WO2014010607A1 - ポリアミド、ポリアミド組成物及び成形品 - Google Patents
ポリアミド、ポリアミド組成物及び成形品 Download PDFInfo
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- WO2014010607A1 WO2014010607A1 PCT/JP2013/068786 JP2013068786W WO2014010607A1 WO 2014010607 A1 WO2014010607 A1 WO 2014010607A1 JP 2013068786 W JP2013068786 W JP 2013068786W WO 2014010607 A1 WO2014010607 A1 WO 2014010607A1
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- dicarboxylic acid
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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
- 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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
- C08G69/30—Solid state polycondensation
-
- 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
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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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
Definitions
- the present invention relates to a polyamide, a polyamide composition, and a molded product.
- Polyamides typified by polyamide 6 and polyamide 66 are excellent in molding processability, mechanical properties, and chemical resistance. Polyamide is widely used as various parts materials for automobiles, electric and electronic, industrial materials, industrial materials, daily use and household goods.
- polyamides are increasingly being used in place of metals as automobile exterior materials and interior materials.
- Polyamides used for automobile exterior materials and interior materials are required to have higher levels of heat resistance, strength, appearance, and other characteristics.
- polyamides used as materials in the engine room are increasingly required to have high heat resistance because the temperature in the engine room tends to increase.
- SMT solder lead-free surface mount solder is being promoted.
- Polyamides used for materials such as home appliances are required to have high heat resistance that can withstand the rise in melting point of solder accompanying such lead-free soldering.
- polyamides such as PA6 and PA66 have a low melting point and cannot satisfy these requirements in terms of heat resistance.
- PA6T terephthalic acid and hexamethylenediamine
- PA6T is a high melting point polyamide having a melting point of about 370 ° C.
- the thermal decomposition of the polyamide occurs vigorously, and a molded product having sufficient characteristics can be obtained. difficult.
- PA6T is made of an aliphatic polyamide such as PA6 and PA66, or an amorphous aromatic polyamide composed of isophthalic acid and hexamethylenediamine (hereinafter abbreviated as “PA6I”).
- PA6I amorphous aromatic polyamide composed of isophthalic acid and hexamethylenediamine
- High melting point semi-aromatic polyamide hereinafter referred to as “6T type co-polymer” composed mainly of terephthalic acid and hexamethylene diamine having a melting point lowered to about 220 to 340 ° C. In some cases, it is abbreviated as “polymerized polyamide”).
- Patent Document 1 discloses an aromatic polyamide composed of an aromatic dicarboxylic acid and an aliphatic diamine, and the aliphatic diamine is a mixture of hexamethylene diamine and 2-methylpentamethylene diamine (hereinafter referred to as “6T-based copolymer polyamide”). , which may be abbreviated as “PA6T / 2MPDT”).
- a high melting point aliphatic polyamide composed of adipic acid and tetramethylene diamine hereinafter sometimes abbreviated as “PA46”
- PA46 tetramethylene diamine
- Patent Documents 2 and 3 describe semialicyclic polyamides of alicyclic polyamides (hereinafter sometimes referred to as “PA6C”) composed of 1,4-cyclohexanedicarboxylic acid and hexamethylenediamine and other polyamides. (Hereinafter, it may be abbreviated as “PA6C copolymer polyamide”).
- PA6C semialicyclic polyamides of alicyclic polyamides
- Patent Document 2 discloses that an electric and electronic member made from a semi-alicyclic polyamide containing 1 to 40% 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit can withstand a temperature under soldering conditions. It has been disclosed to have excellent heat resistance.
- Patent Document 3 discloses that an automobile part manufactured from a polyamide composition substantially composed of a unit derived from an aliphatic dicarboxylic acid and an aliphatic diamine is excellent in fluidity and toughness. Has been.
- Patent Document 4 discloses that a polyamide comprising a dicarboxylic acid unit containing 1,4-cyclohexanedicarboxylic acid and a diamine unit containing 2-methyl-1,8-octanediamine has light resistance, toughness, moldability, lightness, and It is disclosed that it is excellent in heat resistance and the like. Further, as a method for producing the polyamide, 1,4-cyclohexanedicarboxylic acid and 1,9-nonanediamine are reacted at 230 ° C. or less to produce a prepolymer, and the prepolymer is solid-phase polymerized at 230 ° C., A method for producing a polyamide having a melting point of 311 ° C. is disclosed.
- Patent Document 5 a polyamide using 1,4-cyclohexanedicarboxylic acid having a trans / cis ratio of 50/50 to 97/3 as a raw material is excellent in heat resistance, low water absorption, light resistance, and the like. It is disclosed.
- Patent Document 6 discloses a polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid and a diamine having a substituent branched from the main chain.
- Patent Document 7 discloses a polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, undecamethylenediamine, and 1,6-diaminohexane.
- Patent Document 8 discloses a polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, 1,12-diaminododecane, and 1,6-diaminohexane.
- Patent Document 9 discloses a copolymerized polyamide obtained by copolymerizing an alicyclic dicarboxylic acid, a diamine, and a predetermined copolymerization component.
- JP-T 6-503590 Japanese National Patent Publication No. 11-512476 JP 2001-514695 A Japanese Patent Laid-Open No. 9-12868 International Publication No. 2002/048239 Pamphlet International Publication No. 2009/113590 Japanese Patent Publication No. 64-2131 International Publication No. 2008/149862 Pamphlet International Publication No. 2012/093722 Pamphlet
- the 6T copolymer polyamide certainly has the characteristics of low water absorption, high heat resistance, and high chemical resistance, it has low fluidity and is sufficient in terms of moldability and molded product surface appearance. The properties are not obtained, and furthermore, the toughness and light resistance are inferior. Therefore, improvement is desired in applications where the surface appearance and light resistance of molded products are required, such as exterior parts. In addition, the specific gravity is large, and improvement in lightness is also desired.
- the PA6T / 2MPDT disclosed in Patent Document 1 can partially improve the problems of the conventional PA6T copolymerized polyamide, but the flowability, moldability, toughness, surface appearance of the molded product, and light resistance However, the level of improvement is insufficient.
- PA46 has good heat resistance and moldability, but has a high water absorption rate, and has a problem that the dimensional change due to water absorption and deterioration of mechanical properties are remarkably large, and is required for automobile applications. There are cases where the requirements cannot be met in terms of dimensional change.
- the PA6C copolymer polyamide disclosed in Patent Documents 2 and 3 also have problems such as high water absorption and insufficient fluidity.
- Patent Documents 4 and 5 are also insufficiently improved in terms of depopulation time stability, vibration fatigue characteristics, slidability and surface appearance.
- the polyamide disclosed in Patent Document 6 has a high water absorption rate, and a phenomenon in which the pellets are blocked during handling of the pellets, particularly at the time of transfer, is seen in terms of low water absorption, low blocking properties, and releasability. Improvement may be necessary.
- the polyamide disclosed in Patent Document 7 may need to be improved in terms of low blocking property, plasticization time stability, and surface appearance.
- the polyamide disclosed in Patent Document 8 may need to be improved in terms of plasticization time stability, vibration fatigue characteristics, slidability, surface appearance, and continuous productivity.
- the polyamide disclosed in Patent Document 9 may need to be improved in terms of vibration fatigue characteristics and slidability.
- the conventionally known polyamide having a high melting point tends to have a very high proportion of polyamide molecules having a three-dimensional structure when the molecular weight is increased for the purpose of improving long-term characteristics such as vibration fatigue characteristics and slidability. It is difficult to increase the molecular weight while maintaining good fluidity, and the polymerization yield in melt polymerization is significantly reduced. Moreover, in practical use, since the polyamide having the three-dimensional structure remains continuously produced, the polyamide having the three-dimensional structure is gelled, causing black spots, and the quality is significantly reduced. have.
- polyamide pellets with a high proportion of polyamide molecules having a three-dimensional structure obtained by polymerization are processed at a high temperature with an extruder or molding machine, the three-dimensional structure of the polyamide molecules further advances and the flow characteristics are not stable. have.
- the problems to be solved by the present invention include polyamides having excellent strength, high temperature strength, low water absorption, low blocking properties, release properties, plasticization time stability, slidability, and polymerization yield in melt polymerization, and It is to provide a polyamide composition excellent in vibration fatigue characteristics and surface appearance.
- the inventors of the present invention contain a unit consisting of a specific dicarboxylic acid and a unit consisting of a specific diamine, and have a sulfuric acid relative viscosity ⁇ r, Mw (weight average molecular weight) / It has been found that a polyamide satisfying specific requirements in Mn (number average molecular weight) can solve the above-mentioned problems, and has completed the present invention. That is, the present invention is as follows.
- (2) Mw (weight average molecular weight) / Mn (number average molecular weight) is 4.0 or less.
- (C-2) The diamine other than the above (b) having a carbon number equal to or less than the carbon number of the diamine (b) is an aliphatic diamine having 4 to 9 carbon atoms, [9] or [10] The polyamide described.
- the diamine other than (b) having a carbon number equal to or less than that of the diamine (b) is at least selected from the group consisting of 1,6-hexamethylenediamine and 2-methylpentamethylenediamine.
- a sliding part comprising the polyamide according to any one of [1] to [18] or the polyamide composition according to [19] or [20].
- the molded article according to [21] which is any one selected from the group consisting of automobile parts, electronic parts, home appliance parts, OA equipment parts, and portable equipment parts.
- the polyamide having excellent strength, high temperature strength, low water absorption, low blocking property, releasability, plasticization time stability, slidability, and polymerization yield in melt polymerization, and vibration fatigue properties and A polyamide composition having an excellent surface appearance can be provided.
- the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
- the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
- the present invention can be implemented with various modifications within the scope of the gist.
- the polyamide of this embodiment is (A) a unit comprising at least one alicyclic dicarboxylic acid; (B) a unit comprising a diamine having 8 or more carbon atoms; And satisfies the following conditions (1) and (2).
- the sulfuric acid relative viscosity ⁇ r at 25 ° C. is 2.3 or more.
- Mw (weight average molecular weight) / Mn (number average molecular weight) is 4.0 or less.
- the polyamide means a polymer having an amide (—NHCO—) bond in the main chain.
- the dicarboxylic acid is not limited to the dicarboxylic acid itself, and may be a compound equivalent to the dicarboxylic acid.
- the compound equivalent to the dicarboxylic acid is not particularly limited as long as it has a dicarboxylic acid structure derived from dicarboxylic acid and can be a dicarboxylic acid structure. Examples include dicarboxylic acid anhydrides and halides.
- the polyamide of this embodiment contains a unit consisting of (a) an alicyclic dicarboxylic acid.
- an alicyclic dicarboxylic acid hereinafter also referred to as “alicyclic dicarboxylic acid” used in the present embodiment, and may be referred to as (a) component or (a) in this specification
- an alicyclic dicarboxylic acid having 3 to 10 carbon atoms in the alicyclic structure preferably an alicyclic dicarboxylic acid having 5 to 10 carbon atoms in the alicyclic structure. Can be mentioned.
- Examples of (a) alicyclic dicarboxylic acids include, but are not limited to, for example, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, and the like. Can be mentioned.
- the (a) alicyclic dicarboxylic acid used in the present embodiment may be unsubstituted or may have a substituent.
- substituents include, but are not limited to, for example, 1 carbon atom such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. -4 alkyl groups and the like.
- 1,4-cyclohexanedicarboxylic acid is preferable from the viewpoint of the heat resistance, low water absorption, strength, rigidity and the like of the polyamide of the present embodiment.
- the (a) alicyclic dicarboxylic acid used in the present embodiment may be used alone or in combination of two or more.
- Alicyclic dicarboxylic acids have trans and cis geometric isomers.
- the alicyclic dicarboxylic acid as a raw material monomer either a trans isomer or a cis isomer may be used, or a mixture of various proportions of a trans isomer and a cis isomer may be used.
- the alicyclic dicarboxylic acid is isomerized at a high temperature to have a certain ratio, and the cis isomer has higher water solubility of the equivalent salt with the diamine than the trans isomer.
- the alicyclic dicarboxylic acid has a trans isomer / cis isomer ratio of preferably 50/50 to 0/100, more preferably 40/60 to 10/90, still more preferably 35 / 65 to 15/85.
- the trans / cis ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR).
- HPLC liquid chromatography
- NMR nuclear magnetic resonance spectroscopy
- the trans isomer / cis isomer ratio (molar ratio) in the present specification can be determined by 1 H-NMR.
- the polyamide of this embodiment contains (b) a unit composed of a diamine having 8 or more carbon atoms.
- C8 or more diamine this specification, (b) component, (b) diamine, may be described as (b) in this specification) used for this embodiment, C8 or more is used.
- C8 or more there is no particular limitation as long as it is a diamine, and even an unsubstituted linear aliphatic diamine such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.
- a branched aliphatic diamine having a substituent such as an alkyl group having 1 to 4 carbon atoms, an alicyclic diamine, or an aromatic diamine may be used.
- the number of carbon atoms in the (b) diamine having 8 or more carbon atoms used in this embodiment is 8 or more from the viewpoint of low water absorption (reducing water absorption), and 20 or less from the viewpoint of increasing the high temperature strength and melting point, that is, It is preferably 8 to 20, more preferably 8 to 15, and still more preferably 8 to 12.
- the diamine having 8 or more carbon atoms used in the present embodiment is not limited to the following, but examples include octamethylene diamine, 2-methyloctamethylene diamine, nonamethylene diamine, decamethylene diamine, undeca Methylenediamine, dodecamethylenediamine, tridecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, 2,4-dimethyloctamethylenediamine, Examples include metaxylylenediamine, orthoxylylenediamine, and paraxylylenediamine.
- the diamine having 8 or more carbon atoms used in the present embodiment includes octamethylene diamine, 2-methyloctamethylene diamine, nonamethylene diamine, decamethylene diamine from the viewpoints of heat resistance, low water absorption, strength and rigidity.
- Undecamethylene diamine and dodecamethylene diamine are preferred, more preferably 2-methyloctamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, and dodecamethylene diamine, and still more preferably decamethylene diamine, Dodecamethylenediamine, and even more preferably decamethylenediamine.
- the decamethylenediamine is preferably 1,10-decamethylenediamine having a linear decane skeleton having an amino group at the 1,10-position from the viewpoint of further improving crystallinity. 1,10-decamethylenediamine is also preferable from the viewpoint of being a biomass-derived raw material.
- the decamethylenediamine may be unsubstituted 1,10-decamethylenediamine or substituted 1,10-decamethylenediamine having a substituent.
- the substituent is not particularly limited, and examples thereof include 1 to C carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. 4 alkyl groups.
- (B) may be used alone or in combination of two or more.
- the diamine having the largest number of carbon atoms is used as the component (b), and other diamines having 8 or more carbon atoms are described later in (c-2). Ingredients.
- the polyamide of this embodiment is a predetermined (c) copolymerization component (in this specification, (c) component, ( c) may also be included)).
- the (c) copolymer component is a dicarboxylic acid other than (c-1) an alicyclic dicarboxylic acid (in this specification, it may be referred to as the component (c-1) or (c-1)).
- (C-2) A diamine other than the above (b) having a carbon number equal to or less than the carbon number of the diamine (b) (in this specification, the component (c-2) may be referred to as (c-2)).
- at least selected from the group consisting of (c-3) lactams and / or aminocarboxylic acids (in this specification, (c-3) component, may be described as (c-3)).
- (C) Copolymerization component combined with (a) alicyclic dicarboxylic acid and (b) diamine having 8 or more carbon atoms may be used alone or in combination of two or more.
- (c-1), (c-2) and (c-3) can be freely combined.
- two types from (c-1) may be used, Two types from c-2) and (c-3) may be combined, or one type from (c-1) and one type from (c-2) may be combined.
- the content of the copolymerization component (c) in the polyamide of this embodiment is preferably 5.0 mol% or more and 22.5 mol% or less, more preferably 7 mol% relative to 100 mol% of the total component amount of the polyamide. It is 0.5 mol% or more and 20.0 mol% or less, More preferably, it is 10.0 mol% or more and 18.0 mol% or less.
- (C) By making content of a copolymerization component into the said range, it can be set as the polyamide excellent in intensity
- the dicarboxylic acid other than the (b) alicyclic dicarboxylic acid is not limited to the following, and examples thereof include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.
- aliphatic dicarboxylic acid examples include, but are not limited to, malonic acid, dimethyl malonic acid, succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl glutaric acid, 2,2- Diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane
- straight chain or branched aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid.
- aromatic dicarboxylic acid examples include, but are not limited to, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5 -Aromatic dicarboxylic acids having 8 to 20 carbon atoms which are unsubstituted or substituted with various substituents such as sodium sulfoisophthalic acid.
- Examples of the various substituents include, but are not limited to, for example, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and a chloro group. And a halogen group such as a bromo group, a silyl group having 1 to 6 carbon atoms, and a sulfonic acid group and a salt thereof such as a sodium salt.
- a halogen group such as a bromo group, a silyl group having 1 to 6 carbon atoms, and a sulfonic acid group and a salt thereof such as a sodium salt.
- the (c-1) dicarboxylic acid other than the (a) alicyclic dicarboxylic acid used in the present embodiment is preferably an aliphatic group from the viewpoint of heat resistance, fluidity, toughness, low water absorption, strength, rigidity, and the like.
- Dicarboxylic acids more preferably aliphatic dicarboxylic acids having 6 or more carbon atoms.
- the dicarboxylic acid other than the (a) alicyclic dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 10 or more carbon atoms from the viewpoint of heat resistance and low water absorption.
- Examples of the aliphatic dicarboxylic acid having 10 or more carbon atoms include, but are not limited to, for example, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid. Can be mentioned.
- the (c-1) dicarboxylic acid other than the (a) alicyclic dicarboxylic acid sebacic acid and / or dodecanedioic acid are preferable from the viewpoint of heat resistance.
- the (c-1) dicarboxylic acid other than the (a) alicyclic dicarboxylic acid used in the present embodiment is preferably aromatic in view of heat resistance, fluidity, toughness, low water absorption, strength, rigidity, and the like.
- (c-1) As the dicarboxylic acid other than (a) the alicyclic dicarboxylic acid, isophthalic acid is preferable from the viewpoint of heat resistance, fluidity, surface appearance, and the like.
- the dicarboxylic acid other than (a) the alicyclic dicarboxylic acid has a trivalent or higher valence such as trimellitic acid, trimesic acid, and pyromellitic acid within the range not impairing the object of the present embodiment.
- a polyvalent carboxylic acid may be included.
- polyvalent carboxylic acid only one kind may be used alone, or two or more kinds may be used in combination.
- the ratio (mol%) of (a) alicyclic dicarboxylic acid in (a) alicyclic dicarboxylic acid and (c-1) dicarboxylic acid other than (a) alicyclic dicarboxylic acid is particularly limited. However, it is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, still more preferably 70 to 100 mol%.
- the ratio of the (a) alicyclic dicarboxylic acid in the total amount of (a) and (c-1) is 50 to 100 mol%, strength, high temperature strength, low water absorption, low blocking property, A polyamide excellent in releasability and plasticization time stability is obtained.
- the polyamide composition containing the polyamide is excellent in vibration fatigue characteristics and surface appearance.
- the diamine other than the above (b) having a carbon number equal to or less than that of the diamine (b) is not limited to the following, but examples include aliphatic diamines, alicyclic diamines, and the like. An aromatic diamine etc. are mentioned.
- aliphatic diamine examples include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylene.
- Linear aliphatic diamines such as diamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine, 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethyl And branched aliphatic diamines such as hexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctamethylenediamine.
- alicyclic diamine examples include, but are not limited to, for example, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclohexanediamine. And cyclopentanediamine.
- the aromatic diamine is a diamine containing an aromatic, and is not limited to the following, and examples thereof include metaxylylenediamine, orthoxylylenediamine, paraxylylenediamine, and the like.
- the diamine other than the above (b) having a carbon number equal to or less than the carbon number of the diamine (b) used in the present embodiment includes the heat resistance, fluidity, toughness and low water absorption of the polyamide of the present embodiment. From the viewpoints of properties, strength, rigidity, etc., aliphatic diamines and alicyclic diamines are preferable, aliphatic diamines having 4 to 13 carbon atoms are more preferable, and those having 4 to 7 carbon atoms are still more preferable. Aliphatic diamines, and more preferably 1,6-hexamethylenediamine and 2-methylpentamethylenediamine.
- a diamine other than (b) having a carbon number equal to or less than the carbon number of the diamine (b) is a trivalent or higher valence such as bishexamethylenetriamine as long as the object of the present embodiment is not impaired.
- the polyvalent aliphatic amine may be included.
- One kind of the polyvalent aliphatic amine may be used alone, or two or more kinds may be used in combination.
- the (mol%) is not particularly limited, but is preferably 40 to 100 mol%, more preferably 50 to 100 mol%, and still more preferably 60 to 100 mol%.
- a lactam and / or aminocarboxylic acid means a lactam and / or aminocarboxylic acid capable of being combined (condensed).
- the polyamide of this embodiment is a copolymerized polyamide obtained by copolymerizing (a) an alicyclic dicarboxylic acid, (b) a diamine having 8 or more carbon atoms, and (c-3) a lactam and / or an aminocarboxylic acid.
- the (c-3) lactam and / or aminocarboxylic acid is preferably a lactam and / or aminocarboxylic acid having 4 to 14 carbon atoms from the viewpoint of fluidity and toughness, and having 6 to 12 carbon atoms. More preferred are lactams and / or aminocarboxylic acids.
- lactam examples include, but are not limited to, butyrolactam, pivalolactam, ⁇ -caprolactam, caprylolactam, enantolactam, undecanolactam, laurolactam (dodecanolactam), and the like.
- lactam from the viewpoint of toughness, ⁇ -caprolactam, undecanolactam, laurolactam and the like are preferable, and ⁇ -caprolactam and laurolactam are more preferable.
- the aminocarboxylic acid is not limited to the following, and examples thereof include ⁇ -aminocarboxylic acid and ⁇ , ⁇ -amino acid that are compounds in which the lactam is ring-opened.
- the aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms substituted with an amino group at the ⁇ position.
- 6-aminocaproic acid, 11-aminoundecanoic acid And 12-aminododecanoic acid, and the like examples of the aminocarboxylic acid include paraaminomethylbenzoic acid.
- aminocarboxylic acid 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like are more preferable from the viewpoint of low water absorption and toughness.
- the addition amount (mol%) of lactam and / or aminocarboxylic acid is not particularly limited, but (a) an alicyclic dicarboxylic acid, (b) a diamine having 8 or more carbon atoms, And (c-3) preferably 0.5 mol% or more and 20 mol% or less, more preferably 2 mol% with respect to the molar amount (100 mol%) of the whole monomer of lactam and / or aminocarboxylic acid. It is 18 mol% or less.
- the content ratio of (a) at least one alicyclic dicarboxylic acid and (b) a diamine having 8 or more carbon atoms is preferably the same molar amount. Therefore, it is preferable that the amount of dicarboxylic acid used and the amount of diamine used as raw materials for obtaining the polyamide of the present embodiment is around the same molar amount. Specifically, the amount of diamine escaped from the reaction system during the polymerization reaction is also considered in terms of the molar ratio, and the molar amount of the entire diamine is 0.9 to 1 with respect to the molar amount 1 of the entire dicarboxylic acid.
- the content of the copolymer component is preferably 5.0 mol% or more and 22.5 mol% or less, more preferably 7.5 mol% or more and 20 mol% or less with respect to 100 mol% of the total component amount of the polyamide. It is 0.0 mol% or less, More preferably, it is 10.0 mol% or more and 18.0 mol% or less.
- End sealant When polymerizing the polyamide of this embodiment, in addition to the components (a) to (c), a known end-capping agent can be further added for molecular weight adjustment.
- the end capping agent include, but are not limited to, acid anhydrides such as monocarboxylic acid, monoamine, and phthalic anhydride; monoisocyanates, monoacid halides, monoesters, and monoalcohols. From the viewpoint of thermal stability, monocarboxylic acids and monoamines are preferable.
- One type of end capping agent may be used alone, or two or more types may be used in combination.
- the monocarboxylic acid that can be used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group.
- monocarboxylic acid you may use by 1 type and may be used in combination of 2 or more types.
- the monoamine that can be used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group.
- methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine Aliphatic monoamines such as decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; Etc.
- Monoamines may be used alone or in combination of two or more.
- the alicyclic dicarboxylic acid structure exists as a geometric isomer of a trans isomer and a cis isomer.
- the trans isomer ratio in the portion derived from the alicyclic dicarboxylic acid represents the ratio of the trans isomer in the entire alicyclic dicarboxylic acid in the polyamide.
- the trans isomer ratio is preferably 50 to 85 mol%, more preferably 50 to 80 mol%, and still more preferably 65 to 80 mol%.
- the raw material (a) alicyclic dicarboxylic acid it is preferable to use an alicyclic dicarboxylic acid having a trans isomer / cis isomer ratio (molar ratio) of 50/50 to 0/100 as described above.
- the trans isomer ratio in the portion derived from (a) alicyclic dicarboxylic acid is preferably within the above range.
- the polyamide of this embodiment has a high melting point, toughness, strength, rigidity, and plasticity time stability. Usually, it has the property of satisfying both the fluidity, which is a property contrary to heat resistance, and high crystallinity at the same time. Moreover, the polyamide composition containing the polyamide is excellent in surface appearance.
- the method for controlling the trans isomer ratio in the portion derived from the (a) alicyclic dicarboxylic acid in the polyamide within the above range include a polyamide polymerization method and a polymerization condition control method. When producing a polyamide by a hot melt polymerization method, it is preferable to maintain a molten state until the polymerization is completed.
- the polymerization pressure is controlled to a high pressure of 23 to 50 kg / cm 2 (gauge pressure), preferably 25 kg / cm 2 (gauge pressure) or higher, and the pressure in the tank is maintained at atmospheric pressure while heating is continued.
- gauge pressure 23 to 50 kg / cm 2
- gauge pressure 25 kg / cm 2
- Examples include a method of decreasing the pressure while taking 30 minutes or more until the gauge pressure becomes 0 kg / cm 2 .
- the trans isomer ratio in the polyamide is determined, for example, by dissolving 30 to 40 mg of polyamide in 1.2 g of hexafluoroisopropanol deuteride and measuring the resulting solution by 1 H-NMR. be able to. Specifically, in the case of 1,4-cyclohexanedicarboxylic acid, 1.98 ppm peak areas derived from the trans isomer and 1.77 ppm and 1.86 ppm derived from the cis isomer in 1 H-NMR measurement. The trans isomer ratio can be determined from the ratio to the peak area.
- the biomass plasticity degree of the polyamide of this embodiment is preferably 25% or more from the viewpoint of reducing the environmental load.
- the biomass plasticity means the proportion of units composed of raw materials derived from biomass in polyamide.
- the bioplastic degree can be calculated by the method described in Examples described later. A more preferable bioplastic degree is 30% or more.
- the upper limit of the biomass plasticity degree of the polyamide of this embodiment is not specifically limited, For example, it is 80% from a heat resistant viewpoint of polyamide.
- the biomass-derived raw material means a monomer that can be synthesized using a component such as a plant as a starting material among the components (a) to (c), which are constituent components of polyamide.
- a component such as a plant as a starting material among the components (a) to (c), which are constituent components of polyamide.
- synthesizing from sebacic acid, decamethylenediamine, and 11-aminoundecanoic acid, azelaic acid which can be synthesized from sunflower seed components
- cellulose which can be synthesized from ricinoleic acid triglyceride, which is the main component of castor oil And pentamethylenediamine, ⁇ -aminobutyric acid, etc.
- Biomass is accumulated by absorbing carbon dioxide in the atmosphere through photosynthesis. Therefore, even when carbon dioxide is released into the atmosphere by combustion after use of plastics made from these materials, it is originally in the atmosphere. Therefore, the carbon dioxide concentration in the atmosphere does not increase.
- Examples of a method for increasing the biomass plasticity degree of polyamide to 25% or more include a method for increasing the blending ratio of the above-described biomass-derived raw materials when producing polyamide.
- the molecular weight of the polyamide of the present embodiment can be determined by using sulfuric acid relative viscosity ⁇ r at 25 ° C. as an index.
- the sulfuric acid relative viscosity ⁇ r at 25 ° C. of the polyamide of this embodiment is set to 2.3 or more from the viewpoint of the strength of the polyamide, the high temperature strength, the vibration fatigue properties of the polyamide composition, and the like. It is preferably 2.3 to 5.0, more preferably 2.4 to 4.0, and even more preferably 2.5 to 3.5.
- a polyamide having excellent tensile strength, high temperature strength and toughness can be obtained by setting the relative sulfuric acid viscosity ⁇ r of polyamide to 2.3 or more, preferably 2.3 to 5.0. Moreover, the polyamide composition containing the component represented by the inorganic filler mentioned later is excellent in vibration fatigue characteristics.
- a known polycondensation catalyst such as phosphoric acid or sodium hypophosphite is added as an additive at the time of hot melt polymerization of polyamide.
- Control method, method of adjusting the amount of diamine added as an additive during hot melt polymerization of polyamide, method of reducing the amount of end-capping agent added, and polymerization conditions such as heating conditions and reduced pressure conditions And a method of promoting dehydration.
- the measurement of the relative viscosity ⁇ r of sulfuric acid at 25 ° C. of polyamide can be performed according to JIS-K6920 as described in the following examples.
- the molecular weight distribution of the polyamide of this embodiment uses Mw (weight average molecular weight) / Mn (number average molecular weight) as an index.
- Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamide of this embodiment is 4.0 or less from the viewpoint of the strength of the polyamide, the high temperature strength, the vibration fatigue properties of the polyamide composition, and the like. Preferably it is 1.5 to 3.5, more preferably 1.5 to 3.3, still more preferably 1.5 to 3.0, and even more preferably 1.5 to 2.5. is there.
- the lower limit of the molecular weight distribution is 1.0.
- Mw weight average molecular weight
- Mn number average molecular weight
- the polyamide of this embodiment has a great feature in that the sulfuric acid relative viscosity ⁇ r at 25 ° C. is 2.3 or more and Mw / Mn is 4.0 or less.
- the proportion of polyamide molecules having a three-dimensional structure is small while having a high molecular weight, and the three-dimensional structuring of molecules can be suppressed during high-temperature processing, and excellent fluidity can be obtained.
- the polyamide of this embodiment has a sulfuric acid relative viscosity ⁇ r at 25 ° C. of 2.3 or more and Mw / Mn of 4.0 or less.
- a high molecular weight distribution indicates a high proportion of polyamide molecules having a three-dimensional molecular structure, and the three-dimensional structuring of the molecule is more likely to proceed during high-temperature processing, resulting in poor fluidity.
- ⁇ r is 2.3 or more by forming a polyamide containing (a) a unit composed of an alicyclic dicarboxylic acid and (b) a unit composed of a diamine having 8 or more carbon atoms. While having a high molecular weight, Mw / Mn was suppressed to 4.0 or less.
- the content of the aromatic compound unit in the polyamide of the present embodiment is preferably 25 mol% or less, more preferably 20 mol% or less, further preferably 15 with respect to 100 mol% of the total component amount of the polyamide. It is less than mol%.
- Mw weight average molecular weight
- Mn number average molecular weight
- the ratio ( ⁇ * 1 / ⁇ * 100) of the shear viscosity ( ⁇ * 1) at an angular velocity of 1 rad / s to the shear viscosity ( ⁇ * 100) at an angular velocity of 100 rad / s is preferably 3 or less. It is. More preferably, it is 2.5 or less, More preferably, it is 2 or less. When the ratio ( ⁇ * 1 / ⁇ * 100) is 3 or less, excellent fluidity is obtained in the polyamide of this embodiment.
- the ratio ( ⁇ * 1 / ⁇ * 100) is related to the molecular weight distribution (Mw / Mn) of the polyamide.
- the melting peak temperature (melting point) T pm-1 described later of the polyamide of the present embodiment is preferably 280 ° C. or higher, more preferably 280 ° C. or higher and 330 ° C. or lower, more preferably 300 ° C. It is 330 degreeC or less, More preferably, it is 310 degreeC or more and 325 degrees C or less.
- Polyamide having a melting peak temperature T pm-1 of 330 ° C. or lower is preferable because thermal decomposition and the like in melt processing such as extrusion and molding can be suppressed.
- the constituent components of the polyamide are the above components (a) to (c), and the blending ratio of the components is within the above range.
- the method of controlling etc. are mentioned.
- the melting peak temperature (melting point), the crystallization peak temperature, and the crystallization enthalpy can be measured by differential scanning calorimetry (DSC) according to JIS-K7121. Specifically, it can be measured as follows.
- DSC differential scanning calorimetry
- Diamond-DSC manufactured by PERKIN-ELMER can be used as a measuring device. The measurement conditions are such that about 10 mg of the sample is heated from 50 ° C. to 350 ° C. at a temperature increase rate of 20 ° C./min in a nitrogen atmosphere. The endothermic peak that appears at this time is the melting peak, and the peak that appears on the highest temperature side is the melting peak temperature Tpm . Subsequently, after being kept at 350 ° C.
- the exothermic peak appearing at this time is defined as a crystallization peak
- the crystallization peak temperature is defined as T pc-1
- the crystallization peak area is defined as a crystallization enthalpy.
- the temperature is increased again from 50 ° C. to 350 ° C. at a temperature increase rate of 20 ° C./min.
- the endothermic peak that appears on the highest temperature side at this time is the melting peak temperature T pm-1
- the endothermic peak that appears on the lowest temperature side is the melting peak temperature T pm-2 .
- the difference (T pm -T pm-1 ) between the melting peak temperature T pm and the melting peak temperature T pm-1 is preferably 30 ° C. or less, preferably 0-20 ° C. The range is more preferable, and the range of 0 to 10 ° C. is more preferable.
- a polyamide having a difference between the melting peak temperature T pm and the melting peak temperature T pm-1 (T pm -T pm-1 ) within the above range is excellent in plasticization time stability.
- the polyamide composition containing the polyamide is excellent in surface appearance.
- the polyamide as a method for controlling the difference (T pm -T pm-1 ) between the melting peak temperature T pm and the melting peak temperature T pm-1 within the above range, for example, the above components (a) to (c) And the blending ratio is within the above range, and the ratio of the trans isomer derived from (a) the alicyclic dicarboxylic acid in the polyamide is controlled within the range of 65 to 80 mol%.
- the melting peak temperature T pm-2 of the polyamide of the present embodiment is preferably 270 ° C. or higher, more preferably 270 to 320 ° C. from the viewpoint of heat resistance, and more preferably 280 to 310 ° C. More preferably.
- Examples of a method for controlling the melting peak temperature (melting point) T pm-2 of the polyamide within the above range include a method for controlling the blending ratio to the above range using the components (a) to (c). It is done.
- the difference between the melting peak temperature T pm-1 and the melting peak temperature T pm-2 is preferably 30 ° C. or less, and 10-20 More preferably, it is in the range of ° C.
- the difference (T pm-1 -T pm-2 ) between the melting peak temperature T pm-1 and the melting peak temperature T pm-2 in the polyamide is preferably in the above range from the viewpoint of releasability and low blocking property. .
- the crystallization peak temperature T pc-1 of the polyamide of the present embodiment is preferably 250 ° C. or higher, more preferably 260 ° C. or higher and 300 ° C. or lower, from the viewpoints of low blocking properties and releasability.
- the crystallization peak temperature T pc-1 can be measured by cooling at 20 ° C./min in differential scanning calorimetry according to JIS-K7121. Examples of a method for controlling the crystallization peak temperature T pc-1 of the polyamide within the above range include a method of controlling the compounding ratio within the above range using the components (a) to (c).
- the crystallization peak temperature T pc-2 of the polyamide of the present embodiment is preferably 240 ° C. or higher, more preferably in the range of 240 to 280 ° C. from the viewpoint of low blocking properties and releasability.
- the crystallization peak temperature T pc-2 is 50 ° C./min after the predetermined operation as described above after the measurement of the crystallization peak temperature T pc-1 in the differential scanning calorimetry according to JIS-K7121. It can be measured by cooling again.
- Examples of a method for controlling the crystallization peak temperature T pc-2 of the polyamide within the above range include a method of controlling the blending ratio within the above range using the components (a) to (c).
- the difference (T pc-1 ⁇ T pc-2 ) between the crystallization peak temperature T pc-1 and the crystallization peak temperature T pc-2 is preferably 10 ° C. or less.
- the viewpoint of low blocking property and releasability To preferred.
- the above (a) Examples thereof include a method of controlling the blending ratio within the above-described range using the components (c) to (c).
- the number of carbon atoms in the components (a) to (c) must be an even number,
- the ratio of carbon number to amide group number (carbon number / amide group number) is preferably 8 or more and less than 9.
- the crystallization enthalpy of the polyamide of this embodiment is preferably 10 J / g or more, more preferably 15 J / g or more, and further preferably 20 J / g, from the viewpoints of heat resistance, low blocking properties, and releasability. That's it.
- the upper limit of the crystallization enthalpy of the polyamide of this embodiment is not particularly limited, it is 100 J / g or less.
- the ratio of the number of carbon atoms to the number of amide groups (carbon number / amide group number) in the polyamide is 8 or more, and the above components (a) to (c) And a method of controlling the blending ratio to the above-described range.
- the ratio of carbon number to amide group in the polyamide (carbon number / amide group number) can be controlled by the method described later.
- the glass transition temperature Tg of the polyamide of the present embodiment is preferably 90 ° C. or higher and 170 ° C. or lower, more preferably 90 ° C. or higher and 140 ° C. or lower, still more preferably 100 ° C. or higher and 140 ° C. or lower, and still more preferably. Is 115 ° C. or higher and 140 ° C. or lower.
- a polyamide having excellent heat resistance and chemical resistance can be obtained.
- a molded article having a good surface appearance can be obtained from polyamide.
- Examples of the method for controlling the glass transition temperature Tg of the polyamide within the above range include a method of using the above components (a) to (c) and controlling the compounding ratio of the components within the above range.
- the glass transition temperature Tg can be measured by differential scanning calorimetry (DSC) according to JIS-K7121. Specifically, it can measure by the method as described in the Example mentioned later.
- the polyamide of this embodiment has a difference (T pc-1 -Tg) between the crystallization peak temperature T pc-1 obtained when cooled at 20 ° C./min and the glass transition temperature Tg in the differential scanning calorimetry. It is preferably 140 ° C. or higher, more preferably 145 ° C. or higher, and further preferably 150 ° C. or higher.
- T pc-1 -Tg the difference between the crystallization peak temperature T pc-1 and the glass transition temperature Tg
- a polyamide having a difference between the crystallization peak temperature T pc-1 and the glass transition temperature Tg (T pc-1 -Tg) of 140 ° C. or more is excellent in low blocking property and releasability.
- the upper limit of the difference (T pc-1 -Tg) between the crystallization peak temperature T pc-1 and the glass transition temperature Tg is not particularly limited, but is preferably 300 ° C. or less from the viewpoint of heat resistance.
- the above components (a) to (c) are used. And the like.
- the number of carbon atoms of the components (a) to (c) must be an even number, or the carbon chain may be linear
- the ratio of carbon number to amide group number (carbon number / amide group number) in the polyamide is 8 or more and less than 9.
- the polymer ends of the polyamide in this embodiment are classified and defined as follows. That is, 1) amino terminal, 2) carboxyl terminal, 3) terminal by a sealant, and 4) other terminal.
- the polymer terminal of polyamide means the terminal part of a polymer chain obtained by polymerizing dicarboxylic acid and diamine by amide bond.
- the polymer terminal of the polyamide is one or more of these terminals 1) to 4).
- the amino terminal is a polymer terminal to which an amino group (—NH 2 group) is bonded, and is derived from a raw material diamine.
- the carboxyl end is a polymer end to which a carboxyl group (—COOH group) is bonded, and is derived from the raw dicarboxylic acid.
- the terminal by a sealing agent is the polymer terminal sealed with carboxylic acid or amine added at the time of superposition
- the other terminal is a polymer terminal not classified in the above 1) to 4). For example, the terminal generated by deammonia reaction at the amino terminal, the terminal generated by decarboxylation from the carboxyl terminal, etc. Can be mentioned.
- the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount of the polyamide of this embodiment ⁇ amino terminal amount / (amino terminal amount + carboxyl terminal amount) ⁇ is not particularly limited. It is preferably 3 or more. More preferably, it is 0.5 or more, More preferably, it is 0.7 or more.
- the upper limit of the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount of the polyamide of the present embodiment ⁇ amino terminal amount / (amino terminal amount + carboxyl terminal amount) ⁇ is less than 1.0. preferable.
- the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount of the polyamide is 0.3 or more, the strength, toughness, thermal stability and hydrolysis resistance of the polyamide can be improved. Moreover, the polyamide composition containing the polyamide is excellent in vibration fatigue characteristics.
- the amount of amino terminal bound to the polymer terminal can be measured by neutralization titration. Specifically, 3.0 g of polyamide is dissolved in 100 mL of a 90 mass% phenol aqueous solution, and the obtained solution is titrated with 0.025N hydrochloric acid to determine the amino terminal amount. The end point is determined from the indicated value of the pH meter.
- the amount of carboxyl terminal bound to the polymer terminal can be measured by neutralization titration. Specifically, 4.0 g of polyamide is dissolved in 50 mL of benzyl alcohol, and the resulting solution is titrated with 0.1 N NaOH to determine the carboxyl end amount. The end point is determined from the discoloration of the phenolphthalein indicator.
- the ratio of carbon number to amide group number is preferably 8 or more, more preferably 8.2 or more and less than 9 from the viewpoint of low water absorption.
- the ratio between the number of carbon atoms and the number of amide groups (carbon number / amide group number) is an index indicating the amino group concentration of polyamide.
- the components (a) to (c) are used, and the compounding ratio of the components is controlled within the above-mentioned range. And the like.
- the index indicating the amino group concentration (carbon number / amide group number) can be obtained by calculating the average value of the number of carbon atoms per amide group in the polyamide. Specifically, it can be determined by the method described in Examples described later.
- the polyamide production method according to this embodiment is particularly limited as long as (1) sulfuric acid relative viscosity ⁇ r at 25 ° C. is 2.3 or more and (2) Mw / Mn is 4.0 or less.
- a method for producing polyamide which includes the step of polymerizing (a) at least one alicyclic dicarboxylic acid and (b) at least one diamine having 8 or more carbon atoms.
- the addition amount of dicarboxylic acid and the addition amount of diamine are the same molar amount vicinity.
- the molar amount of the diamine should be 0.9 to 1.2 with respect to the molar amount of the dicarboxylic acid as a whole. Is more preferably 0.95 to 1.1, and still more preferably 0.98 to 1.05.
- the method for producing a polyamide according to the present embodiment preferably further includes a step of increasing the degree of polymerization of the polyamide.
- Examples of the method for producing a polyamide according to this embodiment include various methods as exemplified below: 1) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid, a diamine salt or a mixture thereof is heated and polymerized while maintaining a molten state (hereinafter sometimes referred to as “hot melt polymerization method”). 2) A method of increasing the degree of polymerization while maintaining the solid state of the polyamide obtained by the hot melt polymerization method at a temperature below the melting point (hereinafter sometimes abbreviated as “hot melt polymerization / solid phase polymerization method”).
- a method of polymerizing using a dicarboxylic acid halide component equivalent to a dicarboxylic acid and a diamine component (“solution method”).
- a production method including a hot melt polymerization method is preferable, and when a polyamide is produced by a hot melt polymerization method, it is preferable to maintain a molten state until the polymerization is completed. In order to maintain a molten state, it is necessary to produce it under polymerization conditions suitable for the polyamide composition.
- the polymerization pressure in the hot melt polymerization method is controlled to a high pressure of 23 to 50 kg / cm 2 (gauge pressure), preferably 25 kg / cm 2 (gauge pressure) or higher, and the pressure in the tank is increased while heating is continued.
- a method of decreasing the pressure while taking 30 minutes or more until atmospheric pressure gauge pressure is 0 kg / cm 2
- the polyamide obtained by such a production method can satisfy the characteristics such as the above-mentioned conditions (1) and (2) and the trans isomer ratio.
- polymerization is performed while maintaining the trans isomer ratio of the portion derived from (a) alicyclic dicarboxylic acid in the obtained polyamide at 85% or less.
- the trans isomer ratio at 80% or less, more preferably at 65 to 80%, it is further excellent in color tone, tensile elongation and plasticization time stability, and a high melting point polyamide is obtained.
- the polyamide composition containing the polyamide is excellent in surface appearance.
- the heating temperature may be increased and / or the heating time may be increased.
- the polyamide may be colored by heating or the tensile elongation may be lowered due to thermal degradation.
- the rate of increase in molecular weight may be significantly reduced.
- a trans isomer It is preferable to carry out the polymerization while maintaining the ratio at 80% or less.
- a method for producing a polyamide according to the present embodiment a method of producing a polyamide by 1) a hot melt polymerization method and 2) a hot melt polymerization / solid phase polymerization method is preferable. With such a production method, it is easy to maintain the trans isomer ratio in the polyamide at 80% or less, and the obtained polyamide is excellent in color tone and plasticization time stability. Furthermore, the polyamide composition containing the polyamide is excellent in surface appearance.
- the polymerization form may be a batch type or a continuous type.
- the polymerization apparatus is not particularly limited, and examples thereof include known apparatuses such as an autoclave type reactor, a tumbler type reactor, and an extruder type reactor such as a kneader.
- the method for producing the polyamide according to the present embodiment is not particularly limited as long as it is a method capable of obtaining a polyamide satisfying the above-described characteristics (1) and (2).
- the batch described below Polyamide can be produced by the hot melt polymerization method of the formula.
- Examples of the method for producing polyamide by the batch type hot melt polymerization method include the following methods.
- When producing a polyamide by a hot melt polymerization method it is preferable to maintain a molten state until the polymerization is completed. In order to maintain a molten state, it is necessary to produce it under polymerization conditions suitable for the polyamide composition.
- a solution of about 40 to 60% by mass containing a polyamide component (components (a) to (c) above) was heated to a temperature of 110 to 180 ° C. and about 0.35 to 6 kg / cm 2 (gauge pressure). ) Is concentrated to about 65 to 90% by mass in a concentration tank operated at a pressure of) to obtain a concentrated solution.
- the concentrated solution is then transferred to an autoclave and heating is continued until the pressure in the vessel is about 23-50 kg / cm 2 (gauge pressure). Thereafter, the pressure is maintained at about 23 to 50 kg / cm 2 (gauge pressure) while removing water and / or gas components.
- a pressure suitable for the polyamide composition is required, and particularly when a diamine having a large carbon number is used, the pressure in the container is 25 kg / cm 2 (gauge pressure) or more. It is preferable.
- the pressure in the container is reduced to atmospheric pressure (gauge pressure is 0 kg / cm 2 ).
- the pressure in order to maintain the molten state, it is preferable to reduce the pressure while continuing heating and taking 20 minutes or more. By reducing the pressure to atmospheric pressure and then reducing the pressure as necessary, by-product water can be effectively removed. Thereafter, pressurization is performed with an inert gas such as nitrogen to extrude the polyamide melt as a strand.
- the final temperature of the resin temperature is preferably higher by 10 ° C. or more than T pm-1 in order to maintain a molten state.
- the strand can be cooled and cut to obtain polyamide pellets.
- the polyamide composition of the present embodiment includes the polyamide described above and one or more components selected from the group consisting of inorganic fillers, nucleating agents, lubricants, stabilizers, and polymers other than polyamide.
- inorganic filler examples include, but are not limited to, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, clay, flaky glass, talc, kaolin, mica , Hydrotalcite, calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, silicic acid Calcium, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swelling Tsu-containing mica and apatite, and the like.
- the group consisting of glass fiber, carbon fiber, wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate fiber, aluminum borate fiber and clay One or more selected are preferred. Among these, one or more selected from the group consisting of glass fiber, carbon fiber, wollastonite, kaolin, mica, talc, calcium carbonate, and clay is more preferable.
- the number average fiber diameter of the glass fiber or carbon fiber is preferably 3 to 30 ⁇ m, more preferably 3 to 20 ⁇ m, further preferably 3 to 12 ⁇ m, from the viewpoint of improving toughness and the surface appearance of the molded product. Even more preferred is 4 to 6 ⁇ m.
- the number average fiber diameter of the glass fiber or carbon fiber By setting the number average fiber diameter of the glass fiber or carbon fiber to 30 ⁇ m or less, it is possible to obtain a polyamide composition excellent in toughness and the surface appearance of a molded product.
- the thickness is 3 ⁇ m or more, a polyamide composition having an excellent balance between cost and powder handling surface and physical properties (fluidity) can be obtained. Further, when the thickness is 3 to 9 ⁇ m, a polyamide composition excellent in vibration fatigue characteristics and slidability can be obtained.
- the cross section of the glass fiber or carbon fiber may be perfect or flat.
- a flat cross section include, but are not limited to, a rectangular shape, an oval shape close to a rectangular shape, an elliptical shape, and a saddle shape with a narrowed central portion in the longitudinal direction.
- the “flattening ratio” in this specification refers to a value represented by D2 / D1, where D2 is the major axis of the fiber cross section and D1 is the minor axis of the fiber cross section (a perfect circle is a flat shape). The rate is about 1.)
- the number average fiber diameter is 3 to 30 ⁇ m
- the weight average fiber length is 100 to 750 ⁇ m
- the weight average fiber length from the viewpoint of imparting excellent mechanical strength to the polyamide composition.
- Those having an aspect ratio (L / D) of 10 to 100 between (L) and the number average fiber diameter (D) can be suitably used.
- the flatness is preferably 1.5 or more, more preferably 1.5 to 10.0, more preferably 2.5 to 10.0, and even more preferably 3.1 to 6.0.
- the flatness is in the above range, it is preferable because crushing can be effectively prevented during the mixing, kneading, molding, and other processing with other components, and a desired effect can be sufficiently obtained for the molded product.
- the thickness of the glass fiber or carbon fiber having an aspect ratio of 1.5 or more is not limited to the following, but the minor axis D1 of the fiber cross section is 0.5 to 25 ⁇ m and the major axis D2 of the fiber cross section is 1.25 to It is preferable that it is 250 micrometers. Within the above range, the difficulty of spinning fibers can be effectively avoided, and the strength of the molded product can be improved without reducing the contact area with the resin (polyamide).
- the minor axis D1 is more preferably 3 to 25 ⁇ m, still more preferably 3 to 25 ⁇ m, and the flatness is preferably larger than 3.
- glass fibers and carbon fibers having an aspect ratio of 1.5 or more are obtained by using the methods described in, for example, Japanese Patent Publication No. 3-59019, Japanese Patent Publication No. 4-13300, Japanese Patent Publication No. 4-32775, and the like. Can be manufactured.
- an orifice plate that surrounds a plurality of orifice outlets and has a convex edge extending downward from the bottom surface, or an outer peripheral tip of a nozzle tip having one or more orifice holes
- a glass fiber having a flatness ratio of 1.5 or more produced by using any one of the nozzle chips for spinning a modified cross-section glass fiber provided with a plurality of convex edges extending downward from the glass fiber is preferred.
- fiber strands may be used as rovings as they are, or a cutting step may be obtained and used as chopped glass strands.
- the number average fiber diameter and the weight average fiber length in the present specification are values obtained by the following method.
- the polyamide composition is put in an electric furnace and the contained organic substances are incinerated. From the residue after the treatment, 100 or more glass fibers (or carbon fibers) are arbitrarily selected and observed with a scanning electron microscope (SEM) to measure the fiber diameter of these glass fibers (or carbon fibers). To obtain the number average fiber diameter.
- the weight average fiber length is obtained by measuring the fiber length using the SEM photograph of the 100 or more glass fibers (or carbon fibers) taken at a magnification of 1,000 times.
- the above glass fiber and carbon fiber may be surface-treated with a silane coupling agent or the like.
- the silane coupling agent include, but are not limited to, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, and N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyl.
- Examples include aminosilanes such as dimethoxysilane, mercaptosilanes such as ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyltriethoxysilane, epoxysilanes, and vinylsilanes.
- one or more selected from the group consisting of the above-mentioned components is preferable, and aminosilanes are more preferable.
- an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer; Copolymer, epoxy compound, polyurethane resin, homopolymer of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and primary, secondary and tertiary amines thereof And a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer.
- These may be used alone or in combination of two or more.
- the sizing agent includes unsaturated vinyl monomers other than the carboxylic acid anhydride-containing unsaturated vinyl monomer and the carboxylic acid anhydride-containing unsaturated vinyl monomer.
- a copolymer containing a monomer as a constituent unit, an epoxy compound, a polyurethane resin, and a combination thereof are preferable. More preferably, a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as a structural unit, and a polyurethane resin, And combinations thereof.
- Glass fiber and carbon fiber are continuously produced by drying the fiber strand produced by applying the sizing agent to the fiber using a known method such as a roller-type applicator in the known fiber production process. Obtained by reaction.
- the fiber strand may be used as a roving as it is, or may be used as a chopped glass strand by further obtaining a cutting step.
- the sizing agent imparts (adds) preferably a solid content of 0.2 to 3% by mass, more preferably 0.3 to 2% by mass, with respect to 100% by mass of glass fiber or carbon fiber. Apply (add).
- the addition amount of the bundling agent is preferably 0.2% by mass or more as a solid content with respect to 100% by mass of the glass fiber or the carbon fiber.
- the amount of sizing agent added is preferably 3% by mass or less.
- Inorganic fillers other than glass fibers and carbon fibers are not limited to the following from the viewpoint of improving the strength, rigidity and surface appearance of the molded product, for example, wollastonite, kaolin, mica, talc, Calcium carbonate, magnesium carbonate, potassium titanate fiber, aluminum borate fiber, and clay are preferred. More preferably wollastonite, kaolin, mica, talc, calcium carbonate and clay, more preferably wollastonite, kaolin, mica, talc, even more preferably wollastonite, mica, especially Wollastonite is preferable.
- These inorganic fillers may be used individually by 1 type, and may be used in combination of 2 or more type.
- the average particle diameter of inorganic fillers other than glass fibers and carbon fibers is preferably 0.01 to 38 ⁇ m, more preferably 0.03 to 30 ⁇ m, from the viewpoint of improving toughness and the surface appearance of the molded product, and 0.05 Is more preferably from 25 to 25 ⁇ m, still more preferably from 0.10 to 20 ⁇ m, particularly preferably from 0.15 to 15 ⁇ m.
- the average particle size of the inorganic filler other than the glass fiber and the carbon fiber is 38 ⁇ m or less.
- a polyamide composition excellent in toughness and the surface appearance of the molded product can be obtained.
- the thickness is 0.1 ⁇ m or more, a polyamide composition having an excellent balance between cost and powder handling surface and physical properties (fluidity) can be obtained.
- those having a needle-like shape such as wollastonite have the number average fiber diameter (hereinafter also simply referred to as “average fiber diameter”) as the average particle diameter.
- average fiber diameter the number average fiber diameter
- the maximum value of the length is defined as the (number average) fiber diameter.
- average fiber length About the weight average fiber length (hereinafter, also simply referred to as “average fiber length”) of the above-mentioned needle-like shape, the preferred range of the above-mentioned number average fiber diameter, and the following weight average fiber length (L)
- L weight average fiber length
- the surface appearance of the molded product is improved, and the metal such as an injection molding machine From the viewpoint of preventing the wear of the adhesive parts, 1.5 to 10 is preferable, 2.0 to 5 is more preferable, and 2.5 to 4 is more preferable.
- the inorganic filler other than the glass fiber and the carbon fiber may be subjected to a surface treatment using a silane coupling agent, a titanate coupling agent, or the like.
- silane coupling agent include, but are not limited to, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, and N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane.
- Examples include aminosilanes, mercaptosilanes such as ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyltriethoxysilane, epoxy silanes, and vinyl silanes. Among these, one or more selected from the components listed above are preferable, and aminosilanes are more preferable.
- a surface treating agent may be previously treated on the surface of the inorganic filler, or may be added when the polyamide and the inorganic filler are mixed. The addition amount of the surface treatment agent is preferably 0.05 to 1.5% by mass with respect to 100% by mass of the inorganic filler.
- the content of the inorganic filler is preferably 1 to 200 parts by weight, more preferably 2 to 150 parts by weight, still more preferably 5 to 120 parts by weight, based on 100 parts by weight of polyamide.
- the amount is preferably 10 to 80 parts by mass.
- the nucleating agent means that the crystallization peak temperature of the polyamide composition is increased by addition, the difference between the extrapolation start temperature and the extrapolation end temperature of the crystallization peak is reduced, or the spherulite of the obtained molded product It means a substance that can achieve the effect of miniaturizing or making the size uniform.
- the nucleating agent include, but are not limited to, talc, boron nitride, mica, kaolin, calcium carbonate, barium sulfate, silicon nitride, carbon black, potassium titanate, and molybdenum disulfide. It is done. Only one type of nucleating agent may be used alone, or two or more types may be used in combination.
- the nucleating agent is preferably talc or boron nitride from the viewpoint of the nucleating agent effect. Further, a nucleating agent having a number average particle diameter of 0.01 to 10 ⁇ m is preferable because of its high nucleating agent effect.
- the number average particle size of the nucleating agent is determined by dissolving the molded product in a solvent in which polyamide such as formic acid is soluble, and arbitrarily selecting, for example, 100 or more nucleating agents from the obtained insoluble components, It can be determined by observing and measuring with an optical microscope or a scanning electron microscope.
- the content of the nucleating agent is preferably 0.001 to 1 part by mass, more preferably 0.001 to 0, relative to 100 parts by mass of the polyamide of the present embodiment. 0.5 parts by mass, and more preferably 0.001 to 0.09 parts by mass.
- lubricant examples include, but are not limited to, higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, and higher fatty acid amides.
- One type of lubricant may be used alone, or two or more types may be used in combination.
- higher fatty acids include, for example, stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and saturated or unsaturated, linear or branched aliphatic having 8 to 40 carbon atoms. Examples thereof include monocarboxylic acids, and stearic acid and montanic acid are preferred. As the higher fatty acid, one kind may be used, or two or more kinds may be used in combination.
- the higher fatty acid metal salt is a metal salt of the higher fatty acid.
- the metal element constituting the higher fatty acid metal salt is preferably a group 1, 2, 3 element of the periodic table, zinc, aluminum or the like, more preferably first, such as calcium, sodium, potassium, magnesium or the like. Examples include Group 2 elements, aluminum, and the like.
- Examples of the higher fatty acid metal salt include, but are not limited to, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate, and the like.
- a metal salt of montanic acid and a metal salt of stearic acid are preferred.
- a higher fatty acid metal salt may be used individually by 1 type, and may be used in combination of 2 or more types.
- the higher fatty acid ester is an esterified product of the higher fatty acid and alcohol.
- An ester of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms is preferable.
- the aliphatic alcohol include, but are not limited to, stearyl alcohol, behenyl alcohol, and lauryl alcohol.
- the higher fatty acid ester include, but are not limited to, stearyl stearate and behenyl behenate.
- a higher fatty acid ester one type may be used alone, or two or more types may be used in combination.
- the higher fatty acid amide is an amide compound of the higher fatty acid.
- the higher fatty acid amide include, but are not limited to, stearic acid amide, oleic acid amide, erucic acid amide, ethylene bisstearyl amide, ethylene bis oleyl amide, N-stearyl stearyl amide, N-stearyl erucamide.
- Examples include amides.
- As the higher fatty acid amide, stearic acid amide, erucic acid amide, ethylene bisstearyl amide, and N-stearyl erucamide are preferable, and ethylene bisstearyl amide and N-stearyl erucamide are more preferable. Only one type of higher fatty acid amide may be used alone, or two or more types may be used in combination.
- the lubricant is preferably a higher fatty acid metal salt or a higher fatty acid amide, and more preferably a higher fatty acid metal salt, from the viewpoint of improving moldability.
- the content of the lubricant in the polyamide composition of the present embodiment is preferably 0.001 to 1 part by weight, more preferably 0.03 to 0.5 part by weight with respect to 100 parts by weight of the polyamide. It is. When the content of the lubricant is within the above range, it is possible to obtain a polyamide composition having excellent releasability and plasticizing time stability and excellent toughness, and a polyamide obtained by breaking the molecular chain. Can be prevented.
- Stabilizer examples include, but are not limited to, for example, phenol-based heat stabilizers, phosphorus-based heat stabilizers, amine-based heat stabilizers, and groups 3, 4, and 11 to 14 of the periodic table of elements. Metal salts of these elements, and halides of alkali metals and alkaline earth metals.
- the phenol-based heat stabilizer is not limited to the following, and examples thereof include hindered phenol compounds.
- the hindered phenol compound has a property of imparting excellent heat resistance and light resistance to resins such as polyamide and fibers.
- hindered phenol compound examples include, but are not limited to, for example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropylene Onamide), pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, 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 -T-butyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl ⁇ -2,4,8,10-tetraoxapyro [5,5] undecane, , 5-Di-tert-butyl-4
- N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide)] is preferable from the viewpoint of improving heat aging resistance.
- the content of the phenol-based heat stabilizer in the polyamide composition is preferably 0.01 to 1% by mass, more preferably 0, with respect to 100% by mass of the polyamide composition. .1 to 1% by mass.
- content of a phenol type heat stabilizer exists in said range, the heat-resistant aging property of a polyamide composition can be improved further, and also the amount of gas generation can be reduced.
- Examples of the phosphorus-based heat stabilizer include, but are not limited to, pentaerythritol phosphite compounds, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl.
- Phosphite phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2 , 4-Di-t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butylidene- Bis (3-methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4
- a pentaerythritol type phosphite compound and / or tris (2,4-di-t-butylphenyl) from the viewpoint of further improving the heat aging resistance of the polyamide composition and reducing the amount of gas generated.
- Phosphites are preferred.
- the pentaerythritol phosphite compound include, but are not limited to, for example, 2,6-di-t-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2,6-diphosphite.
- the content of the phosphorus-based heat stabilizer in the polyamide composition is preferably 0.01 to 1% by mass, more preferably 100% by mass with respect to 100% by mass of the polyamide composition. 0.1 to 1% by mass.
- the content of the phosphorus-based heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved and the amount of gas generated can be reduced.
- amine heat stabilizers include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetra Methylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6, 6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6 6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethyl Piperidine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyl
- the content of the amine heat stabilizer in the polyamide composition is preferably 0.01 to 1% by mass, more preferably 0 to 100% by mass of the polyamide composition. .1 to 1% by mass.
- 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 generated can be reduced.
- the metal salts of the elements of Groups 3, 4, and 11-14 of the Periodic Table of Elements are not limited as long as they are salts of metals belonging to these groups. From the viewpoint of further improving the heat aging resistance of the polyamide composition, a copper salt is preferable.
- the copper salt include, but are not limited to, copper halides (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, benzoic acid.
- Examples thereof include copper, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and a copper complex in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid. These may be used alone or in combination of two or more.
- copper salts listed above preferably one or more selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate, more preferably Copper iodide and / or copper acetate.
- a polyamide composition having excellent heat aging resistance and capable of effectively suppressing metal corrosion of the screw and cylinder part during extrusion (hereinafter also simply referred to as “metal corrosion”) is provided. can get.
- the content of the copper salt in the polyamide composition is preferably 0.01 to 0.60% by mass, more preferably 0.02 to 0.40 with respect to 100% by mass of the polyamide. % By mass.
- the content of the copper salt is within the above range, the heat aging resistance of the polyamide composition can be further improved, and copper precipitation and metal corrosion can be effectively suppressed.
- concentration of the copper elements derived from the copper salts described above from the viewpoint of improving the thermal aging resistance of the polyamide composition, the polyamic 10 6 parts by weight, preferably 10 to 2,000 parts by mass, more preferably It is 30 to 1500 parts by mass, and more preferably 50 to 500 parts by mass.
- Alkali metal and alkaline earth metal halides include, but are not limited to, for example, potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof. .
- potassium iodide and / or potassium bromide is preferable from the viewpoint of improving heat aging resistance and suppressing metal corrosion, and more preferably potassium iodide.
- the content of alkali metal and alkaline earth metal halides in the polyamide composition is preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the polyamide. Part, more preferably 0.2 to 10 parts by weight.
- the polyamide composition can be further improved in heat aging resistance, and copper precipitation and metal corrosion can be effectively suppressed.
- the components of the heat stabilizer described above may be used alone or in combination of two or more.
- a mixture of a copper salt and a halide of an alkali metal and an alkaline earth metal is preferable.
- the ratio of the copper salt to the halide of the alkali metal and alkaline earth metal is preferably 2/1 to 40/1, more preferably 5 /, as the molar ratio of halogen to copper (halogen / copper). 1 to 30/1. In the above-mentioned range, the heat aging resistance of the polyamide composition can be further improved.
- halogen / copper When the above halogen / copper is 2/1 or more, it is preferable because precipitation of copper and metal corrosion can be effectively suppressed. On the other hand, when the halogen / copper is 40/1 or less, corrosion of the screw of the molding machine and the like can be prevented without substantially impairing mechanical properties (toughness and the like).
- Polymers other than polyamide examples include, but are not limited to, for example, polyamides other than polyamide of the present embodiment, polyester, liquid crystal polyester, polyphenylene sulfide, polyphenylene ether, polycarbonate, polyarylate, phenol resin, epoxy resin, and the like. Is mentioned.
- Polyamides other than the polyamide according to the present embodiment are not limited to the following, but, for example, polyamide 66, polyamide 56, polyamide 46, polyamide 610, polyamide 612, polyamide 6T, polyamide 6I, polyamide 6, polyamide 11 , Polyamide 12, polyamide MXD6, and the like, and homopolymers or copolymers thereof.
- polyester examples include, but are not limited to, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene terephthalate, and polyethylene naphthalate.
- the content of the polymer other than the polyamide according to the present embodiment is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass, and further preferably 5 to 50 parts by mass with respect to 100 parts by mass of the polyamide. is there.
- content of polymers other than polyamide in the polyamide composition of this embodiment into said range, it can be set as the polyamide composition excellent in heat resistance and mold release property.
- additives conventionally used for polyamide for example, colorants such as pigments and dyes (including colored master batches), are difficult within the range that does not impair the purpose of the present embodiment.
- a flame retardant, a fibrillating agent, a fluorescent bleaching agent, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a fluidity improver, a spreading agent, an elastomer and the like can also be contained.
- the content of the other raw materials varies depending on the type and use of the polyamide composition. Therefore, there is no particular limitation as long as it does not impair the object of the present embodiment.
- the method for producing the polyamide composition of the present embodiment is not particularly limited as long as it is a production method including a step of melt-kneading the raw material components containing the above-mentioned polyamide.
- a step of melt-kneading the raw material components containing the above-mentioned polyamide it is preferable to include a step of melting and kneading the raw material component containing the above-mentioned polyamide with an extruder, and setting the temperature of the extruder to the above-mentioned polyamide melting peak temperature T pm-1 + 30 ° C. or less.
- melt-kneading raw material components including polyamide for example, a method in which polyamide and other raw materials are mixed using a tumbler, a Henschel mixer, etc., and supplied to a melt-kneader, kneaded, or single-screw or twin-screw extrusion Examples include a method of blending other raw materials from the side feeder into the polyamide melted by a machine.
- all the components may be supplied to the same supply port at once, or the components may be supplied from different supply ports.
- the melt kneading temperature is preferably about 250 to 375 ° C. as the resin temperature.
- the melt kneading time is preferably about 0.25 to 5 minutes.
- the apparatus for performing the melt kneading is not particularly limited, and a known apparatus such as a single or twin screw extruder, a Banbury mixer, a mixing roll, or the like can be used.
- the molded article of this embodiment contains the above-mentioned polyamide or polyamide composition.
- the molded article of the present embodiment is prepared by using the above-described polyamide or polyamide composition from a known molding method such as press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, It is obtained by molding using generally known plastic molding methods such as multilayer molding and melt spinning.
- the molded article of this embodiment is obtained from the above-mentioned polyamide or polyamide composition, it is excellent in heat resistance, moldability, mechanical strength, low water absorption, vibration fatigue characteristics, and surface appearance. Therefore, the molded product of the present embodiment, as various parts such as various sliding parts, automobile parts, electrical and electronic parts, home appliance parts, OA equipment parts, portable equipment parts, industrial equipment parts, daily necessities and household goods, It can be suitably used for extrusion applications and the like. Among these, the molded product of the present embodiment is suitably used as an automobile part, an electronic part, a home appliance part, an OA equipment part, or a portable equipment part.
- the automobile parts are not particularly limited, and examples thereof include intake system parts, cooling system parts, fuel system parts, interior parts, exterior parts, and electrical parts.
- the automobile intake system parts are not particularly limited, and examples include an air intake manifold, an intercooler inlet, an exhaust pipe cover, an inner bush, a bearing retainer, an engine mount, an engine head cover, a resonator, and a throttle body. .
- the automobile cooling system parts are not particularly limited, and examples thereof include a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an oil netter, and a delivery pipe.
- the automobile fuel system parts are not particularly limited, and examples thereof include a fuel delivery pipe and a gasoline tank case.
- the automobile interior part is not particularly limited, and examples thereof include an instrument panel, a console box, a glove box, a steering wheel, and a trim.
- the automobile exterior parts are not particularly limited, and examples thereof include a mall, a lamp housing, a front grille, a mud guard, a side bumper, a door mirror stay, and a roof rail.
- the automobile electrical component is not particularly limited, and examples thereof include a connector, a wire harness connector, a motor component, a lamp socket, a sensor on-vehicle switch, and a combination switch.
- a connector for light-emitting devices, a switch, a relay, a printed wiring board, the housing of an electronic component, an electrical outlet, a noise filter, a coil bobbin, a motor end cap, etc.
- LEDs light-emitting diodes
- reflectors for light-emitting devices are used in semiconductor packages such as photo-diodes such as laser diodes (LD), photo diodes, charge-coupled devices (CCD), and complementary metal oxide semiconductors (CMOS).
- CMOS complementary metal oxide semiconductors
- portable apparatus components For example, housing
- Industrial equipment parts are not particularly limited, and examples thereof include gears, cams, insulating blocks, valves, electric tool parts, agricultural equipment parts, engine covers, and the like.
- the daily necessities and household goods are not particularly limited, and examples include buttons, food containers, and office furniture.
- extrusion application is not particularly limited, for example, it is used for a film, a sheet, a filament, a tube, a rod, and a hollow molded product.
- the molded product obtained from the polyamide composition of the present embodiment has a thin-walled portion (for example, a thickness of 0.5 mm), and further undergoes a heat treatment process (for example, SMT). It is particularly suitable for electrical and electronic parts such as connectors, reflectors for light emitting devices and switches. Moreover, since the molded product obtained from the polyamide composition of this embodiment is excellent in surface appearance, it is preferably used as a molded product in which a coating film is formed on the surface of the molded product.
- the formation method of the coating film is not particularly limited as long as it is a known method, and for example, it can be performed by coating such as a spray method or an electrostatic coating method.
- the paint used for the coating is not particularly limited as long as it is a known one, and a melamine cross-linked polyester polyol resin paint, an acrylic urethane paint, or the like can be used.
- the polyamide composition of the present embodiment is suitable as a component material for automobiles because it is excellent in mechanical strength, toughness, heat resistance, and vibration fatigue resistance, and is also excellent in slidability. It is particularly suitable as a component material for gears and bearings. Moreover, since it is excellent in mechanical strength, toughness, heat resistance, and dimensional stability, it is suitable as a component material for electric and electronic use.
- ⁇ Inorganic filler> (1) Glass fiber (GF-1) Product name ECS03T275H Number average fiber diameter (average particle diameter) 10 ⁇ m (cross-sectional shape: perfect circle), cut length 3 mm (2) Glass fiber (GF-2) treated with a sizing agent containing maleic anhydride copolymer as in Production Example A below. Number average fiber diameter of GF-2: 7 ⁇ m (cross-sectional shape: perfect circle).
- the solid content is 2% by mass of polyurethane resin, 4% by mass of maleic anhydride-butadiene copolymer, 0.6% by mass of ⁇ -aminopropyltriethoxysilane, and 0.1% by mass of carnauba wax. Dilution with water gave a glass fiber sizing agent. The obtained glass fiber sizing agent was adhered to a melt-proofed glass fiber having a number average fiber diameter of 7 ⁇ m by an applicator provided in the middle of being wound around a rotating drum.
- the glass fiber bundle surface-treated with the said glass fiber sizing agent was obtained by drying the glass fiber to which the glass fiber sizing agent was adhered. At that time, the glass fiber was made to be a bundle of 1,000 pieces. The adhesion amount of the glass fiber sizing agent to the glass fiber was 0.6% by mass. This was cut to a length of 3 mm to obtain a chopped strand (hereinafter also abbreviated as “GF-2”).
- GF-2 chopped strand
- the average fiber diameter of the glass fibers was measured as follows. First, the polyamide composition was placed in an electric furnace, and the organic matter contained in the polyamide composition was incinerated. From the residue after the treatment, 100 or more glass fibers arbitrarily selected were observed with a scanning electron microscope (SEM), and the number average fiber diameter was determined by measuring the fiber diameter of these glass fibers. .
- the peak that appeared on the highest temperature side at this time was defined as the melting peak temperature Tpm-1, and the peak that appeared on the lowest temperature side was defined as the melting peak temperature Tpm-2 . Further, after being kept at 350 ° C. for 3 minutes, it was cooled from 350 ° C. to 50 ° C. at a cooling rate of 50 ° C./min. The crystallization peak temperature appearing at this time was defined as T pc-2 .
- T pm -T pm-1 Difference between melting peak temperature T pm and melting peak temperature T pm-1 (T pm -T pm-1 ), difference between melting peak temperature T pm-1 and melting peak temperature T pm-2 (T pm-1- T pm-2 ), the difference between the crystallization peak temperature T pc-1 and the crystallization peak temperature T pc-2 (T pc-1 -T pc-2 ), the crystallization peak temperature T pc-1 and the glass described later.
- the difference (T pc-1 -Tg) from the transition temperature Tg was measured.
- the glass transition temperature (Tg) of the polyamides obtained in Examples and Comparative Examples was measured using Diamond-DSC manufactured by PERKIN-ELMER according to JIS-K7121.
- the measurement conditions were as follows. A sample in a molten state obtained by melting the sample on a hot stage (EP80 manufactured by Mettler) was rapidly cooled using liquid nitrogen and solidified to obtain a measurement sample. Using 10 mg of the measurement sample, the glass transition temperature (Tg) was measured by raising the temperature in the range of 30 to 350 ° C. under the condition of a temperature elevation rate of 20 ° C./min.
- Mw (weight average molecular weight) / Mn (number average molecular weight) Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamides obtained in the examples and comparative examples are GPC (gel permeation chromatography, manufactured by Tosoh Corporation, HLC-8020, hexafluoroisopropanol solvent, PMMA ( It was calculated using Mw (weight average molecular weight) and number average molecular weight (Mn) measured by a standard sample (polymethyl methacrylate) (converted by Polymer Laboratories).
- Trans isomerization rate The trans isomerization rate in the polyamides obtained in Examples and Comparative Examples was determined as follows. 30-40 mg of polyamide was dissolved in 1.2 g of hexafluoroisopropanol deuteride, and 1 H-NMR was measured using the resulting solution. In the case of 1,4-cyclohexanedicarboxylic acid, from the ratio of the peak area of 1.98 ppm derived from the trans isomer and the peak areas of 1.77 ppm and 1.86 ppm derived from the cis isomer in 1 H-NMR measurement. The trans isomer ratio in the polyamide was determined.
- Ratio of shear viscosity at an angular velocity of 1 rad / s to shear viscosity at an angular velocity of 100 rad / s ( ⁇ * 1 / ⁇ * 100) Test pieces were produced from the polyamide pellets obtained in the examples and comparative examples using a compression molding machine. Specific molding conditions were such that the processing temperature was set to the melting peak temperature (T pm-1 ) + 20 ° C. on the high temperature side of the polyamide, the preheating time was 2 minutes, the heating time was 2 minutes, and the cooling time was 3 minutes. Melt viscoelasticity measurement was performed using the obtained molded piece and ARES-G2 (manufactured by TA Instruments Japan Co., Ltd.).
- Measurement mode Oscillation Frequency Sweep Test, measurement jig: cone & plate, gap gap: 0.05 mm, stabilization time: 5 minutes, strain: 20%, angular velocity: 0.01 rad / sec to 100 rad / sec, load cell: 2 kg, Environmental state: nitrogen stream, measurement temperature: melting peak temperature (T pm-1 ) + 20 ° C. on the high temperature side of polyamide.
- the ratio of the shear viscosity ( ⁇ * 1) at an angular velocity of 1 rad / s to the shear viscosity ( ⁇ * 100) at an angular velocity of 100 rad / s was calculated. When ( ⁇ * 1 / ⁇ * 100) was 3 or less, it was judged that the flow characteristics were good.
- Amino terminal amount ([NH 2 ]) In the polyamides obtained in the examples and comparative examples, the amount of amino terminal bound to the polymer terminal was measured by neutralization titration as follows. 3.0 g of polyamide was dissolved in 100 mL of a 90 mass% phenol aqueous solution, and the obtained solution was titrated with 0.025N hydrochloric acid to determine the amino terminal amount ( ⁇ equivalent / g). The end point was determined from the indicated value of the pH meter.
- Ratio of carbon number to amide group number (carbon number / amide group number)
- the average value of carbon number per amide group (carbon number / amide group number) was obtained by calculation. Specifically, the ratio of the number of carbons to the number of amide groups (carbon number / number of amide groups) was determined by dividing the number of carbons contained in the molecular main chain by the number of amide groups contained in the molecular main chain. The ratio of the number of carbon atoms to the number of amide groups (carbon number / amide group number) was used as an index indicating the amino group concentration in the polyamide.
- a tensile test was performed at a tensile speed of 50 mm / min under a temperature condition of 23 ° C., and a tensile yield stress was measured to obtain a tensile strength. . Further, the temperature condition was set at 120 ° C., and the other conditions were the same as above, and the tensile strength at 120 ° C. was measured.
- the increment of the mass after water absorption with respect to the mass before water absorption was taken as the water absorption amount
- plasticization time stability Multi-purpose test of polyamide pellets obtained in Examples and Comparative Examples using an injection molding machine [PS-40E: manufactured by Nissei Plastic Co., Ltd.] in accordance with ISO 3167 Molded into a piece A-shaped molded piece.
- the specific molding conditions are: injection + holding time 25 seconds, cooling time 15 seconds, mold temperature 120 ° C., molten resin temperature set to the high-temperature side melting peak temperature (T pm-1 ) + 20 ° C. , Up to 1000 shots to obtain ISO test pieces.
- T pm-1 high-temperature side melting peak temperature
- Plasticization time for each of Ai 1000 shots
- X1 arithmetic average of plasticization time for 1000 shots It was determined that the smaller the standard deviation ( ⁇ ), the better the plasticization time stability.
- Polymerization yield in melt polymerization The polymerization yield of the resin during polymerization was evaluated from the amount of polyamide pellets obtained in Examples and Comparative Examples. The ratio of the obtained pellet to the theoretical polyamide amount obtained from an equimolar aqueous solution of about 50% by mass of the raw material monomer charged in the autoclave was calculated. The evaluation criteria are shown below. A (very good): Polymerization yield is 90% or more. ⁇ (Good): The polymerization yield is 85 to 90%. ⁇ (level of no problem in practical use): polymerization yield of 80 to 85%. X (Poor): Polymerization yield is 80% or less.
- dumbbell injection molding test pieces were obtained from the polyamide composition pellets.
- the halogen concentration is combusted in a flask in which the sample is replaced with high-purity oxygen, and the generated gas is collected in an absorbing solution.
- the iodine in the collected solution is 1 / 100N silver nitrate solution.
- Quantification was performed using potentiometric titration.
- the molar ratio of halogen to copper (halogen / Cu) was calculated by converting the molecular weight into a mole using the above quantitative values.
- the strength half-life (days) of the polyamide composition pellets obtained in the examples and comparative examples was measured as follows.
- the dumbbell injection-molded test piece (3 mm thickness) for ASTM tensile test (17) was treated in a hot air oven at 200 ° C. for a predetermined time, and then the tensile strength was measured according to ASTM-D638.
- the tensile strength after the heat treatment with respect to the tensile strength measured before the heat treatment was calculated as the tensile strength retention, and the heat treatment time at which the tensile strength retention was 50% was defined as the strength half-life.
- Example 1 (Production of polyamide)
- the polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
- (A) 750 g (4.35 mol) of CHDC as an alicyclic dicarboxylic acid, and (b) 750 g (4.35 mol) of C10DA as a diamine having 8 or more carbon atoms are dissolved in 1500 g of distilled water, and equimolar amounts of raw material monomers of about 50 A mass% homogeneous aqueous solution was prepared.
- the obtained aqueous solution and 17 g (0.10 mol) of C10DA, which is an additive at the time of melt polymerization, are charged into an autoclave (made by Nitto Koatsu) with an internal volume of 5.4 L, and the liquid temperature (internal temperature) is 50.
- the temperature was kept at 0 ° C., and the inside of the autoclave was replaced with nitrogen.
- gauge pressure hereinafter, all pressure in the tank is expressed as gauge pressure.
- the liquid temperature was continuously heated from about 50 ° C. (the liquid temperature in this system was about 145 ° C.).
- the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 350 ° C. While the resin temperature was kept at about 325 ° C., the inside of the tank was maintained under a reduced pressure of about 13.3 kPa (about 100 torr) for 10 minutes with a vacuum apparatus to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.
- Example 2 to 12 (A) an alicyclic dicarboxylic acid, (b) a diamine having 8 or more carbon atoms, (c) a copolymerization component, and an additive used during melt polymerization, the compounds and amounts shown in Table 1 were used, and Except that the final temperature of the resin temperature was set to the temperature shown in Table 1, a polyamide polymerization reaction was performed by the method described in Example 1 (“hot melt polymerization method”) to obtain polyamide pellets.
- Table 3 shows the measurement results. Moreover, after manufacturing polyamide by the method described in Example 1 using the obtained polyamide, it measured based on the said method about each physical property of a polyamide composition. Table 3 shows the measurement results.
- the polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
- (A) 750 g (4.35 mol) of CHDC as an alicyclic dicarboxylic acid and (b) 750 g (4.35 mol) of C10DA as a diamine having 8 or more carbon atoms are dissolved in 1500 g of distilled water, and equimolar amount of the raw material monomer is about 50 mass. % Homogeneous aqueous solution was prepared.
- the obtained aqueous solution was charged into an autoclave (made by Nitto High Pressure Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the autoclave was purged with nitrogen.
- the liquid temperature was continuously heated from about 50 ° C. until the pressure in the autoclave tank reached about 2.5 kg / cm 2 as gauge pressure (hereinafter, all pressure in the tank was expressed as gauge pressure). (The liquid temperature in this system was about 145 ° C.).
- the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 325 ° C.
- the resin temperature was kept at about 325 ° C., and the inside of the tank was maintained under a reduced pressure of about 13.3 kPa (about 100 torr) for 25 minutes with a vacuum apparatus to obtain a polymer.
- the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.
- Table 4 shows the measurement results.
- the polyamide composition was manufactured by the method described in Example 1 using the obtained polyamide, and each physical property of the polyamide composition was measured based on the above method. Table 4 shows the measurement results.
- the polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
- the polymerization method was in accordance with the production method described in Patent Document 7 (Japanese Patent Publication No. Sho 64-2131).
- (c-2) C6DA161 g (1.39 mol) were dissolved in 500 g of distilled water to obtain about 80 equimolar amounts of raw material monomers.
- a mass% homogeneous aqueous solution was made.
- the obtained aqueous solution was charged into an autoclave (made by Nitto High Pressure Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the autoclave was purged with nitrogen.
- the liquid temperature is continuously heated from about 50 ° C. to 210 ° C., and the pressure in the autoclave tank is expressed as gauge pressure (hereinafter, all pressure in the tank is expressed as gauge pressure) to 17.5 kg / cm 2 . Heating was continued while removing water out of the system to keep it.
- the internal temperature was raised to 320 ° C., and the pressure was reduced while taking about 120 minutes until the pressure in the tank reached atmospheric pressure (gauge pressure was 0 kg / cm 2 ). Thereafter, nitrogen gas was allowed to flow through the tank for 30 minutes, and the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 323 ° C. to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut and discharged in a pellet form to obtain copolymer polyamide pellets. Each physical property of the obtained polyamide was measured based on the above method. Table 4 shows the measurement results. Moreover, after manufacturing the polyamide composition by the method described in Example 1 using the obtained polyamide, each physical property of the polyamide composition was measured based on the above method. Table 4 shows the measurement results.
- the polyamide polymerization reaction was carried out as follows by the “prepolymer / solid phase polymerization method”.
- the polymerization method was in accordance with the production method described in Patent Document 8 (International Publication No. 2002/048239 pamphlet).
- Polymerization reaction of polyamide was carried out by “prepolymer / solid phase polymerization method”.
- (A) 1251.2 g (7.266 mol) of CHDA and (b) 1048.2 g (7.266 mol) of C8DA were dissolved in 3000 g of distilled water to prepare a 50% by mass aqueous solution containing equimolar raw material monomers.
- the reaction was continued for 1 hour until the internal temperature reached 253 ° C., and the reaction was continued for 1 hour while maintaining the pressure at 22 kg / cm 2 to obtain a prepolymer having a number average molecular weight (Mn) of 5000.
- the obtained polyamide was pulverized to a size of 3 mm or less and dried at 100 ° C. for 24 hours while flowing nitrogen gas at a flow rate of 20 L / min.
- This dried prepolymer is extruded using a kneader type reaction extruder (BT-30 manufactured by Plastic Engineering Laboratory Co., Ltd.) under conditions of 300 ° C., a degree of vacuum of 0.03 MPa, and a residence time of 10 minutes. It was.
- Table 4 shows the measurement results.
- the polyamide composition was manufactured by the method described in Example 1 using the obtained polyamide, and each physical property of the polyamide composition was measured based on the above method. Table 4 shows the measurement results.
- the polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”. 836 g (5.72 mol) of ADA and 664 g (5.72 mol) of HMD were dissolved in 1500 g of distilled water to prepare an equimolar aqueous solution of about 50% by mass of the raw material monomer. The obtained aqueous solution was charged into an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the inside of the autoclave was purged with nitrogen. The liquid temperature was continuously heated from about 50 ° C.
- gauge pressure The liquid temperature in this system was about 145 ° C.
- water was removed from the system while heating was continued until the concentration of the aqueous solution reached about 75% by mass (the liquid temperature in this system was It was about 160 ° C.). The removal of water was stopped, and heating was continued until the pressure in the tank reached about 18 kg / cm 2 (the liquid temperature in this system was about 245 ° C.). In order to keep the pressure in the tank at about 30 kg / cm 2 , heating was continued until the final temperature (290 ° C.
- the resin temperature was kept at about 290 ° C., and the inside of the tank was maintained under a reduced pressure of about 13.3 kPa (about 100 torr) for 25 minutes with a vacuum apparatus to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.
- Each physical property of the obtained polyamide was measured based on the above method.
- Table 4 shows the measurement results.
- the polyamide composition was manufactured by the method described in Example 1 using the obtained polyamide, and each physical property of the polyamide composition was measured based on the above method. Table 4 shows the measurement results.
- the polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”. 836 g (5.72 mol) of ADA and 664 g (5.72 mol) of HMD were dissolved in 1500 g of distilled water to prepare an equimolar aqueous solution of about 50% by mass of the raw material monomer. The obtained aqueous solution was charged into an autoclave (made by Nitto High Pressure Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the autoclave was purged with nitrogen. The liquid temperature was continuously heated from about 50 ° C.
- gauge pressure The liquid temperature in this system was about 145 ° C.
- water was removed from the system while heating was continued until the concentration of the aqueous solution reached about 75% by mass (the liquid temperature in this system was It was about 160 ° C.). The removal of water was stopped, and heating was continued until the pressure in the tank reached about 18 kg / cm 2 (the liquid temperature in this system was about 245 ° C.). In order to keep the pressure in the tank at about 30 kg / cm 2 , heating was continued until the final temperature (290 ° C.
- the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.
- Each physical property of the obtained polyamide was measured based on the above method.
- Table 4 shows the measurement results.
- the polyamide composition was manufactured by the method described in Example 1 using the obtained polyamide, and each physical property of the polyamide composition was measured based on the above method. Table 4 shows the measurement results.
- the polyamide obtained by polymerizing (a) at least one alicyclic dicarboxylic acid and (b) a diamine having 8 or more carbon atoms has strength, high temperature strength, low water absorption. It was confirmed that it was excellent in stability and plasticization time stability, and was also excellent in low blocking properties and releasability. It was confirmed that the polyamide compositions containing the polyamide and glass fibers obtained in Examples 1 to 12 were excellent in surface appearance and vibration fatigue characteristics.
- Example 13 [Comparative Examples 10 and 11] The following polyamide, the inorganic filler described above, a copper compound, and a metal halide were used as a raw material for the polyamide composition.
- polyamide The polyamides obtained in Example 2, Comparative Example 3 and Comparative Example 8 were dried in a nitrogen stream to adjust the moisture content to about 0.2% by mass and used as a raw material for the polyamide composition.
- Example 14 Polyamide composition pellets were produced in the same manner as described in Example 13 except that glass fiber (GF-2) was used.
- Example 12 was excellent in durability and slidability. Furthermore, it was found that the polyamide composition of Example 13 using GF having a number average fiber diameter of 7 ⁇ m was more excellent in slidability.
- the polyamide and the polyamide composition according to the present invention can be suitably used as molding materials for various parts such as automobiles, electric and electronic, industrial materials, industrial materials, and daily and household products. Have industrial applicability.
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Abstract
Description
中でも、エンジンルーム内の材料に用いられるポリアミドは、エンジンルーム内の温度が上昇傾向にあるため、高耐熱化の要求が強まっている。
また、特許文献3には、脂肪族ジカルボン酸と脂肪族ジアミンとから誘導される単位から実質的に成るポリアミド組成物から製造された自動車部品が、流動性及び靭性等に優れていることが開示されている。
特許文献7には、1,4-シクロヘキサンジカルボン酸とウンデカメチレンジアミンと1,6-ジアミノヘキサンとを重合したポリアミドが開示されている。
特許文献8には、1,4-シクロヘキサンジカルボン酸と1,12-ジアミノドデカンと1,6-ジアミノヘキサンとを重合したポリアミドが開示されている。
特許文献9には、脂環族ジカルボン酸と、ジアミンと、所定の共重合成分とを共重合させた共重合ポリアミドが開示されている。
特許文献9に開示されたポリアミドは振動疲労特性及び摺動性の面で改善が必要な場合がある。
さらに、重合により得られた三次元構造を有するポリアミド分子の割合の高いポリアミドペレットを押出機や成形機等で高温加工すると、さらにポリアミド分子の三次元構造化が進み、流動特性が安定しないという問題を有している。
すなわち、本発明は、以下のとおりである。
(a)少なくとも1種の脂環族ジカルボン酸からなる単位と、
(b)炭素数8以上のジアミンからなる単位と、
を、含有し、下記条件(1)、(2)を満足する、ポリアミド。
(1)25℃の硫酸相対粘度ηrが2.3以上である。
(2)Mw(重量平均分子量)/Mn(数平均分子量)が4.0以下である。
〔2〕
融解ピーク温度Tpm-1が、280℃以上である、前記〔1〕に記載のポリアミド。
〔3〕
前記(a)脂環族ジカルボン酸が、1,4-シクロヘキサンジカルボン酸である、前記〔1〕又は〔2〕に記載のポリアミド。
〔4〕
前記(a)脂環族ジカルボン酸に由来する部分におけるトランス異性体比率が65~80モル%である、前記〔1〕乃至〔3〕のいずれか一に記載のポリアミド。
〔5〕
角速度1rad/sの剪断粘度(η*1)の、角速度100rad/sの剪断粘度(η*100)に対する比率(η*1/η*100)が3以下である、前記〔1〕乃至〔4〕のいずれか一に記載のポリアミド。
〔6〕
Tgが90℃以上である、前記〔1〕乃至〔5〕のいずれか一に記載のポリアミド。
〔7〕
Tgが115℃以上である、前記〔1〕乃至〔6〕のいずれか一に記載のポリアミド。
〔8〕
Mw(重量平均分子量)/Mn(数平均分子量)が3.3以下である、前記〔1〕乃至〔7〕のいずれか一に記載のポリアミド。
〔9〕
前記ポリアミドが、(c)下記(c-1)~(c-3)からなる群より選ばれる少なくとも1種の共重合成分からなる単位を、さらに含有する、前記〔1〕乃至〔8〕のいずれか一に記載のポリアミド。
(c-1)前記(a)脂環族ジカルボン酸以外のジカルボン酸
(c-2)炭素数が前記(b)のジアミンの炭素数以下の前記(b)以外のジアミン
(c-3)ラクタム及び/又はアミノカルボン酸
〔10〕
前記(b)炭素数8以上のジアミンがデカメチレンジアミンである、前記〔1〕乃至〔9〕のいずれか一に記載のポリアミド。
〔11〕
前記(c-2)炭素数が前記(b)のジアミンの炭素数以下の前記(b)以外のジアミンが、炭素数4~9の脂肪族ジアミンである、前記〔9〕又は〔10〕に記載のポリアミド。
〔12〕
前記(c-2)炭素数が前記(b)のジアミンの炭素数以下の前記(b)以外のジアミンが、1,6-ヘキサメチレンジアミン、2-メチルペンタメチレンジアミンからなる群より選ばれる少なくとも一種である、前記〔9〕乃至〔11〕のいずれか一に記載のポリアミド。
〔13〕
JIS-K7121に準じた示差走査熱量測定において、20℃/minで冷却したときに得られる結晶化ピーク温度Tpc-1と、ガラス転移温度Tgとの差(Tpc-1-Tg)が140℃以上である、前記〔1〕乃至〔12〕のいずれか一に記載のポリアミド。
〔14〕
炭素数とアミド基数との比(炭素数/アミド基数)が8以上である、前記〔1〕乃至〔13〕のいずれか一に記載のポリアミド。
〔15〕
JIS-K7121に準じた示差走査熱量測定において、20℃/minで冷却したときに得られる結晶化ピーク温度Tpc-1と、当該結晶化ピーク温度Tpc-1の測定後、50℃/minで再度冷却したときに得られる結晶化ピーク温度Tpc-2との差(Tpc-1-Tpc-2)が10℃以下である、前記〔1〕乃至〔14〕のいずれか一に記載のポリアミド。
〔16〕
前記(c)共重合成分の含有量が、ポリアミドの全構成成分量100モル%に対し、7.5モル%以上20.0モル%以下である、前記〔9〕乃至〔15〕のいずれか一に記載のポリアミド。
〔17〕
前記ポリアミドが、重合工程の少なくとも一部において固相重合工程を経て得られるポリアミドである、前記〔1〕乃至〔16〕のいずれか一に記載のポリアミド。
〔18〕
バイオマスプラスチック度が25%以上である、前記〔1〕乃至〔17〕のいずれか一に記載のポリアミド。
〔19〕
前記〔1〕乃至〔18〕のいずれか一に記載のポリアミドと、
無機充填材、造核剤、潤滑剤、安定剤、及び前記ポリアミド以外のポリマーからなる群より選ばれる1種以上の成分と、
を含むポリアミド組成物。
〔20〕
前記〔1〕乃至〔18〕のいずれか一に記載のポリアミドと、
数平均繊維径が3~9μmであるガラス繊維と、
を含むポリアミド組成物。
〔21〕
前記〔1〕乃至〔18〕のいずれか一に記載のポリアミド、又は前記〔19〕若しくは〔20〕に記載のポリアミド組成物を含む成形品。
〔22〕
前記〔1〕乃至〔18〕のいずれか一に記載のポリアミド、又は前記〔19〕若しくは〔20〕に記載のポリアミド組成物を含む摺動部品。
〔23〕
自動車部品、電子部品、家電部品、OA機器部品、携帯機器部品からなる群より選ばれるいずれかである、前記〔21〕に記載の成形品。
本実施形態のポリアミドは、
(a)少なくとも1種の脂環族ジカルボン酸からなる単位と、
(b)炭素数8以上のジアミンからなる単位と、
を、含有し、下記条件(1)、(2)を満足するポリアミドである。
(1)25℃の硫酸相対粘度ηrが2.3以上である。
(2)Mw(重量平均分子量)/Mn(数平均分子量)が4.0以下である。
本実施形態において、ジカルボン酸としては、ジカルボン酸そのものに限定されるものではなく、当該ジカルボン酸と等価な化合物であってもよい。
当該ジカルボン酸と等価な化合物としては、ジカルボン酸に由来するジカルボン酸構造を有し、ジカルボン酸構造となり得る化合物であれば特に限定されるものではない。例えば、ジカルボン酸の無水物及びハロゲン化物等が挙げられる。
本実施形態のポリアミドは、(a)脂環族ジカルボン酸からなる単位を含有する。
本実施形態に用いる(a)脂環族ジカルボン酸(以下「脂環式ジカルボン酸」とも記され、本明細書中、(a)成分、(a)と記載する場合がある。)としては、以下に限定されるものではないが、例えば、脂環構造の炭素数が3~10である脂環族ジカルボン酸、好ましくは脂環構造の炭素数が5~10である脂環族ジカルボン酸が挙げられる。(a)脂環族ジカルボン酸としては、以下に限定されるものではないが、例えば、1,4-シクロヘキサンジカルボン酸、1,3-シクロヘキサンジカルボン酸、及び1,3-シクロペンタンジカルボン酸等が挙げられる。
前記置換基としては、以下に限定されるものではないが、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、及びtert-ブチル基等の炭素数1~4のアルキル基等が挙げられる。
本実施形態のポリアミドは、(b)炭素数8以上のジアミンからなる単位を含有する。
本実施形態に用いる(b)炭素数8以上のジアミン(本明細書において、(b)成分、(b)のジアミン、(b)と記載する場合がある。)としては、炭素数8以上のジアミンであれば特に限定されず、無置換の直鎖脂肪族ジアミンでも、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、及びtert-ブチル基等の炭素数1~4のアルキル基等の置換基を有する分岐状脂肪族ジアミンでも、脂環族ジアミンでも、芳香族ジアミンでもよい。
本実施形態に用いる(b)炭素数8以上のジアミンにおける炭素数は、低吸水性(吸水性を低くする)の観点から8以上とし、高温強度及び融点を高くする観点から、20以下、すなわち8~20であることが好ましく、8~15であることがより好ましく、8~12であることがさらに好ましい。
また、1,10-デカメチレンジアミンは、バイオマス由来の原料であるという観点からも好ましい。
デカメチレンジアミンとしては、無置換の1,10-デカメチレンジアミンでも、置換基を有する置換1,10-デカメチレンジアミンでもよい。当該置換基としては、特に限定されるものではないが、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、及びtert-ブチル基等の炭素数1~4のアルキル基が挙げられる。
なお、本実施形態において、炭素数8以上のジアミンを2種類以上組み合わせる場合、最も炭素数の多いジアミンを(b)成分とし、それ以外の炭素数8以上のジアミンを後述の(c-2)成分とする。
本実施形態のポリアミドは、本実施形態の目的を損なわない範囲で、上述した(a)、(b)の他、所定の(c)共重合成分(本明細書中、(c)成分、(c)と記載する場合がある。)を含有させることもできる。
前記(c)共重合成分とは、(c-1)脂環族ジカルボン酸以外のジカルボン酸(本明細書中、(c-1)成分、(c-1)と記載する場合がある。)、(c-2)炭素数が前記(b)のジアミンの炭素数以下の前記(b)以外のジアミン(本明細書中、(c-2)成分、(c-2)と記載する場合がある。)、及び(c-3)ラクタム及び/又はアミノカルボン酸(本明細書中、(c-3)成分、(c-3)と記載する場合がある。)からなる群より選ばれる少なくとも1種である。
組み合わせる例としては、(c-1)、(c-2)及び(c-3)の中から自由に組み合わせることができ、例えば、(c-1)から2種類を用いてもよいし、(c-2)や(c-3)から2種類を組み合わせてもよいし、(c-1)から1種類と(c-2)から1種類のように組み合わせてもよい。
(c)共重合成分の含有量を前記範囲とすることで、強度、高温強度、低吸水性、低ブロッキング性、離型性及び可塑化時間安定性に優れるポリアミドとすることができる。また、該ポリアミドを含むポリアミド組成物は、振動疲労特性及び表面外観に優れる。
(c-1)前記(b)脂環族ジカルボン酸以外のジカルボン酸としては、以下に限定されるものではないが、例えば、脂肪族ジカルボン酸及び芳香族ジカルボン酸等が挙げられる。
本実施形態に用いる(c-1)前記(a)脂環族ジカルボン酸以外のジカルボン酸としては、耐熱性、流動性、靭性、低吸水性、強度及び剛性等の観点で、好ましくは芳香族ジカルボン酸であり、より好ましくは、炭素数8の芳香族ジカルボン酸である。
中でも、(c-1)前記(a)脂環族ジカルボン酸以外のジカルボン酸としては、耐熱性、流動性、表面外観等の観点で、イソフタル酸が好ましい。
前記(a)脂環族ジカルボン酸の(a)と(c-1)との合計量中の割合が50~100モル%であることにより、強度、高温強度、低吸水性、低ブロッキング性、離型性及び可塑化時間安定性に優れるポリアミドが得られる。また、当該ポリアミドを含むポリアミド組成物は、振動疲労特性及び表面外観に優れる。
(c-2)炭素数が前記(b)のジアミンの炭素数以下の前記(b)以外のジアミンとしては、以下に限定されるものではないが、例えば、脂肪族ジアミン、脂環族ジアミン及び芳香族ジアミン等が挙げられる。
前記多価脂肪族アミンは、1種類を単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
(c-3)ラクタム及び/又はアミノカルボン酸とは、重(縮)合可能なラクタム及び/又はアミノカルボン酸を意味する。
中でも、アミノカルボン酸としては、低吸水、靭性の観点で、11-アミノウンデカン酸、12-アミノドデカン酸等がより好ましい。
本実施形態のポリアミドにおいて、(a)少なくとも1種の脂環族ジカルボン酸と、(b)炭素数8以上のジアミンとの含有割合は、同モル量であることが好ましい。そのため、本実施形態のポリアミドを得る際の原料として、ジカルボン酸の使用量とジアミンの使用量とは、同モル量付近であることが好ましい。具体的には、重合反応中のジアミンの反応系外への逃散分もモル比においては考慮して、ジカルボン酸全体のモル量1に対して、ジアミン全体のモル量は、0.9~1.2であることが好ましく、より好ましくは0.95~1.1であり、さらに好ましくは0.98~1.05である。
(c)共重合成分の含有割合は、ポリアミドの全構成成分量100モル%に対し、好ましくは5.0モル%以上22.5モル%以下であり、より好ましくは7.5モル%以上20.0モル%以下であり、さらに好ましくは10.0モル%以上18.0モル%以下である。(c)共重合成分の含有割合を前記範囲とすることで、強度、高温強度、低吸水性、低ブロッキング性、離型性及び可塑化時間安定性に優れるポリアミドが得られる。
本実施形態のポリアミドを重合する際に、上記(a)~(c)成分以外に、分子量調節のために公知の末端封止剤をさらに添加することができる。
末端封止剤としては、以下に限定されるものではないが、例えば、モノカルボン酸、モノアミン、無水フタル酸等の酸無水物;モノイソシアネート、モノ酸ハロゲン化物、モノエステル類、及びモノアルコール類等が挙げられ、熱安定性の観点で、モノカルボン酸、及びモノアミンが好ましい。
末端封止剤は、1種類を単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
モノカルボン酸としては、1種類で用いてもよいし、2種類以上を組み合わせて用いてもよい。
モノアミンとしては、1種類で用いてもよいし、2種類以上を組み合わせて用いてもよい。
<トランス異性体比率>
本実施形態のポリアミドにおいて、脂環族ジカルボン酸構造は、トランス異性体及びシス異性体の幾何異性体として存在する。
本実施形態のポリアミド中、(a)脂環族ジカルボン酸に由来する部分におけるトランス異性体比率は、ポリアミド中の脂環族ジカルボン酸全体中のトランス異性体である比率を表す。当該トランス異性体比率は、好ましくは50~85モル%であり、より好ましくは50~80モル%であり、さらに好ましくは65~80モル%である。
ポリアミド中の(a)脂環族ジカルボン酸に由来する部分におけるトランス異性体比率を上記範囲内に制御する方法としては、例えば、ポリアミドの重合方法、並びに重合条件を制御する方法等が挙げられる。熱溶融重合法によりポリアミドを製造する際には、重合が終了するまで、溶融状態を保持することが好ましい。溶融状態を保持するためには、ポリアミド組成に適した重合条件で製造することが必要となる。具体的には、例えば、重合圧力を23~50kg/cm2(ゲージ圧)、好ましくは25kg/cm2(ゲージ圧)以上の高圧に制御し、加熱を続けながら、槽内の圧力が大気圧(ゲージ圧は0kg/cm2)になるまで30分以上かけながら降圧する方法等が挙げられる。
本実施形態のポリアミドのバイオマスプラスチック度は、環境負荷の低減の観点から25%以上であることが好ましい。ここで、バイオマスプラスチック度とは、ポリアミドのうち、バイオマス由来の原料にて構成されるユニットの割合を意味する。バイオプラスチック度は、後述する実施例に記載する方法により算出することができる。より好ましいバイオプラスチック度としては30%以上である。本実施形態のポリアミドのバイオマスプラスチック度の上限値は、特に限定されないが、ポリアミドの耐熱性の観点から例えば80%である。
本実施形態のポリアミドの分子量は、25℃の硫酸相対粘度ηrを指標とすることができる。
本実施形態のポリアミドの25℃の硫酸相対粘度ηrは、ポリアミドの強度、高温強度、及びポリアミド組成物の振動疲労特性等の観点から、2.3以上とする。好ましくは2.3~5.0であり、より好ましくは2.4~4.0であり、さらに好ましくは2.5~3.5である。
本実施形態のポリアミドの分子量分布は、Mw(重量平均分子量)/Mn(数平均分子量)を指標とする。
本実施形態のポリアミドのMw(重量平均分子量)/Mn(数平均分子量)は、ポリアミドの強度、高温強度、及びポリアミド組成物の振動疲労特性等の観点から、4.0以下である。好ましくは1.5~3.5であり、より好ましくは1.5~3.3であり、さらに好ましくは1.5~3.0であり、よりさらに好ましくは1.5~2.5である。分子量分布の下限は1.0である。
これにより、高分子量でありながら、三次元構造を有するポリアミド分子の割合が少なく、さらに高温加工時において分子の三次元構造化を抑制でき、優れた流動性が得られる。
また、本実施形態のポリアミドは、上述したように、25℃の硫酸相対粘度ηrが2.3以上であり、かつMw/Mnが4.0以下である。
ポリアミドの分子構造中に芳香族化合物単位が含有していると、高分子量化に伴い、分子量分布(Mw/Mn)が高くなる傾向がある。分子量分布が高いことは分子の三次元構造を有するポリアミド分子の割合が高いことを示し、高温加工時において分子の三次元構造化がさらに進行しやすく、流動性が悪化する。
本実施形態のポリアミドにおいては、(a)脂環族ジカルボン酸からなる単位と、(b)炭素数8以上のジアミンからなる単位とを含有するポリアミドとすることによって、ηrが2.3以上の高分子量でありながら、Mw/Mnを4.0以下に抑制した。
本実施形態のポリアミドにおける芳香族化合物単位の含有量は、ポリアミドの全構成成分量100モル%に対し、好ましくは25モル%以下であり、より好ましくは20モル%以下であり、さらに好ましくは15モル%以下である。
本実施形態のポリアミドは、角速度1rad/sの剪断粘度(η*1)の、角速度100rad/sの剪断粘度(η*100)に対する比率(η*1/η*100)が、好ましくは3以下である。
より好ましくは2.5以下であり、さらに好ましくは2以下である。
上記比率(η*1/η*100)が3以下であることにより、本実施形態のポリアミドにおいて優れた流動性が得られる。
上記比率(η*1/η*100)は、ポリアミドの分子量分布(Mw/Mn)と関係がある。すなわち、Mw/Mnが4以下であることにより、三次元構造化している比率が少なく、さらに高温加工時における分子の三次元化が抑制でき、良好な流動性が得られ、上記比率(η*1/η*100)≦3が実現できる。
所定の角速度におけるポリアミドの剪断粘度は、後述する実施例に記載する方法により測定することができる。
本実施形態のポリアミドの、後述する融解ピーク温度(融点)Tpm-1は、耐熱性の観点から、好ましくは280℃以上、より好ましくは280℃以上330℃以下であり、さらに好ましくは300℃以上330℃以下であり、さらにより好ましくは310℃以上325℃以下である。
融解ピーク温度Tpm-1が330℃以下であるポリアミドは、押出、成形等の溶融加工における熱分解等を抑制することができるため好ましい。
ポリアミドの融解ピーク温度(融点)Tpm-1を前記範囲内に制御する方法としては、例えば、ポリアミドの構成成分を上記(a)~(c)成分とし、成分の配合比率を上述した範囲に制御する方法等が挙げられる。
測定することができる。具体的には、以下のとおり測定することができる。
測定装置としては、PERKIN-ELMER社製Diamond-DSCを用いることができる。
測定条件は、窒素雰囲気下、試料約10mgを昇温速度20℃/minで50℃から350℃まで昇温する条件とする。このときに現れる吸熱ピークを融解ピークとし、もっとも高温側に現れるピークを融解ピーク温度Tpmとする。
続いて、350℃で3分間保った後、冷却速度20℃/minで350℃から50℃まで冷却する。このときに現れる発熱ピークを結晶化ピークとし、結晶化ピーク温度をTpc-1、結晶化ピーク面積を結晶化エンタルピーとする。
続いて、50℃で3分間保った後、再度昇温速度20℃/minで50℃から350℃まで昇温する。このときに現れるもっとも高温側に現れる吸熱ピークを融解ピーク温度Tpm-1とし、もっとも低温側に現れる吸熱ピークを融解ピーク温度Tpm-2とする。
なお、このときに現れる吸熱ピークが1つの場合は、該吸熱ピークを融解ピーク温度Tpm-1及びTpm-2(Tpm-1=Tpm-2)とする。さらに、350℃で3分間保った後、冷却速度50℃/minで350℃から50℃まで冷却する。このときに現れる結晶化ピーク温度をTpc-2とする。
ポリアミドの融解ピーク温度(融点)Tpm-2を前記範囲内に制御する方法としては、例えば、上記(a)~(c)成分を用い、配合比率を上述した範囲に制御する方法等が挙げられる。
ポリアミドにおける融解ピーク温度Tpm-1と融解ピーク温度Tpm-2との差(Tpm-1-Tpm-2)を前記範囲内に制御する方法としては、例えば、上記(a)~(c)成分を用い、配合比率を上述した範囲に制御する方法等が挙げられる。
本実施形態のポリアミドの結晶化ピーク温度Tpc-1は、低ブロッキング性、離型性の観点から、好ましくは250℃以上であり、より好ましくは260℃以上300℃以下である。
結晶化ピーク温度Tpc-1は、JIS-K7121に準じた示差走査熱量測定において、20℃/minで冷却することにより測定することができる。
ポリアミドの結晶化ピーク温度Tpc-1を前記範囲内に制御する方法としては、例えば、上記(a)~(c)成分を用い、配合比率を上述した範囲に制御する方法等が挙げられる。
結晶化ピーク温度Tpc-2は、JIS-K7121に準じた示差走査熱量測定において、前記結晶化ピーク温度Tpc-1の測定後、上記のように所定の操作を経た後、50℃/minで再度冷却することにより測定できる。
ポリアミドの結晶化ピーク温度Tpc-2を前記範囲内に制御する方法としては、例えば、上記(a)~(c)成分を用い、配合比率を上述した範囲に制御する方法等が挙げられる。
ポリアミドにおいて、結晶化ピーク温度Tpc-1と結晶化ピーク温度Tpc-2との差(Tpc-1-Tpc-2)が小さいほど、結晶化速度が速く、ポリアミドの結晶構造が安定であることを意味する。ポリアミドにおける結晶化ピーク温度Tpc-1と結晶化ピーク温度Tpc-2との差(Tpc-1-Tpc-2)が前記範囲内であると、低ブロッキング性、離型性の観点から好ましい。
ポリアミドにおける結晶化ピーク温度Tpc-1と結晶化ピーク温度Tpc-2との差(Tpc-1-Tpc-2)を前記範囲内に制御する方法としては、例えば、上記(a)~(c)成分を用い、配合比率を上述した範囲に制御する方法等が挙げられる。また、(Tpc-1-Tpc-2)を小さくし、ポリアミドを安定な結晶構造にするためには、(a)~(c)成分の炭素数を偶数とすることや、ポリアミド中の炭素数とアミド基数との比(炭素数/アミド基数)を8以上9未満とすることが好ましい。
ポリアミドの結晶化エンタルピーを前記範囲内に制御する方法としては、例えば、ポリアミド中の炭素数とアミド基数との比(炭素数/アミド基数)を8以上とし、上記(a)~(c)成分を用い、配合比率を上述した範囲に制御する方法等が挙げられる。
ポリアミド中の炭素数とアミド基との比(炭素数/アミド基数)は、後述する方法により制御できる。
本実施形態のポリアミドのガラス転移温度Tgは、好ましくは90℃以上170℃以下であり、より好ましくは90℃以上140℃以下であり、さらに好ましくは100℃以上140℃以下であり、よりさらに好ましくは115℃以上140℃以下である。該ガラス転移温度Tgを90℃以上とすることにより、耐熱性や耐薬品性に優れるポリアミドとすることができる。また、ガラス転移温度を170℃以下とすることにより、ポリアミドから表面外観のよい成形品を得ることができる。
ポリアミドのガラス転移温度Tgを前記範囲内に制御する方法としては、例えば、成分を上記(a)~(c)成分を用い、成分の配合比率を上述した範囲に制御する方法等が挙げられる。
ポリアミドにおいて、結晶化ピーク温度Tpc-1と、ガラス転移温度Tgとの差(Tpc-1-Tg)が大きいほど、結晶化できる温度範囲が広く、ポリアミドの結晶構造が安定であることを意味する。
結晶化ピーク温度Tpc-1とガラス転移温度Tgとの差(Tpc-1-Tg)が140℃以上であるポリアミドは、低ブロッキング性、離型性に優れる。結晶化ピーク温度Tpc-1とガラス転移温度Tgとの差(Tpc-1-Tg)の上限は、特に限定されないが、耐熱性の観点から、300℃以下であることが好ましい。
本実施形態におけるポリアミドのポリマー末端は、以下のように分類し、定義される。
すなわち、1)アミノ末端、2)カルボキシル末端、3)封止剤による末端、及び4)その他の末端である。
ポリアミドのポリマー末端とは、ジカルボン酸とジアミンとがアミド結合により重合したポリマー鎖の末端部分を意味する。前記ポリアミドのポリマー末端は、これら1)~4)の末端のうちの1種以上である。
2)カルボキシル末端は、カルボキシル基(-COOH基)が結合したポリマー末端であり、原料のジカルボン酸に由来する。
3)封止剤による末端は、重合時に添加した、カルボン酸又はアミンにより封止されたポリマー末端である。
4)その他の末端は、上記の1)~4)に分類されないポリマー末端であり、例えば、アミノ末端が脱アンモニア反応して生成した末端や、カルボキシル末端から脱炭酸反応して生成した末端等が挙げられる。
具体的には、ポリアミド4.0gをベンジルアルコール50mLに溶解し、得られた溶液について0.1NのNaOHで滴定を行い、カルボキシル末端量を求める。終点はフェノールフタレイン指示薬の変色から決定する。
本実施形態のポリアミドにおいて、炭素数とアミド基数との比(炭素数/アミド基数)は、低吸水の観点から8以上であることが好ましく、より好ましくは8.2以上9未満である。
当該炭素数とアミド基数との比(炭素数/アミド基数)は、ポリアミドのアミノ基濃度を示す指標である。
当該炭素数とアミド基数との比(炭素数/アミド基数)を前記範囲内とすることにより、強度、高温強度、低吸水性、低ブロッキング性、離型性及び可塑化時間安定性に優れたポリアミド、並びに振動疲労特性及び表面 外観に優れたポリアミド組成物を提供できる。
本実施形態に係るポリアミドの製造方法としては、(1)25℃の硫酸相対粘度ηrが2.3以上であり、(2)Mw/Mnが4.0以下であれば、特に限定されるものではなく、上述した(a)少なくとも1種の脂環族ジカルボン酸と、(b)少なくとも1種の炭素数8以上のジアミンとを重合させる工程を含む、ポリアミドの製造方法が挙げられる。
本実施形態のポリアミドを得る際に、ジカルボン酸の添加量とジアミンの添加量とは、同モル量付近であることが好ましい。重合反応中のジアミンの反応系外への逃散分もモル比においては考慮して、ジカルボン酸全体のモル量1に対して、ジアミン全体のモル量は、0.9~1.2であることが好ましく、より好ましくは0.95~1.1であり、さらに好ましくは0.98~1.05である。
1)ジカルボン酸、ジアミン塩又はその混合物の、水溶液又は水の懸濁液を加熱し、溶融状態を維持したまま重合させる方法(以下「熱溶融重合法」と略称する場合がある。)。
2)熱溶融重合法で得られたポリアミドを融点以下の温度で固体状態を維持したまま重合度を上昇させる方法(以下「熱溶融重合・固相重合法」と略称する場合がある。)。
3)ジカルボン酸と等価なジカルボン酸ハライド成分と、ジアミン成分とを用いて重合させる方法(「溶液法」)。
中でも、熱溶融重合法を含む製造方法が好ましく、熱溶融重合法によりポリアミドを製造する際には、重合が終了するまで、溶融状態を保持することが好ましい。溶融状態を保持するためには、ポリアミド組成に適した重合条件で製造することが必要となる。例えば、該熱溶融重合法における重合圧力を23~50kg/cm2(ゲージ圧)、好ましくは25kg/cm2(ゲージ圧)以上の高圧に制御し、加熱を続けながら、槽内の圧力が大気圧(ゲージ圧は0kg/cm2)になるまで30分以上かけながら降圧する方法などが挙げられる。このような製造方法により得られるポリアミドは、上述した条件(1)、(2)やトランス異性体比率等の特性を満たすことができる。
このような製造方法であると、ポリアミドにおけるトランス異性体比率を80%以下に維持することが容易であり、また、得られるポリアミドは色調及び可塑化時間安定性に優れる。さらに、該ポリアミドを含むポリアミド組成物は、表面外観に優れる。
熱溶融重合法によりポリアミドを製造する際には、重合が終了するまで、溶融状態を保持することが好ましい。溶融状態を保持するためには、ポリアミド組成に適した重合条件で製造することが必要となる。
水を溶媒として、ポリアミド成分(上記(a)~(c)成分)を含有する約40~60質量%の溶液を、110~180℃の温度及び約0.35~6kg/cm2(ゲージ圧)の圧力で操作される濃縮槽で、約65~90質量%に濃縮して濃縮溶液を得る。次いで、該濃縮溶液をオートクレーブに移し、容器における圧力が約23~50kg/cm2(ゲージ圧)になるまで加熱を続ける。その後、水及び/又はガス成分を抜きながら圧力を約23~50kg/cm2(ゲージ圧)に保つ。ここで、溶融状態を保持するためには、ポリアミド組成に適した圧力が必要であり、特に炭素数の大きいジアミンを用いた際には容器における圧力が25kg/cm2(ゲージ圧)以上であることが好ましい。容器における温度が約250~350℃に達した時点で、容器における圧力を大気圧まで降圧する(ゲージ圧は、0kg/cm2)。ここで、溶融状態を保持するためには、加熱を続けながら、20分以上かけながら降圧することが好ましい。大気圧に降圧後、必要に応じて減圧することにより、副生する水を効果的に除くことができる。その後、窒素などの不活性ガスで加圧し、ポリアミド溶融物をストランドとして押し出す。樹脂温度(液温)の最終温度は溶融状態を保持するためTpm-1より10℃以上高い方が好ましい。該ストランドを、冷却、カッティングしてポリアミドのペレットを得ることができる。
本実施形態のポリアミド組成物は、上述したポリアミドと、無機充填材、造核剤、潤滑剤、安定剤、及びポリアミド以外のポリマーからなる群から選ばれる1種以上の成分と、を含む。
無機充填材としては、以下に限定されるものではないが、例えば、ガラス繊維、炭素繊維、ケイ酸カルシウム繊維、チタン酸カリウム繊維、ホウ酸アルミニウム繊維、クレー、フレーク状ガラス、タルク、カオリン、マイカ、ハイドロタルサイト、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、酸化亜鉛、リン酸一水素カルシウム、ウォラストナイト、シリカ、ゼオライト、アルミナ、ベーマイト、水酸化アルミニウム、酸化チタン、酸化ケイ素、酸化マグネシウム、ケイ酸カルシウム、アルミノケイ酸ナトリウム、ケイ酸マグネシウム、ケッチェンブラック、アセチレンブラック、ファーネスブラック、カーボンナノチューブ、グラファイト、黄銅、銅、銀、アルミニウム、ニッケル、鉄、フッ化カルシウム、モンモリロナイト、膨潤性フッ素雲母及びアパタイトが挙げられる。
ガラス繊維や炭素繊維の数平均繊維径は、靭性、及び成形品の表面外観を向上させる観点から、3~30μmが好ましく、3~20μmがより好ましく、3~12μmがさらに好ましく、3~9μmがさらにより好ましく、4~6μmがよりさらに好ましい。
上記のガラス繊維や炭素繊維の数平均繊維径を30μm以下とすることにより、靭性、及び成形品の表面外観に優れたポリアミド組成物とすることができる。一方、3μm以上とすることにより、コスト面及び粉体のハンドリング面と物性(流動性など)とのバランスに優れたポリアミド組成物が得られる。さらに3~9μmとすることにより、振動疲労特性、摺動性に優れたポリアミド組成物とすることができる。
前記繊維ストランドをロービングとしてそのまま使用してもよく、さらに切断工程を得て、チョップドガラスストランドとして使用してもよい。
前記集束剤は、ガラス繊維又は炭素繊維100質量%に対し、固形分率として、好ましくは0.2~3質量%相当を付与(添加)し、より好ましくは0.3~2質量%相当を付与(添加)する。すなわち、当該繊維の集束を維持する観点から、集束剤の添加量が、ガラス繊維又は炭素繊維100質量%に対し、固形分率として0.2質量%以上であることが好ましい。一方、得られるポリアミド組成物の熱安定性を向上させる観点から、集束剤の添加量は3質量%以下であることが好ましい。ストランドの乾燥は切断工程後に行ってもよいし、ストランドを乾燥した後に切断してもよい。
造核剤とは、添加によりポリアミド組成物の、結晶化ピーク温度を上昇させたり、結晶化ピークの補外開始温度と補外終了温度との差を小さくしたり、得られる成形品の球晶を微細化又はサイズの均一化させたりする効果が得られる物質のことを意味する。
造核剤としては、以下に限定されるものではないが、例えば、タルク、窒化ホウ素、マイカ、カオリン、炭酸カルシウム、硫酸バリウム、窒化珪素、カーボンブラック、チタン酸カリウム、及び二硫化モリブデン等が挙げられる。
造核剤は、1種類のみを単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
また、造核剤効果が高いため、数平均粒径が0.01~10μmである造核剤が好ましい。
造核剤の数平均粒径は、成形品をギ酸等のポリアミドが可溶な溶媒で溶解し、得られた不溶成分の中から、例えば、100個以上の造核剤を任意に選択し、光学顕微鏡や走査型電子顕微鏡等で観察して測定することにより求めることができる。
造核剤の含有量を、ポリアミド100質量部に対して、0.001質量部以上とすることにより、ポリアミド組成物の耐熱性が向上し、また、造核剤の含有量を、ポリアミド100質量部に対して1質量部以下とすることにより、靭性に優れるポリアミド組成物が得られる。
潤滑剤としては、以下に限定されないが、例えば、高級脂肪酸、高級脂肪酸金属塩、高級脂肪酸エステル、及び高級脂肪酸アミド等が挙げられる。
潤滑剤は、1種類を単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
高級脂肪酸としては、1種類で用いてもよいし、2種類以上を組み合わせて用いてもよい。
高級脂肪酸金属塩を構成する金属元素としては、元素周期律表の第1,2,3族元素、亜鉛、及びアルミニウム等が好ましく、より好ましくはカルシウム、ナトリウム、カリウム、及びマグネシウム等の第1,2族元素、並びにアルミニウム等が挙げられる。
高級脂肪酸金属塩としては、以下に限定されるものではないが、例えば、ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸亜鉛、ステアリン酸マグネシウム、モンタン酸カルシウム、及びモンタン酸ナトリウム、パルミチン酸カルシウム等が挙げられ、モンタン酸の金属塩及びステアリン酸の金属塩等が好ましい。
高級脂肪酸金属塩は、1種類を単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
脂肪族アルコールとしては、以下に限定されるものではないが、例えば、ステアリルアルコール、ベヘニルアルコール、及びラウリルアルコール等が挙げられる。
高級脂肪酸エステルとしては、以下に限定されるものではないが、例えば、ステアリン酸ステアリル、ベヘン酸ベヘニル等が挙げられる。
高級脂肪酸エステルとしては、1種類を単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
高級脂肪酸アミドとしては、以下に限定されるものではないが、例えば、ステアリン酸アミド、オレイン酸アミド、エルカ酸アミド、エチレンビスステアリルアミド、エチレンビスオレイルアミド、N-ステアリルステアリルアミド、N-ステアリルエルカアミド等が挙げられる。
高級脂肪酸アミドとしては、好ましくはステアリン酸アミド、エルカ酸アミド、エチレンビスステアリルアミド、及びN-ステアリルエルカアミドであり、より好ましくはエチレンビスステアリルアミド及びN-ステアリルエルカアミドである。
高級脂肪酸アミドは、1種類のみを単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。
潤滑剤の含有量が上記範囲内にあることにより、離型性及び可塑化時間安定性に優れ、また、靭性に優れるポリアミド組成物とすることができると共に、分子鎖が切断されることによるポリアミドの極端な分子量低下を防止することができる。
安定剤としては、以下に制限されないが、例えば、フェノール系熱安定剤、リン系熱安定剤、アミン系熱安定剤、並びに元素周期律表の第3族、第4族及び第11~14族の元素の金属塩、並びにアルカリ金属及びアルカリ土類金属のハロゲン化物等が挙げられる。
これらは、1種のみを単独で用いてもよく、2種以上を組み合わせて用いてもよい。
特に、耐熱エージング性向上の観点から、好ましくはN,N'-へキサン-1,6-ジイルビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニルプロピオンアミド)]である。
これらは、1種のみを単独で用いてもよく、2種以上を組み合わせて用いてもよい。
これらは、1種のみを単独で用いてもよく、2種以上を組み合わせて用いてもよい。
ポリアミド以外のポリマーとしては、以下に限定されるものではないが、例えば、本実施形態のポリアミド以外のポリアミド、ポリエステル、液晶ポリエステル、ポリフェニレンスルフィド、ポリフェニレンエーテル、ポリカーボネート、ポリアリレート、フェノール樹脂、エポキシ樹脂等が挙げられる。
本実施形態のポリアミド組成物の製造方法としては、上述のポリアミドを含む原料成分を溶融混練する工程を含む製造方法であれば、特に限定されるものではない。例えば、上述のポリアミドを含む原料成分を押出機で溶融混練する工程を含み、前記押出機の設定温度を、上述のポリアミドの融解ピーク温度Tpm-1+30℃以下とする方法が好ましい。
溶融混練時間は、0.25~5分程度であることが好ましい。
溶融混練を行う装置としては、特に限定されるものではなく、公知の装置、例えば、単軸又は2軸押出機、バンバリーミキサー、及びミキシングロールなどの溶融混練機を用いることができる。
本実施形態の成形品は、上述のポリアミド又はポリアミド組成物を含む。
本実施の形態の成形品は、上述のポリアミド又はポリアミド組成物を、公知の成形方法、例えばプレス成形、射出成形、ガスアシスト射出成形、溶着成形、押出成形、吹込成形、フィルム成形、中空成形、多層成形、及び溶融紡糸等、一般に知られているプラスチック成形方法を用いて成形することにより得られる。
携帯機器部品としては、特に限定されるものではないが、例えば、携帯電話、スマートフォン、パソコン、携帯ゲーム機器、デジタルカメラ等の筐体、及び構造体等が挙げられる。
また、本実施形態のポリアミド組成物から得られる成形品は、表面外観に優れているので、成形品表面に塗装膜を形成させた成形品としても好ましく用いられる。塗装膜の形成方法は公知の方法であれば特に限定されるものではなく、例えば、スプレー法、静電塗装法等の塗装によることができる。また、塗装に用いる塗料は、公知のものであれば特に限定されず、メラミン架橋タイプのポリエステルポリオール樹脂塗料、アクリルウレタン系塗料などを用いることができる。
中でも、本実施形態のポリアミド組成物は、機械的強度、靱性、耐熱性に優れ、耐振動疲労性にも優れることから自動車用の部品材料として好適であり、さらに、摺動性に優れることから、ギヤ、ベアリング用の部品材料として特に好適である。また、機械的強度、靱性、耐熱性、寸法安定性に優れることから、電気及び電子用の部品材料として好適である。
なお、本実施例において、1kg/cm2は、0.098MPaを意味する。
本実施例及び比較例においては、下記化合物を用いた。
(1)1,4-シクロヘキサンジカルボン酸(CHDC)
商品名:1,4-CHDA HPグレード(トランス体/シス体=25/75)(イーストマンケミカル社製)
(2)セバシン酸(C10DC)
商品名:セバシン酸TA(伊藤製油社製)
(3)イソフタル酸(IPA)(和光純薬工業社製)
(4)アジピン酸(ADA)(和光純薬工業社製)
(1)1,10-ジアミノデカン(1,10-デカメチレンジアミン)(C10DA)
商品名:1,10-デカンジアミン(小倉合成工業社製)
(2)1,12-ジアミノドデカン(1,12-ドデカメチレンジアミン)(C12DA)(東京化成工業社製)
(3)1,6-ジアミノヘキサン(1,6-ヘキサメチレンジアミン)(C6DA)(東京化成工業社製)
(4)2-メチルペンタメチレンジアミン(2MC5DA)(東京化成工業製)
(5)オクタメチレンジアミン(C8DA)(東京化成工業社製)
(6)ウンデカメチレンジアミン(C11DA)(東京化成工業社製)
(7)1,9-ノナメチレンジアミン(C9DA)(アルドリッチ社製)
(8)2-メチルオクタメチレンジアミン(2MOD) 特開平05-17413号公報に記載されている製法を参考にして製造した。
(9)ヘキサメチレンジアミン(HMD)(和光純薬工業社製)
(1)ε-カプロラクタム(CPL)(和光純薬工業社製)
(1)ガラス繊維(GF-1) 日本電気硝子製 商品名 ECS03T275H 数平均繊維径(平均粒径)10μm(断面形状:真円状)、カット長3mm
(2)下記製造例Aのとおり無水マレイン酸共重合体を含む集束剤により処理されたガラス繊維(GF-2)。GF-2の数平均繊維径:7μm(断面形状:真円状)。
〔ガラス繊維の製造例〕
<製造例A>
まず、固形分として、ポリウレタン樹脂2質量%、無水マレイン酸-ブタジエン共重合体4質量%、γ-アミノプロピルトリエトキシシラン0.6質量%、及びカルナウバワックス0.1質量%となるように水で希釈し、ガラス繊維集束剤を得た。
得られたガラス繊維集束剤を、溶融防糸された数平均繊維径7μmのガラス繊維に対して、回転ドラムに巻き取られる途中に設けたアプリケーターによって付着させた。
その後、ガラス繊維集束剤を付着させたガラス繊維を乾燥することによって、上記ガラス繊維集束剤で表面処理されたガラス繊維束のロービングを得た。
その際、ガラス繊維は1,000本の束となるようにした。ガラス繊維に対するガラス繊維集束剤の付着量は、0.6質量%であった。これを3mmの長さに切断して、チョップドストランド(以下、「GF-2」とも略記する。)を得た。
なお、本実施例において、ガラス繊維の平均繊維径は、以下のとおり測定した。
まず、ポリアミド組成物を電気炉に入れて、ポリアミド組成物中に含まれる有機物を焼却処理した。当該処理後の残渣分から、任意に選択した100本以上のガラス繊維を、走査型電子顕微鏡(SEM)で観察して、これらのガラス繊維の繊維径を測定することにより数平均繊維径を求めた。
(ポリアミド中の各構成単位の含有量)
ポリアミド中の各構成単位の含有量を1H-NMR測定により以下のように定量した。
実施例及び比較例で得られたポリアミドのペレットを約5質量%の濃度になるように重ヘキサフルオロイソプロパノールに加熱して溶解し、日本電子製核磁気共鳴分析装置JNM ECA-500を用いて1H-NMRの分析を行い、積分比を計算することによって、下記の含有量を決定した。
実施例及び比較例で得られたポリアミドの、融解ピーク温度(融点)、結晶化ピーク温度及び結晶化エンタルピーを、JIS-K7121に準じて、PERKIN-ELMER社製Diamond-DSCを用いて測定した。
測定は、窒素雰囲気下で行った。
先ず、試料約10mgを昇温速度20℃/minで50℃から350℃まで昇温する条件とした。このときに現れる吸熱ピークを融解ピークとし、もっとも高温側に現れたピークを融解ピーク温度Tpmとした。
続いて、350℃で3分間保った後、冷却速度20℃/minで350℃から50℃まで冷却した。このときに現れる発熱ピークを結晶化ピークとし、結晶化ピーク温度をTpc-1、結晶化ピーク面積を結晶化エンタルピーとした。
続いて、50℃で3分間保った後、再度昇温速度20℃/minで50℃から350℃まで昇温した。このときに現れるもっとも高温側に現れたピークを融解ピーク温度Tpm-1とし、もっとも低温側に現れたピークを融解ピーク温度Tpm-2とした。
さらに、350℃で3分間保った後、冷却速度50℃/minで350℃から50℃まで冷却した。このときに現れる結晶化ピーク温度をTpc-2とした。
融解ピーク温度Tpmと融解ピーク温度Tpm-1との差(Tpm-Tpm-1)、融解ピーク温度Tpm-1と融解ピーク温度Tpm-2との差(Tpm-1-Tpm-2)、結晶化ピーク温度Tpc-1と結晶化ピーク温度Tpc-2との差(Tpc-1-Tpc-2)、結晶化ピーク温度Tpc-1と後述するガラス転移温度Tgとの差(Tpc-1-Tg)を測定した。
実施例及び比較例で得られたポリアミドのガラス転移温度(Tg)を、JIS-K7121に準じて、PERKIN-ELMER社製Diamond-DSCを用いて測定した。
測定条件は、以下のとおりとした。
試料をホットステージ(Mettler社製EP80)で溶融させて得られた溶融状態のサンプルを、液体窒素を用いて急冷し、固化させ、測定サンプルとした。
当該測定サンプル10mgを用いて、昇温速度20℃/minの条件下、30~350℃の範囲で昇温して、ガラス転移温度(Tg)を測定した。
実施例及び比較例で得られたポリアミドの25℃における硫酸相対粘度ηrを、JIS-K6920に準じて測定した。具体的には、98%硫酸を用いて、1%の濃度の溶解液((ポリアミド1g)/(98%硫酸100mL)の割合)を作成し、得られた溶解液を用いて25℃の温度条件下で硫酸相対粘度ηrを測定した。
実施例及び比較例で得られたポリアミドのMw(重量平均分子量)/Mn(数平均分子量)は、GPC(ゲルパーミエーションクロマトグラフィー、東ソー株式会社製、HLC-8020、ヘキサフルオロイソプロパノール溶媒、PMMA(ポリメチルメタクリレート)標準サンプル(ポリマーラボラトリー社製)換算)で測定したMw(重量平均分子量)と数平均分子量(Mn)を用いて計算した。
実施例及び比較例で得られたポリアミドにおけるトランス異性化率を以下のとおり求めた。
ポリアミド30~40mgをヘキサフルオロイソプロパノール重水素化物1.2gに溶解し、得られた溶液を用い、1H-NMRを測定した。
1,4-シクロヘキサンジカルボン酸の場合、1H-NMR測定における、トランス異性体に由来する1.98ppmのピーク面積とシス異性体に由来する1.77ppm及び1.86ppmのピーク面積との比率からポリアミドにおけるトランス異性体比率を求めた。
実施例及び比較例で得られたポリアミドのペレットを、コンプレッション成形機を用いて、試験片を製造した。
具体的な成形条件は、加工温度をポリアミドの高温側の融解ピーク温度(Tpm-1)+20℃に設定し、余熱時間2分、加熱時間2分、冷却時間3分とした。
得られた成形片、及びARES-G2(ティー・エイ・インスツルメント・ジャパン株式会社製)を用いて、溶融粘弾性測定を行った。測定モード:Oscillation Freqency Sweep Test、測定治具:コーン & プレート、ギャップ間:0.05mm、安定時間:5分、歪:20%、角速度:0.01rad/sec~100rad/sec、ロードセル:2kg、環境状態:窒素気流、測定温度:ポリアミドの高温側の融解ピーク温度(Tpm-1)+20℃とした。
角速度1rad/sの剪断粘度(η*1)の、角速度100rad/sの剪断粘度(η*100)に対する比率を算出した。(η*1/η*100)が3以下であると、流動特性が良好であると判断した。
実施例及び比較例で得られたポリアミドにおいて、ポリマー末端に結合するアミノ末端量を、中和滴定により以下のとおり測定した。
ポリアミド3.0gを90質量%フェノール水溶液100mLに溶解し、得られた溶液を用い、0.025Nの塩酸で滴定を行い、アミノ末端量(μ当量/g)を求めた。終点はpH計の指示値から決定した。
実施例及び比較例で得られたポリアミドにおいて、ポリマー末端に結合するカルボキシル末端量を、中和滴定により以下のとおり測定した。
ポリアミド4.0gをベンジルアルコール50mLに溶解し、得られた溶液を用い、0.1NのNaOHで滴定を行い、カルボキシル末端量(μ当量/g)を求めた。終点はフェノールフタレイン指示薬の変色から決定した。
実施例及び比較例で得られたポリアミドにおいて、アミド基1個あたりの炭素数の平均値(炭素数/アミド基数)を計算により求めた。
具体的には、分子主鎖中に含まれる炭素数を分子主鎖中に含まれるアミド基数で除することにより、炭素数とアミド基数との比(炭素数/アミド基数)を求めた。
該炭素数とアミド基数との比(炭素数/アミド基数)を、ポリアミドにおけるアミノ基濃度を示す指標とした。
実施例及び比較例で得られたポリアミドにおいて、バイオマス由来の原料にて構成されるユニットの質量%をバイオマスプラスチック度として算出した。
具体的には、ひまし油を原料としている、セバシン酸、1,10-ジアミノデカンを、バイオマス由来の原料とした。
そして、実施例及び比較例で得られたポリアミドにおいて、セバシン酸及び1,10-ジアミノデカンに由来するユニットの割合を算出し、当該割合をバイオマスプラスチック度とした。
尚、ポリアミドの重合においては、アミド結合の形成の際に、ジアミン中の2つの水素原子と、ジカルボン酸中の2つの酸素原子と、2つの水素原子とから、2モルの水分子が生成することを考慮して算出した。
実施例及び比較例で得られたポリアミドのペレットを、射出成形機[PS-40E:日精樹脂株式会社製]を用いて、ISO 3167に準拠し、多目的試験片A型の成形片に成形した。具体的な成形条件は、射出+保圧時間25秒、冷却時間15秒、金型温度を80℃、溶融樹脂温度をポリアミドの高温側の融解ピーク温度(Tpm-1)+20℃に設定した。
得られた多目的試験片A型の成形片を用いて、ISO 527に準拠し、23℃の温度条件下、引張速度50mm/minで引張試験を行い、引張降伏応力を測定し、引張強度とした。
また、温度条件を120℃下にし、その他の条件は上記と同様にして、120℃における引張強度を測定した。
上記(11)のとおり多目的試験片A型の成形片を成形した後の絶乾状態(dry as mold)で、多目的試験片A型の成形片の試験前質量(吸水前質量)を測定した。次に、多目的試験片A型の成形片を、80℃の純水中に72時間浸漬させた。その後、水中から多目的試験片A型の成形片を取り出し、表面の付着水分をふき取り、恒温恒湿(23℃、50RH%)雰囲気下に30分放置後、試験後質量(吸水後質量)を測定した。吸水前質量に対しての吸水後質量の増分を吸水量とし、吸水前質量に対する吸水量の割合を、試行数n=3で求め、その平均値を吸水率とした。
実施例及び比較例で得られたポリアミドのペレットを、L/D(押出機のシリンダーの長さ/押出機のシリンダー径)=48(バレル数:12)の二軸押出機[ZSK-26MC:コペリオン社製(ドイツ)]を用いて、押出機の上流側供給口からダイまでを340℃に設定し、スクリュー回転数200rpm、吐出量25kg/hで溶融混練した。ダイから排出されたストランド1.5mを20℃の水浴に浸漬し、ストランドカッターによりカッティングしてペレットを得た。このとき水浴の浸漬時間を約2秒になるようにした。得られたペレット5kgを、角度:45度、投入口の径:500mm、排出口の径:50mmのステンレス製漏斗に投入し、漏斗上でブロッキングし、残留したポリアミドの割合を測定した。
上記(11)における射出成形機[PS-40E:日精樹脂株式会社製]を用いて、射出+保圧時間5秒、金型温度をポリアミドのTgと同じ温度に設定し、溶融樹脂温度をポリアミドの高温側の融解ピーク温度(Tpm-1)+20℃に設定して、実施例及び比較例で得られたポリアミドから、長さ128mm×巾12.8mm×厚さ0.75mmの成形片を成形した。冷却時間を調整し、金型から成形品が問題なく離型する最短の冷却時間を、離型性として評価した。当該冷却時間を短縮することは、生産性の向上に繋がると判断した。
実施例及び比較例で得られたポリアミドのペレットを、射出成形機[PS-40E:日精樹脂株式会社製]を用いて、ISO 3167に準拠し、多目的試験片A型の成形片に成形した。
具体的な成形条件は、射出+保圧時間25秒、冷却時間15秒、金型温度を120℃、溶融樹脂温度をポリアミドの高温側の融解ピーク温度(Tpm-1)+20℃に設定し、1000ショットまで成形し、ISO試験片を得た。
該射出成形の各ショットにおいて、ポリアミドのペレットが可塑化状態となるまでの時間(以下「可塑化時間」とも記す。)を測定した。該測定値に基づき、可塑化時間安定性(標準偏差)を下記式により求めた。
X1=1000ショットの可塑化時間の相加平均
上記の標準偏差(σ)が小さいほど、可塑化時間安定性に優れるものと判断した。
実施例及び比較例で得られたポリアミドのペレット量から、重合時の樹脂の重合収率の評価を行った。
得られたペレットの、オートクレーブに仕込んだ原料モノマーの等モル約50質量%均一水溶液から得られる理論ポリアミド量に対する比率を算出した。
以下、評価基準を示す。
◎(極めて良好):重合収率が90%以上。
○(良好):重合収率が85~90%。
△(実用上問題ないレベル):重合収率が80~85%。
×(不良):重合収率が80%以下。
ASTM引張試験用のダンベル射出成形試験片(3mm厚)を用いて、ASTM D638に準じて破壊応力(MPa)の測定を行った。
実施例及び比較例で得られたポリアミド組成物のペレットからダンベル射出成形試験片を以下のとおり成形した。
射出成形機(日精樹脂(株)製PS40E)にASTM引張試験(ASTM D638)用のダンベル試験片(3mm厚)の金型(金型温度=Tg+20℃)を取り付けて、シリンダー温度=(Tpm-1+10)℃~(Tpm-1+30)℃で成形を行って、ポリアミド組成物のペレットからダンベル射出成形試験片を得た。
得られたASTM引張試験用のダンベル射出成形試験片(3mm厚)について、株式会社鷺宮製作所製油圧サーボ疲労試験機EHF-50-10-3を用い、120℃の雰囲気下、周波数20Hzの正弦波にて引張り荷重を負荷し、100,000回で破壊する応力(MPa)を求めた。求めた破壊応力(MPa)が大きいほど振動疲労特性に優れると評価した。
実施例及び比較例で得られたポリアミド組成物のペレットから平板プレート成形片を以下のとおり製造した。
射出成形機[FN-3000:日精樹脂株式会社製]を用いて、冷却時間25秒、スクリュー回転数200rpm、金型温度をTg+20℃、シリンダー温度=(Tpm-1+10)℃~(Tpm-1+30)℃に設定し、充填時間が1.0±0.1秒の範囲となるように、射出圧力及び射出速度を適宜調整し、ポリアミド組成物ペレットから平板プレート成形片(13cm×13cm、厚さ1mm)を製造した。
このようにして作製した平板プレート成形片の中央部を、光沢計(HORIBA製IG320)を用いてJIS-K7150に準じて60度グロスを測定した。
該測定値が大きいほど表面外観に優れると判断した。
実施例及び比較例で得られたポリアミド組成物のペレットについて、銅濃度、ハロゲン濃度、及びハロゲンと銅とのモル比(ハロゲン/Cu)を以下のとおり測定した。
銅濃度は、試料に硫酸を加え、加熱しながら硝酸を滴下し有機分を分解し、該分解液を純水にて定容しICP発光分析(高周波プラズマ発光分析)法により定量した。ICP発光分析装置は、SEIKO電子工業社製Vista-Proを用いた。
ハロゲン濃度は、ヨウ素を例にとると、試料を高純度酸素で置換したフラスコ中で燃焼し、発生したガスを吸収液に捕集し、該捕集液中のヨウ素を1/100N硝酸銀溶液による電位差滴定法を用いて定量した。
ハロゲンと銅とのモル比(ハロゲン/Cu)は、上記それぞれの定量値を用いて分子量からモルに換算し算出した。
実施例及び比較例で得られたポリアミド組成物のペレットの強度半減期(日)を以下のとおり測定した。
上記(17)のASTM引張試験用のダンベル射出成形試験片(3mm厚)を熱風オーブン中で200℃、所定時間処理した後、ASTM-D638に準じて引張強度を測定した。そして熱処理前に測定した引張強度に対する熱処理後の引張強度を引張強度保持率として算出し、引張強度保持率が50%となる熱処理時間を強度半減期とした。
実施例及び比較例で得られたポリアミド組成物のペレットの浸漬後の引張強度保持率(%)を以下のとおり測定した。
上記(17)のASTM引張試験用のダンベル射出成形試験片(3mm厚)を、120℃のエチレングリコール50%水溶液に、24時間、720時間浸漬し、室温に放置した後、上記(11)の方法の引張試験を行い、引張強度を測定した。720時間浸漬後に測定した引張強度の、24時間浸漬後に測定した引張強度に対する割合を浸漬後の引張強度保持率として求めた。
上記(11)で製造した多目的試験片(A型)を用いて、往復動摩擦摩耗試験機(AFT-15MS:東洋精密株式会社製)により荷重150g、線速度400mm/sec、往復距離30mmの条件下、環境温度23℃で100,000回の往復試験を行った。相手材料としては、SUS球(SUS304、R=2.5mm)を用いた。
往復試験を実施した後の多目的試験片の削られた部分について、表面粗さ計(Surfcom:東京精密社製)を用いて、Rmaxを測定し、摩耗深さを評価した。
(ポリアミドの製造)
「熱溶融重合法」によりポリアミドの重合反応を以下のとおり実施した。
(a)脂環族ジカルボン酸としてCHDC750g(4.35モル)、(b)炭素数8以上のジアミンとしてC10DA750g(4.35モル)を、蒸留水1500gに溶解させ、原料モノマーの等モル約50質量%均一水溶液を調製した。
上記のポリアミド及びガラス繊維を用いてポリアミド組成物の製造を実施した。
2軸押出機(東芝機械(株)製TEM35、L/D=47.6(D=37mmφ)、設定温度Tm2+20℃(実施例1で得られたポリアミドを用いた場合、325+20=345℃)、スクリュー回転数300rpm)を用いて、以下のとおりポリアミド組成物を製造した。該2軸押出機の最上流部に設けられたトップフィード口より、上記水分率を調整したポリアミド(100質量部)を供給し、前記2軸押出機の下流側(トップフィード口より供給された樹脂が充分溶融している状態)のサイドフィード口より無機充填材としてガラス繊維を(ポリアミド:ガラス繊維(GF)=50:50)の質量比で供給し、ダイヘッドより押し出された溶融混練物をストランド状で冷却し、ペレタイズしてポリアミド組成物のペレットを得た。
測定結果を表3に示す。
(a)脂環族ジカルボン酸、(b)炭素数8以上のジアミン、(c)共重合成分、及び、溶融重合時の添加物として、表1に記載の化合物及び量を用いたこと、並びに樹脂温度の最終温度を表1に記載の温度にしたこと以外は、実施例1に記載した方法でポリアミドの重合反応を行って(「熱溶融重合法」)、ポリアミドのペレットを得た。
測定結果を表3に示す。
また、得られたポリアミドを用いて、実施例1に記載した方法でポリアミドを製造した後、ポリアミド組成物の各物性について上記方法に基づいて測定した。
測定結果を表3に示す。
「熱溶融重合法」によりポリアミドの重合反応を以下のとおり実施した。
(a)脂環族ジカルボン酸としてCHDC750g(4.35モル)、(b)炭素数8以上のジアミンとしてC10DA750g(4.35モル)を蒸留水1500gに溶解させ、原料モノマーの等モル約50質量%均一水溶液を調製した。
得られたポリアミドの各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
また、得られたポリアミドを用いて、実施例1に記載した方法でポリアミド組成物を製造し、ポリアミド組成物の各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
(a)脂環族ジカルボン酸、(b)炭素数8以上のジアミン、(c)共重合成分として、表1に記載の化合物及び量を用いたこと、並びに樹脂温度の最終温度を表2に記載の温度にしたこと以外は、比較例1に記載した方法でポリアミドの重合反応を行って(「熱溶融重合法」)、ポリアミドのペレットを得た。
得られたポリアミドの各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
また、得られたポリアミドを用いて、実施例1に記載した方法でポリアミド組成物を製造し、ポリアミド組成物の各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
(a)脂環族ジカルボン酸、(b)炭素数8以上のジアミン、(c)共重合成分として、表2に記載の化合物及び量を用いたこと、並びに溶融重合における樹脂温度の最終温度を表2に記載の温度にしたこと、さらに樹脂温度が表2に記載の最終温度の状態で、槽内を真空装置で約53.3kPa(約400torr)の減圧下に25分間維持したこと以外は、比較例1に記載した方法で、ポリアミドの重合反応を行い、ポリアミドのペレットを得た。
得られたポリアミドの各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
また、得られたポリアミドを用いて、実施例1に記載した方法でポリアミド組成物を製造した後、ポリアミド組成物の各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
(a)脂環族ジカルボン酸、(b)炭素数8以上のジアミン、(c)共重合成分として、表2に記載の化合物及び量を用いたこと、並びに溶融重合における樹脂温度の最終温度を表2に記載の温度にしたこと、さらに樹脂温度が表2に記載の最終温度の状態で、槽内を真空装置で約80kPa(約600torr)の減圧下に3分間維持したこと以外は、実施例1に記載した方法で、ポリアミドの重合反応を行い、ポリアミドのペレットを得た。
得られたポリアミドの各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
また、得られたポリアミドを用いて、実施例1に記載した方法でポリアミド組成物を製造した後、ポリアミド組成物の各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
「熱溶融重合法」によりポリアミドの重合反応を以下のとおり実施した。
該重合法は、前記特許文献7(特公昭64-2131号公報)に記載されている製法に準じた。
(a)CHDC1007g(5.85モル)、(b)C11DA832g(4.46モル)、及び(c-2)C6DA161g(1.39モル)を蒸留水500gに溶解させ、原料モノマーの等モル約80質量%均一水溶液を作った。
得られた水溶液を内容積5.4Lのオートクレーブ(日東高圧製)に仕込み、液温(内温)が50℃になるまで保温して、オートクレーブ内を窒素置換した。液温を約50℃から加熱を続けて210℃とし、オートクレーブの槽内の圧力を、ゲージ圧として(以下、槽内の圧力は全てゲージ圧として表記する。)、17.5kg/cm2に保つため水を系外に除去しながら、加熱を続けた。その後、内温を320℃まで昇温し、槽内の圧力が大気圧(ゲージ圧は0kg/cm2)になるまで120分ほどかけながら降圧した。その後、槽内に窒素ガスを30分間流し、樹脂温度(液温)の最終温度が約323℃になるようにヒーター温度を調整し、重合体を得た。その後、得られた重合体を、窒素で加圧し下部紡口(ノズル)からストランド状にし、水冷、カッティングを行いペレット状で排出して、共重合ポリアミドのペレットを得た。
得られたポリアミドの各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
また、得られたポリアミドを用いて、実施例1に記載した方法でポリアミド組成物を製造した後、ポリアミド組成物の各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
「プレポリマー・固相重合法」によりポリアミドの重合反応を以下のとおり実施した。
該重合法は、前記特許文献8(国際公開第2002/048239号パンフレット)に記載されている製法に準じた。
「プレポリマー・固相重合法」によりポリアミドの重合反応を実施した。
(a)CHDA1251.2g(7.266モル)、及び(b)C8DA1048.2g(7.266モル)を蒸留水3000gに溶解させ、等モルの原料モノマーを含む50質量%水溶液を作製した。
液温約50℃から、オートクレーブの槽内の圧力が、ゲージ圧として(以下、槽内の圧力は全てゲージ圧として表記する。)、約2.5kg/cm2になるまで、加熱を続けた。
槽内の圧力を約2.5kg/cm2に保つため水を系外に除去しながら、加熱を続けて、水溶液の濃度が約70%になるまで濃縮した。
その後、内部温度を218℃に昇温した。この時、オートクレーブは22Kg/cm2まで昇圧した。そのまま1時間、内温が253℃に到達するまで、水蒸気を徐々に抜いて圧力を22kg/cm2に保ちながら1時間反応させ、数平均分子量(Mn)5000のプレポリマーを得た。
得られたポリアミドを3mm以下の大きさまで粉砕し、窒素ガスを20L/分の流量でフローさせながら100℃で24時間乾燥した。この乾燥したプレポリマーをニーダー型反応押出機((株)プラスチック工学研究所製BT-30)を用いて、300℃、減圧度0.03MPa、滞留時間10分の条件下で押出してポリアミドを得た。
得られたポリアミドの各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
また、得られたポリアミドを用いて、実施例1に記載した方法でポリアミド組成物を製造し、ポリアミド組成物の各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
「熱溶融重合法」によりポリアミドの重合反応を以下のとおり実施した。
ADA836g(5.72モル)、HMD664g(5.72モル)を蒸留水1500gに溶解させ、原料モノマーの等モル約50質量%均一水溶液を調製した。
得られた水溶液を、内容積5.4Lのオートクレーブ(日東高圧製)に仕込み、液温(内温)が50℃になるまで保温して、オートクレーブ内を窒素置換した。オートクレーブの槽内の圧力が、ゲージ圧として(以下、槽内の圧力は全てゲージ圧として表記する。)、約2.5kg/cm2になるまで、液温を約50℃から加熱を続けた(この系での液温は約145℃であった。)。槽内の圧力を約2.5kg/cm2に保つため水を系外に除去しながら、加熱を続けて、水溶液の濃度が約75質量%になるまで濃縮した(この系での液温は約160℃であった。)。水の除去を止め、槽内の圧力が約18kg/cm2になるまで加熱を続けた(この系での液温は約245℃であった。)。槽内の圧力を約30kg/cm2に保つため、水を系外に除去しながら、最終温度(後述の290℃)-20℃(ここでは270℃)になるまで加熱を続けた。液温が最終温度(後述の290℃)-20℃(ここでは270℃)まで上昇した後に、加熱は続けながら、槽内の圧力が大気圧(ゲージ圧は0kg/cm2)になるまで30分ほどかけながら降圧した。
その後、樹脂温度(液温)の最終温度が約290℃になるようにヒーター温度を調整した。樹脂温度は約290℃のまま、槽内を真空装置で約13.3kPa(約100torr)の減圧下に25分維持し、重合体を得た。その後、得られた重合体を、窒素で加圧し下部紡口(ノズル)からストランド状にし、水冷、カッティングを行いペレット状で排出して、ポリアミドのペレットを得た。
得られたポリアミドの各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
また、得られたポリアミドを用いて、実施例1に記載した方法でポリアミド組成物を製造し、ポリアミド組成物の各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
「熱溶融重合法」によりポリアミドの重合反応を以下のとおり実施した。
ADA836g(5.72モル)、HMD664g(5.72モル)を蒸留水1500gに溶解させ、原料モノマーの等モル約50質量%均一水溶液を調製した。
得られた水溶液を内容積5.4Lのオートクレーブ(日東高圧製)に仕込み、液温(内温)が50℃になるまで保温して、オートクレーブ内を窒素置換した。オートクレーブの槽内の圧力が、ゲージ圧として(以下、槽内の圧力は全てゲージ圧として表記する。)、約2.5kg/cm2になるまで、液温を約50℃から加熱を続けた(この系での液温は約145℃であった。)。槽内の圧力を約2.5kg/cm2に保つため水を系外に除去しながら、加熱を続けて、水溶液の濃度が約75質量%になるまで濃縮した(この系での液温は約160℃であった。)。水の除去を止め、槽内の圧力が約18kg/cm2になるまで加熱を続けた(この系での液温は約245℃であった。)。槽内の圧力を約30kg/cm2に保つため、水を系外に除去しながら、最終温度(後述の290℃)-20℃(ここでは270℃)になるまで加熱を続けた。液温が最終温度(後述の290℃)-20℃(ここでは270℃)まで上昇した後に、加熱は続けながら、槽内の圧力が大気圧(ゲージ圧は0kg/cm2)になるまで60分ほどかけながら降圧した。
その後、樹脂温度(液温)の最終温度が約290℃になるようにヒーター温度を調整した。樹脂温度は約290℃のまま、槽内を真空装置で約13.3kPa(約100torr)の減圧下に25分維持し、重合体を得た。その後、得られた重合体を、窒素で加圧し下部紡口(ノズル)からストランド状にし、水冷、カッティングを行いペレット状で排出して、ポリアミドのペレットを得た。
得られたポリアミドの各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
また、得られたポリアミドを用いて、実施例1に記載した方法でポリアミド組成物を製造し、ポリアミド組成物の各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
樹脂温度の最終温度を表2に記載の温度にしたこと以外は、比較例8に記載した方法でポリアミドの重合反応を行って(「熱溶融重合法」)、ポリアミドのペレットを得た。
得られたポリアミドの各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
また、得られたポリアミドを用いて、実施例1に記載した方法でポリアミド組成物を製造し、ポリアミド組成物の各物性について上記方法に基づいて測定した。
測定結果を表4に示す。
実施例1~12で得られたポリアミドとガラス繊維とを含むポリアミド組成物は、表面外観、振動疲労特性に優れることが確認された。
ポリアミド組成物の原料として、以下のポリアミド、上述した無機充填材、銅化合物及び金属ハロゲン化物を用いた。
(ポリアミド)
実施例2、比較例3、及び比較例8で得られたポリアミドを、窒素気流中で乾燥し水分率を約0.2質量%に調整して、ポリアミド組成物の原料として用いた。
(銅化合物及び金属ハロゲン化物を含む顆粒(1)の製造)
KI 85.1質量部、エチレンビスステアリルアミド10質量部を混合し、KIとエチレンビスステアリルアミドとの混合物を得た。該混合物にCuI 4.9質量部をよく混合し、ディスクペレッター(不二パウダル社製F5-11-175)で顆粒化し、顆粒(1)を得た。
(ポリアミド組成物の製造及び物性評価)
2軸押出機(東芝機械(株)製TEM35、L/D=47.6(D=37mmφ)、設定温度Tpm-1+20℃(この場合、300+20=320℃)、スクリュー回転数300rpm)を用いて、以下のとおりポリアミド組成物を製造した。
前記2軸押出機の最上流部に設けられたトップフィード口より、上記水分率を調整したポリアミド(100質量部)、上記で製造した顆粒(1)(6.1質量部)を供給し、前記2軸押出機の下流側(トップフィード口より供給された樹脂が充分溶融している状態)のサイドフィード口より無機充填材としてガラス繊維(GF-1)を、下記表5に示す割合(質量部)で供給し、ダイヘッドより押し出された溶融混練物をストランド状で冷却し、ペレタイズしてポリアミド組成物のペレットを得た。
得られたポリアミド組成物の各物性について上記方法に基づいて測定した。
なお、引張試験における引張速度は5mm/minで実施した。
測定結果を表5に示す。
ガラス繊維(GF-2)を用いたこと以外は、実施例13に記載した方法と同様にして、ポリアミド組成物ペレットを作製した。
なお、引張試験における引張速度は5mm/minで実施した。
測定結果を表5に示す。
さらに数平均繊維径が7μmであるGFを使用した実施例13のポリアミド組成物は、より摺動性に優れることが分かった。
Claims (23)
- (a)少なくとも1種の脂環族ジカルボン酸からなる単位と、
(b)炭素数8以上のジアミンからなる単位と、
を、含有し、下記条件(1)、(2)を満足する、ポリアミド。
(1)25℃の硫酸相対粘度ηrが2.3以上である。
(2)Mw(重量平均分子量)/Mn(数平均分子量)が4.0以下である。 - 融解ピーク温度Tpm-1が、280℃以上である、請求項1に記載のポリアミド。
- 前記(a)脂環族ジカルボン酸が、1,4-シクロヘキサンジカルボン酸である、請求項1又は2に記載のポリアミド。
- 前記(a)脂環族ジカルボン酸に由来する部分におけるトランス異性体比率が65~80モル%である、請求項1乃至3のいずれか一項に記載のポリアミド。
- 角速度1rad/sの剪断粘度(η*1)の、角速度100rad/sの剪断粘度(η*100)に対する比率(η*1/η*100)が3以下である、請求項1乃至4のいずれか一項に記載のポリアミド。
- Tgが90℃以上である、請求項1乃至5のいずれか一項に記載のポリアミド。
- Tgが115℃以上である、請求項1乃至6のいずれか一項に記載のポリアミド。
- Mw(重量平均分子量)/Mn(数平均分子量)が3.3以下である、請求項1乃至7のいずれか一項に記載のポリアミド。
- 前記ポリアミドが、(c)下記(c-1)~(c-3)からなる群より選ばれる少なくとも1種の共重合成分からなる単位を、さらに含有する、請求項1乃至8のいずれか一項に記載のポリアミド。
(c-1)前記(a)脂環族ジカルボン酸以外のジカルボン酸
(c-2)炭素数が前記(b)のジアミンの炭素数以下の前記(b)以外のジアミン
(c-3)ラクタム及び/又はアミノカルボン酸 - 前記(b)炭素数8以上のジアミンがデカメチレンジアミンである、請求項1乃至9のいずれか一項に記載のポリアミド。
- 前記(c-2)炭素数が前記(b)のジアミンの炭素数以下の前記(b)以外のジアミンが、炭素数4~9の脂肪族ジアミンである、請求項9又は10に記載のポリアミド。
- 前記(c-2)炭素数が前記(b)のジアミンの炭素数以下の前記(b)以外のジアミンが、1,6-ヘキサメチレンジアミン、2-メチルペンタメチレンジアミンからなる群より選ばれる少なくとも一種である、請求項9乃至11のいずれか一項に記載のポリアミド。
- JIS-K7121に準じた示差走査熱量測定において、20℃/minで冷却したときに得られる結晶化ピーク温度Tpc-1と、ガラス転移温度Tgとの差(Tpc-1-Tg)が140℃以上である、請求項1乃至12のいずれか一項に記載のポリアミド。
- 炭素数とアミド基数との比(炭素数/アミド基数)が8以上である、請求項1乃至13のいずれか一項に記載のポリアミド。
- JIS-K7121に準じた示差走査熱量測定において、20℃/minで冷却したときに得られる結晶化ピーク温度Tpc-1と、当該結晶化ピーク温度Tpc-1の測定後、50℃/minで再度冷却したときに得られる結晶化ピーク温度Tpc-2との差(Tpc-1-Tpc-2)が10℃以下である、請求項1乃至14のいずれか一項に記載のポリアミド。
- 前記(c)共重合成分の含有量が、ポリアミドの全構成成分量100モル%に対し、7.5モル%以上20.0モル%以下である、請求項9乃至15のいずれか一項に記載のポリアミド。
- 前記ポリアミドが、重合工程の少なくとも一部において固相重合工程を経て得られるポリアミドである、請求項1乃至16のいずれか一項に記載のポリアミド。
- バイオマスプラスチック度が25%以上である、請求項1乃至17のいずれか一項に記載のポリアミド。
- 請求項1乃至18のいずれか一項に記載のポリアミドと、
無機充填材、造核剤、潤滑剤、安定剤、及び前記ポリアミド以外のポリマーからなる群より選ばれる1種以上の成分と、
を含むポリアミド組成物。 - 請求項1乃至18のいずれか一項に記載のポリアミドと、
数平均繊維径が3~9μmであるガラス繊維と、
を含むポリアミド組成物。 - 請求項1乃至18のいずれか一項に記載のポリアミド、又は請求項19若しくは20に記載のポリアミド組成物を含む成形品。
- 請求項1乃至18のいずれか一項に記載のポリアミド、又は請求項19若しくは20に記載のポリアミド組成物を含む摺動部品。
- 自動車部品、電子部品、家電部品、OA機器部品、携帯機器部品からなる群より選ばれるいずれかである、請求項21に記載の成形品。
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KR1020177003969A KR20170019493A (ko) | 2012-07-09 | 2013-07-09 | 폴리아미드, 폴리아미드 조성물 및 성형품 |
EP13816545.1A EP2871201A4 (en) | 2012-07-09 | 2013-07-09 | POLYAMIDE, POLYAMIDE COMPOSITION, AND MOLDED ARTICLE |
CN201380034311.3A CN104428346B (zh) | 2012-07-09 | 2013-07-09 | 聚酰胺、聚酰胺组合物及成形品 |
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JP2015155537A (ja) * | 2014-01-20 | 2015-08-27 | 旭化成ケミカルズ株式会社 | ポリアミド樹脂組成物、成形体、及びポリアミド樹脂組成物の製造方法 |
CN105524458A (zh) * | 2014-10-15 | 2016-04-27 | 旭化成化学株式会社 | 聚酰胺树脂组合物及成型体 |
JP2017095536A (ja) * | 2015-11-18 | 2017-06-01 | 旭化成株式会社 | ポリアセタール樹脂組成物 |
JP2019199540A (ja) * | 2018-05-16 | 2019-11-21 | 旭化成株式会社 | セルロース含有樹脂組成物の製造方法 |
JP2020033571A (ja) * | 2018-05-16 | 2020-03-05 | 旭化成株式会社 | セルロース含有樹脂組成物の製造方法 |
JP2020535248A (ja) * | 2017-09-25 | 2020-12-03 | アルケマ フランス | 反りを制限するための、円形断面を有するガラス繊維を有する充填剤のマトリックスとしてのコポリアミド組成物の使用 |
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CN105802202A (zh) * | 2016-05-16 | 2016-07-27 | 苏州新区华士达工程塑胶有限公司 | 一种改性聚酰胺填充型塑料 |
US11326024B2 (en) * | 2016-11-10 | 2022-05-10 | Kaneka Corporation | Polyamide resin, molded body, laminate, medical device, and polyamide resin production method |
EP3743475A1 (en) | 2018-01-23 | 2020-12-02 | Eastman Chemical Company | Novel polyesteramides, processes for the preparation thereof, and polyesteramide compositions |
CN108659524B (zh) * | 2018-05-23 | 2020-11-24 | 江苏金发科技新材料有限公司 | 低浮纤长玻纤增强聚酰胺复合材料及其制备方法 |
KR102204083B1 (ko) * | 2018-11-26 | 2021-01-18 | 롯데케미칼 주식회사 | 폴리아미드 수지의 제조방법 |
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EP2871201A4 (en) | 2015-06-24 |
JP5964964B2 (ja) | 2016-08-03 |
US9228057B2 (en) | 2016-01-05 |
EP2871201A1 (en) | 2015-05-13 |
KR20170019493A (ko) | 2017-02-21 |
CN104428346A (zh) | 2015-03-18 |
JPWO2014010607A1 (ja) | 2016-06-23 |
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