of 10℃per minute and kept at 50℃for 5 minutes. When a plurality of melting peaks exist, the peak temperature of the melting peak at the highest temperature side is set to the melting point (. Degree. C.).
Terminal amino content
1g of the semiaromatic polyamide obtained in production example was dissolved in 35mL of phenol, and 2mL of methanol was mixed with the solution to prepare a sample solution. Titration with 0.01 equivalent of aqueous hydrochloric acid was performed using thymol blue as an indicator to determine the terminal amino group content ([ NH ]) of the semiaromatic polyamide 2 ]Units: mu eq/g).
Terminal carboxyl content
A sample solution was prepared by dissolving 0.5g of the semiaromatic polyamide obtained in the production example in 40mL of o-cresol. The obtained sample solution was titrated with 0.01 equivalent of alcoholic potassium hydroxide solution using a potential difference titration apparatus manufactured by Kyoto electronic industries, inc., and the inflection point of the potential was detected, whereby the terminal carboxyl group content ([ COOH ], unit: μeq/g) of the semiaromatic polyamide was determined.
Polydispersity index
The number average molecular weight Mn and the weight average molecular weight Mw of the semiaromatic polyamide obtained in the production example were measured by gel permeation chromatography, and the polydispersity index was determined by the following formula.
Polydispersity index=mw/Mn
The number average molecular weight and the weight average molecular weight were calculated by conversion from polymethyl methacrylate using HLC-8320GPC, manufactured by TOSOH Co., ltd., and a column TSK-gel SuperHM-N, manufactured by TOSOH Co., ltd., using hexafluoro-2-propanol 10mM trifluoroacetic acid as an eluent, and measuring at a measurement temperature of 40 ℃.
[ evaluation item of Polyamide composition ]
Functional group concentration
The concentration of the functional group in the polyamide compositions obtained in the examples and comparative examples was calculated from the following formula (1) based on the amounts of the components used.
(1)
Z＝1000×(|[ANH]-[EPO]|+[EPO])/X 2
In the above formula (1), each of [ EPO ], [ ANH ], and X is as follows.
[ EPO ]: the concentration of unsaturated epoxide from polyolefin per unit mass (mmol/kg) of the polyamide composition.
[ ANH ]: the concentration (mmol/kg) of unsaturated dicarboxylic anhydride from polyolefin per unit mass of the polyamide composition.
X: the content (mass%) of polyolefin in the polyamide composition.
The concentration [ EPO ] of the unsaturated epoxide and the concentration [ ANH ] of the unsaturated dicarboxylic acid in the above formula (1) are calculated according to the following formula (2).
(2)
[ EPO ] or [ ANH ] =100×N×W/M
In the above formula (2), M, W, N are each shown below.
M: molecular weight of unsaturated epoxide or unsaturated dicarboxylic anhydride.
W: the mass% of the unsaturated epoxide or unsaturated dicarboxylic anhydride contained in the polyolefin (A) or the polyolefin (B). In this embodiment, W is a product catalog value.
N: the mass% of the polyolefin (A) or the polyolefin (B) per unit mass of the polyamide composition.
In examples and comparative examples, the molecular weight of glycidyl methacrylate was 142.2 (g/mol) and the molecular weight of maleic anhydride was 98.06 (g/mol).
Stability at melt kneading
In examples and comparative examples, the processing stability in producing a polyamide composition by using a biaxial extruder was evaluated according to the following 4 grades. The stability was judged to be excellent in the order of A, B, B', C.
A: the vacuum exhaust port has no material discharge and broken strip, and can be stably manufactured.
B: although the strand is stable, there is a tendency that the oozed polyolefin is deposited at the vacuum vent, and there is a concern about foreign matters.
The reason for the bleeding out of the polyolefin is thought to be that the polyamide has a low affinity for the polyolefin.
B': although the strands are stable, the viscosity of the composition is high and the pressure of the twin-screw extruder is very high. In addition, a large amount of adherent substances were present near the die after blending. It is considered that the phenomenon is caused by the high reactivity of epoxide with polyamide.
C: the broken strips are numerous, and the granules are difficult to obtain.
In the composition of the plurality of broken strands of C, it is considered that the reason is that the polyolefin in the matrix of the polyamide is enlarged in the domain size and the affinity of the polyolefin for the polyamide is low. Regarding the polyamide composition judged as "C", since pellets were not obtained, melt viscosity, tensile test, impact test were not performed.
Melt viscosity
The melt viscosities of the polyamide compositions obtained in the examples and comparative examples were measured at a cylinder temperature of 300℃and a shear rate of 121.6sec using a Capirograph (manufactured by Toyo Seisakusho Co., ltd.) -1 (capillary: inner diameter 1.0 mm. Times.length 10mm, extrusion speed 10 mm/min) melt viscosity (Pa.s) was measured as an index of fluidity.
Test piece production
The polyamide compositions obtained in examples and comparative examples were molded using a T-type runner mold at a mold temperature of 140℃using an injection molding machine (clamping force: 100 tons, screw diameter: phi 32 mm) manufactured by Sumitomo heavy mechanical Co., ltd.) to prepare a plurality of test pieces A1 (test pieces of dumbbell type as described in JIS K7139; 4mm thick, full length: 170mm, parallel length: 80mm, parallel width: 10 mm) at a barrel temperature of 20 to 30℃higher than the melting point of the polyamide. Thereafter, rectangular parallelepiped test pieces (dimensions: length×width×thickness=80 mm×10mm×4 mm) were cut out from the above-mentioned multi-purpose test pieces, and were used as test pieces for evaluation of tensile test and impact test.
Tensile test
The tensile strength (maximum point) (MPa), tensile elongation at break (%) and tensile elastic modulus (GPa) at 23℃were measured by using a universal tester (manufactured by Instron) in accordance with ISO527-1 (2012, 2 nd edition) using a multi-purpose test piece type A1 (4 mm thickness) manufactured by the above method. The tensile modulus was measured at a tensile speed of 1mm/min in the range of 0.05 to 0.25% strain, and after 0.3% the tensile modulus was measured at a tensile speed of 50 mm/min.
Impact test
Test pieces (4 mm thick, full length 80mm, width 10mm, notched) were cut from the multipurpose test pieces A1 (4 mm thick) produced by the above method, and the notched impact values at 23℃and-40℃were measured using an impact tester (manufactured by Toyo Seiki Seisaku-Sho-Kagaku) in accordance with ISO179-1 (2010 edition 2) to evaluate impact resistance (kJ/m) 2 )。
Impact strength retention
The test piece for impact resistance test prepared by the above method was allowed to stand in a constant temperature bath (DE-303, santa Clara) set at 160℃for 1000 hours. After 1000 hours, the test piece taken out of the thermostatic bath was subjected to an impact resistance test at 23℃in the same manner as described above, and the impact resistance of the heated test piece was measured.
The impact strength retention was obtained from the following formula (X), and the long-term heat resistance was evaluated.
Impact strength retention (%) = { impact strength after 1000 hours/initial impact strength } ×100 (X)
Tube production
The polyamide compositions obtained in the examples and comparative examples were discharged at a barrel temperature of 280℃and a die temperature of 280℃and a screw rotation speed of 30rpm using a tube molding apparatus connected to a straight-through die (die inner diameter: phi 21.0mm, core outer diameter: phi 14.9 mm) by a single-screw extruder (screw diameter: phi 50mm, L/D=28) manufactured by IKG Co., ltd. Next, the tube having an outer diameter of 8.0mm and an inner diameter of 6.0mm was produced by controlling the dimensions and cooling in a vacuum forming tank at a drawing speed of 10 m/min.
Whitening resistance test
The end of the pipe obtained by the above method was subjected to flaring with a conical heater heated to 80 ℃, and after confirming that the temperature was lowered to room temperature, a quick connector having an outermost diameter of 8.9mm of the tree head was press-fitted, and the presence or absence of whitening occurring on the surface of the pipe end was visually confirmed. Regarding the whitening resistance, a sample in which whitening was not observed was evaluated as a, and a sample in which whitening had occurred was evaluated as C. The flaring is performed to facilitate alignment of the centers when the joint is pressed in.
Production example
Production example 1[ production of Polyamide PA-1 ]
9870.6g (59.42 mol) of terephthalic acid, a mixture [50/50 (molar ratio) ]9497.4g (60.30 mol) of 1, 9-nonanediamine and 2-methyl-1, 8-octanediamine, 142.9g (1.17 mol) of benzoic acid, 9.8g (0.05 mass% relative to the total mass of the starting materials) of sodium hypophosphite monohydrate, and 5 liters of distilled water were charged into an autoclave having an inner volume of 40 liters, and nitrogen substitution was performed. While stirring, the temperature in the autoclave was raised to 220℃over 2 hours. At this time, the pressure inside the autoclave was raised to 2MPa. After the reaction was continued as it was for 2 hours, the temperature was raised to 230℃and thereafter the temperature was maintained at 230℃for 2 hours, and the reaction was carried out while the pressure was maintained at 2MPa by slowly discharging water vapor. Then, the pressure was reduced to 1MPa for 30 minutes, and the reaction was further carried out for 1 hour to obtain a prepolymer having an intrinsic viscosity [ eta ] of 0.2 dl/g. The prepolymer was pulverized to a particle size of 2mm or less by a sheet breaker made of Hosokawa Micorn, dried at 100℃under reduced pressure for 12 hours, and then subjected to solid-phase polymerization at 230℃under 13Pa (0.1 mmHg) for 10 hours to give a white polyamide resin (polyamide PA-1).
The polyamide PA-1 comprises terephthalic acid units, 1, 9-nonanediamine units and 2-methyl-1, 8-octanediamine units (1, 9-nonanediamine units/2-methyl-1, 8-octanediamine units=50/50 (molar ratio)), and has a melting point of 265 ℃ and an intrinsic viscosity [ η ] inh ]At 1.26dl/g, terminal amino group content ([ NH ] 2 ]) 15.6. Mu. Eq/g, terminal carboxyl content ([ COOH)]) 55.1. Mu. Eq/g. In addition, the polydispersity index was 5.0 as determined by gel permeation chromatography.
PREPARATION EXAMPLE 2 preparation of Polyamide PA-2
9870.6g (59.42 mol) of terephthalic acid, a mixture [50/50 (molar ratio) ]9497.4g (60.90 mol) of 1, 9-nonanediamine and 2-methyl-1, 8-octanediamine, 142.9g (1.17 mol) of benzoic acid, 9.8g (0.05 mass% relative to the total mass of the starting materials) of sodium hypophosphite monohydrate, and 5 liters of distilled water were charged into an autoclave having an inner volume of 40 liters, and nitrogen substitution was performed. Thereafter, polymerization was carried out in the same manner as in production example 1 to obtain a white polyamide resin (polyamide PA-2).
In polyamide PA-2, the melting point is 265℃and the intrinsic viscosity [. Eta. inh ]At 1.28dl/g, terminal amino group content ([ NH ] 2 ]) 51.5. Mu. Eq/g, terminal carboxyl content ([ COOH)]) 23.4. Mu. Eq/g. In addition, the polydispersity index was 4.1 as determined by gel permeation chromatography.
Examples and comparative examples
Examples 1 to 7 and comparative examples 1 to 13 were prepared according to the formulations shown in Table 1 or Table 2 to obtain polyamide compositions.
Specifically, the polyamide shown in table 1 or table 2, the copper-based stabilizer, the antioxidant, the lubricant, and the colorant were mixed in advance at a predetermined mass ratio, and fed into the upstream side feed port of a biaxial extruder (TEM-26 SS manufactured by toshiba corporation) together with the polyolefin (a) in comparative example 10 and the polyolefin (C) in comparative examples 11 to 13. The pellet-shaped polyamide composition is produced by melt-kneading at a barrel temperature of 300 to 320 ℃ (melt-kneading temperature of 310 to 340 ℃, the melt-kneading temperature showing a resin temperature), a rotational speed of 150rpm, and a discharge rate of 10kg/hr, followed by extrusion, cooling and cutting.
Test pieces for evaluation of various physical properties were produced using the pellets, and various evaluations were performed by the methods described above. The results are shown in tables 1 and 2. In this case, the presence or absence of the discharge of the vacuum exhaust port in the downstream portion was checked.
In table 1, 1 indicates that measurement was impossible.
The components shown in tables 1 and 2 are as follows.
< Polyamide >)
Polyamide PA-1 obtained in production example 1
Polyamide PA-2 obtained in production example 2
< polyolefin (A) >)
Lotader (registered trademark) AX8930: copolymers of ethylene, methyl acrylate and glycidyl methacrylate [ Et/MA/gma=72/25/3 (mass ratio) ]
Lotader (registered trademark) AX8900: copolymers of ethylene, methyl acrylate and glycidyl methacrylate [ Et/MA/gma=68/24/8 (mass ratio) ]
< polyolefin (B) >)
Lotader (registered trademark) 4700: copolymers of ethylene, ethyl acrylate and maleic anhydride [ Et/EA/mah=68.7/30/1.3 (mass ratio) ]
Lotader (registered trademark) 3410: copolymers of ethylene, butyl acrylate and maleic anhydride [ Et/BA/mah=80/17/3.1 (mass ratio) ]
< polyolefin (C) >)
Tafmer (registered trademark) MH7010: elastomer modified with maleic anhydride ethylene-butene copolymer [ anhydride group concentration: 50. Mu. Eq/g ], sanjing chemical Co., ltd (for comparative example)
< copper stabilizer >)
KG HS01-P: molar ratio: cuI/KI=10/1, polyAd Services System
< antioxidant >
Naugard (registered trademark) 445:4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine manufactured by Addivant
< Lubricant >
WH-255: amide wax LightAmide, co., ltd
< colorant >
#980B: carbon black, mitsubishi chemical Co., ltd. [ Table 1]
TABLE 2
TABLE 2
As is clear from Table 1, the polyamide compositions of examples 1 to 7 are excellent in both high heat resistance and melt-kneading production stability, high tensile elongation at break, low-temperature impact resistance and whitening resistance.
Since the composition of comparative example 1 does not contain the polyolefin (a), the affinity with polyamide is insufficient, and a compatibilized composition cannot be obtained by blending.
Since the compositions of comparative examples 2, 3 and 5 do not contain a copper-based stabilizer, the impact strength retention rate is lowered and the thermal aging resistance is insufficient.
Since the compositions of comparative examples 4, 6 and 8 have a Z value smaller than the range defined in the present embodiment, the stability during melt kneading was insufficient. In addition, in comparative example 6, a compatibilized composition could not be obtained.
Since the composition of comparative example 7 [ B ]/[ A ] does not fall within the range defined in the present embodiment, the tensile elongation at break is insufficient.
Since the composition of comparative example 9 has a value of Z larger than the range defined in the present embodiment, the tensile elongation at break and the tensile elastic modulus are poor, the flexibility is insufficient, the impact strength retention is reduced, and the thermal aging resistance is also insufficient.
Since the composition of comparative example 10 does not contain the polyolefin (B), the melt viscosity becomes extremely high, and the balance between flexibility and viscosity becomes poor.
Since the compositions of comparative examples 11 to 13 do not contain the polyolefin (a) and the polyolefin (B), the whitening resistance is insufficient even if the polyolefin (C) is contained instead of these.

Claims (17)

1. A polyamide composition comprising a polyamide, a polyolefin and a copper-based stabilizer,
the polyolefin contains at least one polyolefin A and at least one polyolefin B, the polyolefin A contains a copolymer of ethylene, alkyl (meth) acrylate and unsaturated epoxide, the polyolefin B contains unsaturated dicarboxylic anhydride, and the mass ratio [ B ]/[ A ] of the content [ B ] of the polyolefin B to the content [ A ] of the polyolefin A is 0.1-2.9,
the value Z calculated according to the following formula (1) is 33-200;
Z＝1000×(|[ANH]－[EPO]|+[EPO])/X 2 (1)
Said [ EPO ] is the concentration of unsaturated epoxide from said polyolefin per unit mass of said composition, in mmol/kg;
said [ ANH ] is the concentration of unsaturated dicarboxylic anhydride from said polyolefin per unit mass of said composition in mmol/kg;
the X is the content of polyolefin in the composition, and the unit is mass%.
2. The polyamide composition as claimed in claim 1, wherein,
the polyamide contains 50 mol% or more of at least 1 selected from terephthalic acid units and naphthalene dicarboxylic acid units, relative to the total dicarboxylic acid units.
3. The polyamide composition according to claim 1 or 2, wherein,
the polyamide contains 60 mol% or more of an aliphatic diamine unit having 4 to 13 carbon atoms or a m-xylylenediamine unit relative to the total diamine units.
4. The polyamide composition according to claim 3, wherein,
the aliphatic diamine unit is a unit derived from at least 1 aliphatic diamine selected from the group consisting of 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 9-nonanediamine, 2-methyl-1, 8-octanediamine and 1, 10-decanediamine.
5. The polyamide composition according to claim 3 or 4, wherein,
the aliphatic diamine unit is a unit derived from at least 1 aliphatic diamine selected from the group consisting of 1, 9-nonanediamine and 2-methyl-1, 8-octanediamine.
6. The polyamide composition according to any one of claims 1 to 5, wherein,
the polyamide has a polydispersity index of 3.7 or more, a terminal amino group content of 10 to 70 [ mu ] eq/g, and a terminal carboxyl group content of 10 to 70 [ mu ] eq/g, as measured by gel permeation chromatography.
7. The polyamide composition according to any one of claims 1 to 6, wherein,
the polyolefin content is 14 to 40 mass%.
8. The polyamide composition according to any one of claims 1 to 7, wherein,
the content of the polyolefin is 15 to 30 mass%.
9. The polyamide composition according to any one of claims 1 to 8, wherein,
the polyolefin B is a copolymer of ethylene, alkyl (meth) acrylate and unsaturated dicarboxylic anhydride.
10. The polyamide composition according to any one of claims 1 to 9, wherein,
the content of the copper stabilizer is 0.01-2% by mass.
11. The polyamide composition according to any one of claims 1 to 10, wherein,
the copper-based stabilizer comprises at least 1 copper compound selected from copper iodide, copper bromide and copper acetate and at least 1 metal halide selected from potassium iodide and potassium bromide.
12. The polyamide composition according to any one of claims 1 to 11, comprising at least 1 additive selected from the group consisting of: other types of polymers than the polyamides and the polyolefins, antioxidants, fillers, crystallization nucleating agents, colorants, antistatic agents, plasticizers, lubricants, flame retardants, and flame retardant aids.
13. A process for producing a polyamide composition according to any one of claims 1 to 12,
the polyamide, the polyolefin and the copper stabilizer were fed to a twin-screw extruder at the top and melt kneaded.
14. Use of the polyamide composition according to any one of claims 1 to 12 for the production of a single layer structure or for the production of at least 1 layer in a multilayer structure.
15. A molded article formed from the polyamide composition of any one of claims 1 to 12.
16. The shaped body of claim 15, which is an extrusion-shaped body, a co-extrusion-shaped body or a blow-molded body.
17. The shaped body according to claim 16, which is a fuel pipe, an engine coolant pipe, a battery coolant pipe, an electric motor coolant pipe, a fuel cell coolant pipe, a urea solution transport pipe, a pipe for air conditioning refrigerant, a blow-by pipe, a brake booster pipe, a brake pipe, an oil cooling pipe, a turbine pipe, an air suspension pipe, or a pipe for petroleum transportation.
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