JP2012102232A - Copolyamide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new polyamide highly satisfying moldability in addition to extremely low water-absorbing properties.SOLUTION: This copolyamide comprises (a) 50-98 mol% of a structural unit obtained from an equimolar salt of 1,10-decamethylenediamine and terephthalic acid and (b) 50-2 mol% of a structural unit obtained from an equimolar salt of an aliphatic diamine with 5 or less methylene units and terephthalic acid. If necessary, a structural unit obtained from an equimolar salt of a diamine and a dicarboxylic acid other than the structural units of (a) or (b), or a structural unit obtained from an aminocarboxylic acid or a lactam can be contained therein up to 30 mol%.

Description

  The present invention relates to a novel polyamide which has a very high moldability in addition to extremely low water absorption.

  Semi-aromatic polyamide is used as an alternative to 6 nylon and 66 nylon because of demands for high melting point and high heat aging resistance for automobile parts and electric / electronic parts. 6T nylon made from hexamethylenediamine, which is a typical semi-aromatic polyamide, and terephthalic acid has a high melting point as a single substance, so a large amount of adipic acid, isophthalic acid, 2-methyl-1,5-pentanediaminediamine, etc. It is used by making it the modified polyamide 6T which lowers | hangs melting | fusing point from 330 degreeC to 270 degreeC by superposing | polymerizing. However, the copolymerization component hinders crystallization of the 6T component, which is a crystal component, causing a decrease in crystallization speed and a decrease in crystallinity, resulting in a problem in that workability and high-temperature physical properties are deteriorated. In addition, the 6T component has a high water absorption because it contains many amide bonds in the skeleton, and the surface of the component is swollen in the reflow soldering process performed in surface mount electrical / electronic applications, and it is a cooling component for automobile parts. Resistance to chemicals such as coolant liquid used is not preferable. On the other hand, 9T nylon obtained from nonamethylenediamine and terephthalic acid has an odd number of carbon atoms in the diamine component, so it has a structure in which hydrogen bonding is difficult to take compared to a diamine having an even number of carbon atoms. As a result, the crystallinity is lowered and the high-temperature properties are lowered in the final product. Further, the swelling in the reflow soldering process is still insufficient, although an improvement trend is seen with respect to the modified 6T nylon. Thus, there is a demand for a polyamide resin having higher processability and having a low water absorption.

  Patent Documents 1 and 2 disclose 10T nylon synthesized by polycondensation reaction of 1,10-decamethylenediamine (10) and terephthalic acid (T) as a polyamide having crystallinity and excellent low water absorption. Is disclosed. These 10T nylons have good crystallinity, but because of their high crystallinity, they crystallize very quickly and freeze in the nozzle during injection molding, or they do not have sufficient fluidity. There are problems, and the molded product has problems such as poor weld strength and impact resistance.

  Patent Documents 3 and 4 disclose polyamides obtained by copolymerizing 10T nylon with other components. The form implemented in any of these documents is a copolymer of 10T nylon and 6T nylon, and the low water absorption characteristic inherent in 10T nylon improves the water absorption rate by the copolymerization of 6T components. It is not preferable (see FIG. 2 of Patent Document 4).

  Thus, none of the conventionally known 10T nylons have a high level of moldability while maintaining extremely low water absorption.

Japanese Patent Laid-Open No. 06-239990 JP 2002-293926 A JP 2002-293927 A JP 2008-274288 A

  The present invention has been made in view of the current state of the prior art, and an object of the present invention is to provide a copolymerized polyamide that is highly satisfactory in moldability in addition to extremely low water absorption.

  In order to achieve the above object, the present inventor has intensively studied the types and amounts of components copolymerized with 10T nylon, and as a result, from an equimolar salt of an aliphatic diamine having 5 or less methylene chains and terephthalic acid. It has been found that by copolymerizing the obtained structural units at a specific ratio, it is possible to provide a copolymerized polyamide that has a very high moldability in addition to extremely low water absorption, and has completed the present invention.

  That is, according to the present invention, (a) 50 to 98 mol% of structural units obtained from an equimolar salt of 1,10-decamethylenediamine and terephthalic acid, and (b) an aliphatic having 5 or less methylene chains. A copolymer polyamide comprising 50 to 2 mol% of a structural unit obtained from an equimolar salt of diamine and terephthalic acid is provided.

Preferred embodiments of the copolymerized polyamide of the present invention are as follows.
(1) The aliphatic diamine having 5 or less methylene chains is 1,5-pentamethylenediamine.
(2) Copolyamide is (c) a structural unit obtained from an equimolar salt of diamine and dicarboxylic acid other than the structural unit of (a) or (b), or a structural unit obtained from aminocarboxylic acid or lactam. Contains up to 30 mol%.
(3) The melting point (Tm) of the copolymerized polyamide is 285 to 315 ° C, and the glass transition temperature (Tg) is 90 to 120 ° C.

  In the copolymerized polyamide of the present invention, a structural unit obtained from an equimolar salt of an aliphatic diamine having a methylene chain number of 5 or less and terephthalic acid is copolymerized at a specific ratio to 10T nylon as a main component. While utilizing the characteristics of 10T nylon such as melting point and slidability, the moldability and low water absorption can be highly satisfied.

  Hereinafter, the copolymerized polyamide of the present invention will be described in detail. The copolymerized polyamide of the present invention has a specific component (b) which is a structural unit obtained from an equimolar salt of (a) component corresponding to 10T nylon, aliphatic diamine having 5 or less methylene chains and terephthalic acid. It is contained in a proportion and has the characteristics that not only the moldability which is a defect of 10T nylon is improved, but also the low water absorption is highly satisfactory.

  The component (a) corresponds to 10T nylon obtained by co-condensation polymerization of equimolar amounts of 1,10-decamethylenediamine (10) and terephthalic acid (T). It is represented by the formula (I).

  The component (a) is a main component of the copolymerized polyamide of the present invention, and has a role of imparting excellent heat resistance, low water absorption, chemical resistance, slidability and the like to the copolymerized polyamide. The blending ratio of the component (a) in the copolymerized polyamide is 50 to 98 mol%, preferably 70 to 98 mol%, more preferably 93 to 98 mol%. When the blending ratio of the component (a) is less than the above lower limit, 10T nylon, which is a crystalline component, is subject to crystal inhibition by the copolymer component, and may cause deterioration of moldability and high temperature characteristics, while when exceeding the above upper limit, This is not preferable because workability is significantly reduced.

  Component (b) is a structural unit obtained from an equimolar salt of an aliphatic diamine having 5 or less methylene chains and terephthalic acid, and is specifically represented by the following formula (II). In the following formula (II), n represents the number of methylene chains. Specifically, the copolymer component used as the component (b) uses terephthalic acid as the dicarboxylic acid component. On the other hand, 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, and 1,5-pentamethylenediamine can be used as the diamine component. Among these, 1,4-tetramethylenediamine and 1,5-pentamethylenediamine are preferable, and 1,5-pentamethylenediamine is more preferable.

  (B) component is for improving the fault of (a) component, and has a role which improves both the workability and low water absorption of copolymerized polyamide. The blending ratio of the component (b) in the copolymerized polyamide is 50 to 2 mol%, preferably 30 to 2 mol%, more preferably 7 to 2 mol%. When the blending ratio of the component (b) is less than the above lower limit, the moldability may not be improved. When the above upper limit is exceeded, the crystallinity of the copolyamide is greatly reduced, the crystallization rate is slowed, the moldability is deteriorated, and the water resistance may be lowered, and the component (a) corresponding to 10T nylon There is a risk that the heat resistance and slidability will be insufficient. In the present invention, it is important to use an aliphatic diamine having a short chain length of 5 or less as the component (b), and a structural unit obtained from an aliphatic diamine having a methylene chain number of 5 or less and terephthalic acid. Since the crystallinity is not significantly disturbed by copolymerizing, it is presumed that the processability was also satisfied while maintaining low water absorption.

  In addition to the components (a) and (b), the copolymerized polyamide of the present invention includes (c) a structural unit obtained from an equimolar salt of a diamine other than the structural unit (a) and a dicarboxylic acid, or the above ( A structural unit obtained from an aminocarboxylic acid or lactam other than the structural unit of b) may be copolymerized at a maximum of 30 mol%. The component (c) gives the copolymer polyamide other properties that cannot be obtained depending on the structural unit obtained from an equimolar salt of 10T nylon or an aliphatic diamine having a methylene chain number of 5 or less and terephthalic acid. It has a role of further improving the characteristics obtained from the structural unit obtained from an equimolar salt of nylon or an aliphatic diamine having 5 or less methylene chains and terephthalic acid.

  Specific examples of the copolymer component used as the component (c) include the following copolymer components. Examples of the diamine component include 2-methyl-1,5-pentamethylenediamine, 1,6-diaminohexane, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 2 -Methyl-1,8-octamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,16-hexa Decamethylenediamine, 1,18-octadecamethylenediamine, aliphatic diamines such as 2,2,4 (or 2,4,4) -trimethylhexamethylenediamine, piperazine, cyclohexanediamine, bis (3-methyl-4 -Aminohexyl) methane, bis- (4,4'-aminocyclohexyl) methane, isophor Alicyclic diamines such as Njiamin, m-xylylenediamine, p-xylylenediamine, p-phenylenediamine, aromatic diamines and their hydrogenated products such as such as meta-phenylenediamine. As the dicarboxylic acid component, the following dicarboxylic acids or acid anhydrides can be used. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and 2,2′-diphenyldicarboxylic acid. 4,4'-diphenyl ether dicarboxylic acid, 5-sulfonic acid sodium isophthalic acid, 5-hydroxyisophthalic acid and other aromatic dicarboxylic acids, fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexa Dicarboxylic acids, such as aliphatic or alicyclic dicarboxylic acids such as dimer acid.

  Moreover, as a copolymerization component used for the component (c), lactam and aminocarboxylic acid having a structure in which these are ring-opened can also be used. Specific examples of the copolymer component include lactams such as ε-caprolactam, undecane lactam, and lauryl lactam, and aminocarboxylic acids having a structure in which they are ring-opened.

  Specific components (c) include polycaproamide (nylon 6), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polytetramethylene adipamide (nylon 46), polyhexamethylene adipa Mido (nylon 66), polyundecamethylene adipamide (nylon 116), polymetaxylylene adipamide (nylon MXD6), polyparaxylylene adipamide (nylon PXD6), polytetramethylene sebacamide (nylon 410) ), Polyhexamethylene sebamide (nylon 610), polydecamethylene adipamide (nylon 106), polydecamethylene sebamide (nylon 1010), polyhexamethylene dodecamide (nylon 612), polydecamethylene dodecamide (Nylon 1012), polyhexa Methylene isophthalamide (nylon 6I), polytetramethylene terephthalamide (nylon 4T), polypentamethylene terephthalamide (nylon 5T), poly-2-methylpentamethylene terephthalamide (nylon M-5T), polyhexamethylene terephthalamide ( Nylon 6T), polyhexamethylene hexahydroterephthalamide (nylon 6T (H)), polynonamethylene terephthalamide (nylon 9T), polyundecamethylene terephthalamide (nylon 11T), polydodecamethylene terephthalamide (nylon 12T), Polybis (3-methyl-4-aminohexyl) methane terephthalamide (nylon PACMT), polybis (3-methyl-4-aminohexyl) methane isophthalamide (nylon PACM) ), Polybis (3-methyl-4-amino-hexyl) methane dodecamide (nylon PACM12), and the like polybis (3-methyl-4-amino-hexyl) methane tetra deca (nylon PACM14).

Among the structural units, examples of a preferable component (c) include polyhexamethylene terephthalamide (nylon 6T), polydodecamethylene terephthalamide (nylon 12T) for improving processability, low water absorption, and impact resistance. Polydecamethylene sebacamide (nylon 1010), polydecanamethylene dodecamide (nylon 1012), polyundecanamide (nylon 11) and the like can be mentioned. The blending ratio of the component (c) in the copolymerized polyamide is preferably up to 30 mol%, more preferably 5 to 20 mol%. When the proportion of the component (c) is less than the above lower limit, the effect of the component (c) may not be sufficiently exhibited. When the proportion exceeds the above upper limit, the amount of the essential component (a) or component (b) is small. Therefore, the originally intended effect of the copolymerized polyamide of the present invention may not be sufficiently exhibited, which is not preferable.
The copolymerized polyamide of the present invention has no significant difference in characteristics, but it is preferable to use plant-derived raw materials in order to achieve a low-carbon society and environmental harmony.

  The melting point of the copolymerized polyamide of the present invention is 240 to 315 ° C, preferably 285 to 315 ° C. When Tm exceeds the above upper limit, the processing temperature required when the copolymerized polyamide is molded by an injection molding method or the like becomes extremely high, so that it may be decomposed during processing and the desired physical properties and appearance may not be obtained. On the other hand, when Tm is less than the above lower limit, the crystallization speed becomes slow, and molding becomes difficult in all cases. The glass transition temperature (Tg) is in the range of 70 ° C to 140 ° C, preferably 90 ° C to 120 ° C, more preferably 90 ° C to 110 ° C. When Tg exceeds the above upper limit, not only the mold temperature required for molding the copolyamide by injection molding method becomes high and molding becomes difficult, but it is sufficient in a short cycle of injection molding. In some cases, crystallization does not proceed, causing molding difficulties such as insufficient mold release, and in subsequent use, crystallization proceeds at a high temperature and deformation due to secondary shrinkage becomes a problem. On the other hand, when Tg is less than the above lower limit, problems such as a large decrease in physical properties and inability to maintain physical properties after water absorption occur.

  In the molding of electronic parts, in addition to a high melting point of 280 ° C. or higher and low water absorption, thin-walled, high-cycle molding is required. The polydecamethylene terephthalamide polymer (10T) has good heat resistance but is inferior in moldability. In addition, since the glass transition temperature is high, a high mold temperature is required at the time of molding, so that there is a difficulty in injection molding processability. Even if it can be molded with a low temperature mold, secondary shrinkage due to crystallization during use becomes a problem. From the background as described above, a resin having a high melting point of 280 ° C. or higher, low water absorption, and easy moldability is required. In the copolymer polyamide of the present invention, 10T nylon has an aliphatic group having 5 or less methylene chains. By copolymerizing structural units obtained from an equimolar salt of diamine and terephthalic acid, the mold temperature during injection molding can be kept low, and the processability of injection molding can be improved. As described above, the copolymerized polyamide of the present invention can be used for various applications. Among them, a copolymerized polyamide having a melting point of 280 ° C. or higher has a melting point of 280 ° C. necessary for use in electronic parts or in an automobile engine room. It is a specific copolyamide composition that is well balanced to maintain excellent heat resistance, easy processability and low water absorption.

  Examples of the catalyst used for producing the copolymerized polyamide of the present invention include phosphoric acid, phosphorous acid, hypophosphorous acid or a metal salt, ammonium salt and ester thereof. Specific examples of the metal species of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony. As the ester, ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, phenyl ester and the like can be added. Moreover, it is preferable to add sodium hydroxide from the viewpoint of improving the melt residence stability.

  The relative viscosity (RV) of the copolymerized polyamide of the present invention measured at 20 ° C. in 96% concentrated sulfuric acid is 0.4 to 4.0, preferably 1.0 to 3.5, more preferably 1.5 to 3.0. Examples of a method for setting the relative viscosity of the polyamide within a certain range include a means for adjusting the molecular weight.

  The copolymer polyamide of the present invention can adjust the end group amount and molecular weight of the polyamide by a method of polycondensation by adjusting the molar ratio of the amino group amount to the carboxyl group or a method of adding a terminal blocking agent. . When polycondensation is performed at a constant ratio of the molar ratio of the amino group and the carboxyl group, the molar ratio of all diamines to all dicarboxylic acids used is diamine / dicarboxylic acid = 1.00 / 1.05 to 1.10 / It is preferable to adjust to the range of 1.00.

  Examples of the timing for adding the end-capping agent include raw material charging, polymerization initiation, polymerization late, or polymerization termination. The end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide, but acid anhydrides such as monocarboxylic acid or monoamine, phthalic anhydride, Monoisocyanates, monoacid halides, monoesters, monoalcohols and the like can be used. Examples of the end capping agent include aliphatic monoacids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid. Alicyclic monocarboxylic acids such as carboxylic acid and cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid and other aromatic monocarboxylic acids, maleic anhydride Acid, phthalic anhydride, acid anhydrides such as hexahydrophthalic anhydride, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, etc. Aliphatic monoamines, Examples thereof include alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine.

  The acid value and amine value of the copolymerized polyamide of the present invention are preferably 0 to 200 eq / ton and 0 to 100 eq / ton, respectively. When the terminal functional group exceeds 200 eq / ton, not only gelation and deterioration are promoted during the melt residence, but also problems such as coloring and hydrolysis are caused in the use environment. On the other hand, when a reactive compound such as glass fiber or maleic acid-modified polyolefin is compounded, it is preferable that the acid value and / or the amine value be 5 to 100 eq / ton in accordance with the reactivity and the reactive group.

  Various conventional additives for polyamide can be used for the copolymerized polyamide of the present invention. Additives include fibrous reinforcements / fillers, stabilizers, impact modifiers, flame retardants, mold release agents, slidability improvers, colorants, plasticizers, crystal nucleating agents, and copolymerized polyamides of the present invention. Are different polyamides, thermoplastic resins other than polyamide, and the like.

  Examples of the fibrous reinforcing material include glass fiber, carbon fiber, metal fiber, ceramic fiber, organic fiber, whisker, etc. Among them, glass fiber is preferable. These fibrous reinforcing materials may be used not only alone but also in combination of several kinds. As the glass fiber used here, chopped strands or continuous filament fibers having a length of 0.1 mm to 100 mm can be used. As the cross-sectional shape of the glass fiber, a glass fiber having a circular cross section and a non-circular cross section can be used. As the cross-sectional shape of the glass fiber, a glass fiber having a non-circular cross-section is preferable from the viewpoint of physical properties. Non-circular cross-sectional glass fibers include those that are substantially oval, substantially oval, and substantially bowl-shaped in a cross section perpendicular to the length direction of the fiber length, and have a flatness of 1.5 to 8. It is preferable. Here, the flatness is assumed to be a rectangle with the smallest area circumscribing a cross section perpendicular to the longitudinal direction of the glass fiber, the length of the long side of the rectangle is the major axis, and the length of the short side is the minor axis. It is the ratio of major axis / minor axis. The thickness of the glass fiber is not particularly limited, but the minor axis is about 1 to 20 μm and the major axis is about 2 to 100 μm. Moreover, the glass fiber becomes a fiber bundle, and the thing of the chopped strand shape cut | disconnected by about 1-20 mm of fiber length can use it preferably. The addition amount of the fibrous reinforcing material may be selected as an optimum amount, but it is possible to add 0 to 250 parts by weight, preferably 20 to 150 parts by weight with respect to 100 parts by weight of the copolyamide.

  As fillers (fillers), reinforcing fillers, conductive fillers, magnetic fillers, flame retardant fillers, thermal conductive fillers and the like are listed according to purpose. Specifically, glass beads, glass flakes, glass balloons, silica, talc , Kaolin, wollastonite, mica, alumina, hydrotalcite, montmorillonite, graphite, carbon nanotube, fullerene, zinc oxide, indium oxide, tin oxide, iron oxide, titanium oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, Examples thereof include red phosphorus, calcium carbonate, potassium titanate, lead zirconate titanate, barium titanate, aluminum nitride, boron nitride, zinc borate, aluminum borate, barium sulfate, and magnesium sulfate. These fillers may be used not only alone but also in combination of several kinds. The filler may be added in an optimum amount, but it is possible to add 250 parts by weight or less, preferably 20 to 150 parts by weight of filler with respect to 100 parts by weight of the copolymer polyamide. Moreover, in order to improve the affinity with the polyamide resin, the fibrous reinforcing material and the filler are preferably used in combination with a coupling agent-treated or coupling agent. As the coupling agent, a silane coupling agent is used. Any of titanate coupling agents and aluminum coupling agents may be used, and among them, aminosilane coupling agents and epoxysilane coupling agents are particularly preferable.

  Stabilizers include organic antioxidants such as hindered phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, heat stabilizers, light stabilizers such as hindered amines, benzophenones, and imidazoles. Examples include ultraviolet absorbers, metal deactivators, and copper compounds. Copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide, cupric phosphate, cupric pyrophosphate, Copper salts of organic carboxylic acids such as copper sulfide, copper nitrate, and copper acetate can be used. Further, as a component other than the copper compound, an alkali metal halide compound is preferably contained. Examples of the alkali metal halide compound include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, bromide. Examples thereof include sodium, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide and the like. These additives may be used alone or in combination of several kinds. The stabilizer may be added in an optimum amount, but 0 to 5 parts by weight can be added to 100 parts by weight of the copolymerized polyamide.

  The copolymer polyamide of the present invention may be polymer blended with a polyamide having a composition different from that of the copolymer polyamide of the present invention. The polyamide having a composition different from that of the copolymerized polyamide of the present invention is not particularly limited, but polycaproamide (nylon 6), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polytetramethylene adipamide (Nylon 46), polyhexamethylene adipamide (nylon 66), polymetaxylylene adipamide (nylon MXD6), polyparaxylylene adipamide (nylon PXD6), polytetramethylene sebacamide (nylon 410), Polyhexamethylene sebamide (nylon 610), polydecamethylene adipamide (nylon 106), polydecamethylene sebamide (nylon 1010), polyhexamethylene dodecamide (nylon 612), polydecamethylene dodecamide (nylon) 1012), Polyhe Samethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polytetramethylene terephthalamide (nylon 4T), polypentamethylene terephthalamide (nylon 5T), poly-2-methylpentamethylene terephthalamide (nylon) M-5T), polyhexamethylene hexahydroterephthalamide (nylon 6T (H)), poly-2-methyl-octamethylene terephthalamide, polynonamethylene terephthalamide (nylon 9T), polydecamethylene terephthalamide (nylon 10T), Polyundecamethylene terephthalamide (nylon 11T), Polydodecamethylene terephthalamide (nylon 12T), Polybis (3-methyl-4-aminohexyl) methane terephthalamide ( Iron PACMT), polybis (3-methyl-4-aminohexyl) methane isophthalamide (nylon PACMI), polybis (3-methyl-4-aminohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl-4- Aminohexyl) methane tetradecamide (nylon PACM14), a polyalkyl ether copolymerized polyamide or the like, or these copolymerized polyamides may be used alone or in combination. Among these, nylon 66, nylon 6T66, or the like may be polymer blended in order to improve the crystallization speed. The addition amount of the polyamide having a composition different from that of the copolymer polyamide of the present invention may be selected, but 0 to 50 parts by weight can be added to 100 parts by weight of the copolymer polyamide.

  A thermoplastic resin other than the polyamide having a composition different from that of the copolymer polyamide of the present invention may be added to the copolymer polyamide of the present invention. As thermoplastic resins other than polyamide, polyphenylene sulfide (PPS), liquid crystal polymer (LCP), aramid resin, polyetheretherketone (PEEK), polyetherketone (PEK), polyetherimide (PEI), thermoplastic polyimide, Polyamideimide (PAI), polyether ketone ketone (PEKK), polyphenylene ether (PPE), polyethersulfone (PES), polysulfone (PSU), polyarylate (PAR), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly Butylene naphthalate, polycarbonate (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethylpentene (TPX), polystyrene (PS), polymethyl methacrylate, acrylonitrile-styrene copolymer (AS), and acrylonitrile-butadiene-styrene copolymer (ABS). If the compatibility is poor, a reactive compound, block polymer, etc. It is important to add a solubilizer or to modify a polymer other than polyamide (particularly acid modification is preferred). These thermoplastic resins can be blended in a molten state by melt kneading. However, the thermoplastic resin may be made into a fiber or particle and dispersed in the copolymerized polyamide of the present invention. An optimum amount of the thermoplastic resin may be selected, but 0 to 50 parts by weight can be added with respect to 100 parts by weight of the copolyamide.

  As impact modifiers, ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene- Polyolefin resins such as methacrylic acid ester copolymer, ethylene vinyl acetate copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene -Polytetramethylene glycol, polycaprolactone, or poly (polyethylene glycol) as a hard segment made of vinyl polymer resin such as styrene copolymer (SIS), acrylate copolymer, polybutylene terephthalate or polybutylene naphthalate. Polyester block copolymer in which the ball sulfonate diol as a soft segment, a nylon elastomer, urethane elastomer, acrylic elastomer, silicone rubber, fluorinated rubber, and the like polymer particles having a core-shell structure constituted from two different polymers. The impact modifier may be added in an optimum amount, but 0 to 30 parts by weight can be added to 100 parts by weight of the copolyamide.

  When a thermoplastic resin other than the polyamide resin in the present invention and an impact resistance improving material are added to the copolymerized polyamide of the present invention, it is preferable that a reactive group capable of reacting with the polyamide is copolymerized. The functional group is a group capable of reacting with an amino group, a carboxyl group and a main chain amide group which are terminal groups of the polyamide resin. Specific examples include a carboxylic acid group, an acid anhydride group, an epoxy group, an oxazoline group, an amino group, an isocyanate group, etc. Among them, an acid anhydride group is most excellent in reactivity. There is also a report that the thermoplastic resin having a reactive group that reacts with the polyamide resin is finely dispersed in the polyamide and is finely dispersed, so that the distance between the particles is shortened and the impact resistance is greatly improved [ S, Wu: Polymer 26, 1855 (1985)].

  As a flame retardant, a combination of a halogen flame retardant and antimony is good, and as a halogen flame retardant, brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, brominated styrene maleic anhydride polymer, Brominated epoxy resins, brominated phenoxy resins, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perchlorocyclopentadecane, brominated cross-linked aromatic polymers, etc. are preferred. Antimony compounds include antimony trioxide and antimony pentoxide. Sodium antimonate and the like are preferable. Among these, a combination of dibromopolystyrene and antimony trioxide is preferable from the viewpoint of thermal stability. Non-halogen flame retardants include melamine cyanurate, red phosphorus, phosphinic acid metal salts, and nitrogen-containing phosphoric acid compounds. In particular, a combination of a phosphinic acid metal salt and a nitrogen-containing phosphoric acid compound is preferable. Examples of the nitrogen-containing phosphoric acid compound include melamine, a condensate of melamine such as melam and melon, and a reactive organism of polyphosphoric acid or those. A mixture of At that time, addition of a hydrotalcite-based compound is preferable for preventing metal corrosion of a mold or the like. The addition amount of the flame retardant may be an optimum amount, but 0 to 50 parts by weight can be added with respect to 100 parts by weight of the copolymer polyamide.

  Examples of the release agent include long chain fatty acids or esters thereof, metal salts, amide compounds, polyethylene wax, silicon, polyethylene oxide, and the like. The long chain fatty acid preferably has 12 or more carbon atoms, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, and montanic acid. Partial or total carboxylic acid is esterified with monoglycol or polyglycol. Or a metal salt may be formed. Examples of the amide compound include ethylene bisterephthalamide and methylene bisstearyl amide. These release agents may be used alone or as a mixture. The addition amount of the release material may be selected as an optimum amount, but 0 to 5 parts by weight can be added to 100 parts by weight of the copolymer polyamide.

  Examples of the sliding property improving material include high molecular weight polyethylene, acid-modified high molecular weight polyethylene, fluorine resin powder, molybdenum disulfide, silicon resin, silicon oil, zinc, graphite, mineral oil, and the like. The resin slidability improving material can be added in a range not impairing the characteristics of the present invention, for example, 0.05 to 3 parts by weight.

  The copolymer polyamide of the present invention can be produced by a conventionally known method. For example, decamethylenediamine, terephthalic acid, which is a raw material monomer of component (a), and methylene chain number, which is component (b), are 5 Obtained from the following aliphatic diamine, terephthalic acid, and if necessary (c) an equimolar salt of a diamine other than the structural unit of (a) and a dicarboxylic acid, or an aminocarboxylic acid or lactam other than the structural unit of (b) It can be easily synthesized by co-condensation reaction of the raw material monomers. The order of the copolycondensation reaction is not particularly limited, and all the raw material monomers may be reacted at once, or a part of the raw material monomers may be reacted first, followed by the remaining raw material monomers. Although the polymerization method is not particularly limited, the process from raw material preparation to polymer production may proceed in a continuous process. After the oligomer is produced once, the polymerization is advanced by an extruder or the like in another process, or the oligomer is solidified. A method of increasing the molecular weight by phase polymerization may be used. By adjusting the charging ratio of the raw material monomer, the proportion of each structural unit in the copolymerized polyamide to be synthesized can be controlled.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the measured value described in the Example is measured by the following method.

(1) 0.25 g of a relative viscosity polyamide resin was dissolved in 25 ml of 96% sulfuric acid and measured at 20 ° C. using an Ostwald viscometer.

(2) Melting point (Tm) and glass transition temperature (Tg)
10 mg of the polyamide dried under reduced pressure at 105 ° C. for 15 hours was weighed in an aluminum pan (TA Instruments, product number 900793.901), sealed with an aluminum lid (TA Instruments, product number 900794.901), and measured. After preparing the sample, use a differential scanning calorimeter DSCQ100 (manufactured by TA INSTRUMENTS) to raise the temperature from room temperature to 20 ° C./min, hold at 350 ° C. for 3 minutes, take out the measurement sample pan, soak in liquid nitrogen, and quench rapidly I let you. Thereafter, the sample was taken out from the liquid nitrogen, allowed to stand at room temperature for 30 minutes, and then heated again from room temperature at 20 ° C./minute using a differential scanning calorimeter DSCQ100 (manufactured by TA INSTRUMENTS) and held at 350 ° C. for 3 minutes. . The endothermic peak temperature due to melting at that time was defined as the melting point (Tm). The glass transition temperature (Tg) is the intersection of the base line extension below the glass transition point and the tangent line indicating the maximum slope from the peak rising portion to the peak apex in the second temperature rising process. Determined by temperature.

(3) Formability Using an injection molding machine EC-100 manufactured by Toshiba Machine, the cylinder temperature was set to the melting point of the resin + 20 ° C. As the mold, a mold for producing a flat plate having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm was used. The mold temperature was set to 140 ° C. or 130 ° C., molding was performed at an injection speed of 50 mm / second, a holding pressure of 30 MPa, an injection time of 10 seconds, and a cooling time of 10 seconds. The moldability was evaluated as follows. .
A: Even when the mold temperature is set to a low temperature condition of 130 ° C. other than 140 ° C., the resin is not decomposed as much as 140 ° C., and a molded product can be obtained without any problem.
○: Only when the mold temperature is set to 140 ° C., the resin is not decomposed, and a molded product can be obtained without any problem.
Δ: In both cases where the mold temperature is 140 ° C. and 130 ° C., signs of decomposition such as foaming and poor appearance are observed during molding.
X: In both cases where the mold temperature is 140 ° C. or 130 ° C., the releasability is insufficient, and the molded product sticks to the mold or deforms.

(4) Saturated water absorption For evaluation of the saturated water absorption, a flat plate having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm was prepared and immersed in 80 ° C. hot water, and obtained from the following formula.
Saturated water absorption (%) = {(weight at time of saturated water absorption−weight at time of drying) / weight at time of drying} × 100

[Example 1]
1,10-Decamethylenediamine 10.34 kg, 12.46 kg of terephthalic acid, 1.53 kg of 1,5-pentamethylenediamine, 9 g of sodium diphosphite as a catalyst, and 40 g of acetic acid as a terminal adjuster (in total carboxylic acid moles) 0.4 mol%) and 17.52 kg of ion-exchanged water were charged into a 50 liter autoclave, pressurized from normal pressure to 0.05 MPa with N ₂ , released, and returned to normal pressure. This operation was performed 3 times, N ₂ substitution was performed, and then uniform dissolution was performed at 135 ° C. and 0.3 MPa with stirring. Thereafter, the solution was continuously supplied by a liquid feed pump, heated to 240 ° C. with a heating pipe, and heated for 1 hour. Thereafter, the reaction mixture was supplied to a pressure reaction can, heated to 290 ° C., and a part of water was distilled off so as to maintain the internal pressure of the can at 3 MPa to obtain a low-order condensate. Thereafter, this low-order condensate is directly supplied to a twin-screw extruder (screw diameter 37 mm, L / D = 60) while maintaining a molten state, the resin temperature is set to 330 ° C., and water is extracted from three vents. Then, polycondensation proceeded under melting to obtain a copolymerized polyamide. Next, the compound of the obtained copolymer polyamide and glass fiber was produced. Specifically, using the same direction twin screw extruder, the cylinder temperature is set to 320 ° C.-330 ° C.-330 ° C.-320 ° C. from the hopper side, and glass fiber (T-275H manufactured by Nippon Electric Glass Co., Ltd.) is used. I put it in from the side feed. After cooling the obtained strand in a water tank, it was pelletized with a strand cutter and dried at 125 ° C. for 5 hours to obtain a reinforced copolymerized polyamide resin composition. Table 1 shows the charge ratio of raw material monomers and the properties of the obtained copolymerized polyamide and copolymerized polyamide resin composition. Table 2 shows the composition and evaluation results of the reinforced copolymerized polyamide resin composition containing glass fibers.

[Example 2]
A copolymerized polyamide was obtained in the same manner as in Example 1 except that 10.34 kg of 1,10-decamethylenediamine was changed to 11.63 kg and 1.53 kg of 1,5-pentamethylenediamine was changed to 0.76 kg. It was. Further, a reinforced copolymerized polyamide resin composition was obtained in the same manner as in Example 1. Table 1 shows the charge ratio of raw material monomers and the properties of the obtained copolymerized polyamide and copolymerized polyamide resin composition. Table 2 shows the composition and evaluation results of the reinforced copolymerized polyamide resin composition containing glass fibers.

Example 3
A copolymerized polyamide was obtained in the same manner as in Example 1 except that 10.34 kg of 1,10-decamethylenediamine was changed to 9.05 kg and 1.53 kg of 1,5-pentamethylenediamine was changed to 2.30 kg. It was. Further, a reinforced copolymerized polyamide resin composition was obtained in the same manner as in Example 1. Table 1 shows the charge ratio of raw material monomers and the properties of the obtained copolymerized polyamide and copolymerized polyamide resin composition. Table 2 shows the composition and evaluation results of the reinforced copolymerized polyamide resin composition containing glass fibers.

Example 4
A copolymerized polyamide was obtained in the same manner as in Example 1 except that 10.34 kg of 1,10-decamethylenediamine was changed to 12.02 kg and 1.53 kg of 1,5-pentamethylenediamine was changed to 0.54 kg. It was. Further, a reinforced copolymerized polyamide resin composition was obtained in the same manner as in Example 1. Table 1 shows the charge ratio of raw material monomers and the properties of the obtained copolymerized polyamide and copolymerized polyamide resin composition. Table 2 shows the composition and evaluation results of the reinforced copolymerized polyamide resin composition containing glass fibers.

Example 5
1.10 kg of 1,10-decamethylenediamine is changed to 12.20 kg, 1.53 kg of 1,5-pentamethylenediamine is changed to 0.31 kg of 1,5-pentamethylenediamine and 0.18 kg of 1,6-hexamethylenediamine A copolymerized polyamide was obtained in the same manner as in Example 1 except for changing to. Further, a reinforced copolymerized polyamide resin composition was obtained in the same manner as in Example 1. Table 1 shows the charge ratio of raw material monomers and the properties of the obtained copolymerized polyamide and copolymerized polyamide resin composition. Table 2 shows the composition and evaluation results of the reinforced copolymerized polyamide resin composition containing glass fibers.

Example 6
A copolymerized polyamide was obtained in the same manner as in Example 1 except that 10.34 kg of 1,10-decamethylenediamine was changed to 12.40 kg and 1.53 kg of 1,5-pentamethylenediamine was changed to 0.31 kg. It was. Further, a reinforced copolymerized polyamide resin composition was obtained in the same manner as in Example 1. Table 1 shows the charge ratio of raw material monomers and the properties of the obtained copolymerized polyamide and copolymerized polyamide resin composition. Table 2 shows the composition and evaluation results of the reinforced copolymerized polyamide resin composition containing glass fibers.

Example 7
Except for changing 10.10 kg of 1,10-decamethylenediamine to 12.46 kg and changing 1.53 kg of 1,5-pentamethylenediamine to 0.26 kg of 1,4-tetramethylenediamine, the same as in Example 1. Thus, a copolyamide was obtained. Further, a reinforced copolymerized polyamide resin composition was obtained in the same manner as in Example 1. Table 1 shows the charge ratio of raw material monomers and the properties of the obtained copolymerized polyamide and copolymerized polyamide resin composition. Table 2 shows the composition and evaluation results of the reinforced copolymerized polyamide resin composition containing glass fibers.

[Comparative Example 1]
A copolyamide was obtained in the same manner as in Example 1, except that 1,5-pentamethylenediamine was not used and 12.46 kg of 1,10-decamethylenediamine was changed to 12.92 kg. Further, a reinforced copolymerized polyamide resin composition was obtained in the same manner as in Example 1. Table 1 shows the charge ratio of raw material monomers and the properties of the obtained copolymerized polyamide and copolymerized polyamide resin composition. Table 2 shows the composition and evaluation results of the reinforced copolymerized polyamide resin composition containing glass fibers.

[Comparative Example 2]
A copolymerized polyamide was obtained in the same manner as in Example 4 except that 0.54 kg of 1,5-pentamethylenediamine was changed to 0.61 kg of 1,6-hexamethylenediamine. Further, a reinforced copolymerized polyamide resin composition was obtained in the same manner as in Example 1. Table 1 shows the charge ratio of raw material monomers and the properties of the obtained copolymerized polyamide and copolymerized polyamide resin composition. Table 2 shows the composition and evaluation results of the reinforced copolymerized polyamide resin composition containing glass fibers.

[Comparative Example 3]
Except for changing 10.34 kg of 1,10-decamethylenediamine to 12.02 kg and changing 1.53 kg of 1,5-pentamethylenediamine to 0.83 kg of 1,9-nonanediamine, the same as in Example 1, A copolymerized polyamide was obtained. Further, a reinforced copolymerized polyamide resin composition was obtained in the same manner as in Example 1. Table 1 shows the charge ratio of raw material monomers and the properties of the obtained copolymerized polyamide and copolymerized polyamide resin composition. Table 2 shows the composition and evaluation results of the reinforced copolymerized polyamide resin composition containing glass fibers.

[Comparative Example 4]
A copolymerized polyamide was obtained in the same manner as in Example 1 except that 10.34 kg of 1,10-decamethylenediamine was changed to 5.82 kg and 1.53 kg of 1,5-pentamethylenediamine was changed to 4.21 kg. It was. Further, a reinforced copolymerized polyamide resin composition was obtained in the same manner as in Example 1. Table 1 shows the charge ratio of raw material monomers and the properties of the obtained copolymerized polyamide and copolymerized polyamide resin composition. Table 2 shows the composition and evaluation results of the reinforced copolymerized polyamide resin composition containing glass fibers.

[Comparative Example 5]
A copolymerized polyamide was obtained in the same manner as in Example 1 except that 10.34 kg of 1,10-decamethylenediamine was changed to 12.79 kg and 1.53 kg of 1,5-pentamethylenediamine was changed to 0.08 kg. It was. Further, a reinforced copolymerized polyamide resin composition was obtained in the same manner as in Example 1. Table 1 shows the charge ratio of raw material monomers and the properties of the obtained copolymerized polyamide and copolymerized polyamide resin composition. Table 2 shows the composition and evaluation results of the reinforced copolymerized polyamide resin composition containing glass fibers.

  As is clear from Tables 1 and 2, the copolymerized polyamides and glass fiber reinforced resins of Examples 1 to 7 highly satisfy both the moldability and the low water absorption rate. On the other hand, as a component b), the copolymerized polyamide of Comparative Example 1 in which a structural unit obtained from an equimolar salt of an aliphatic diamine having 5 or less methylene chains and terephthalic acid is not copolymerized is molded by foaming at the time of molding. Caused a defect. In the copolymerized polyamide of Comparative Example 2 in which hexamethylenediamine was copolymerized with a portion of decamethylenediamine, crystallization did not proceed sufficiently, and deformation occurred during mold release in non-reinforced molding. Moreover, since hexamethylenediamine was copolymerized, the water absorption rate increased significantly. The copolymerized polyamide of Comparative Example 3 in which a structural unit obtained from an equimolar salt of an aliphatic diamine having a methylene chain number exceeding 5 and terephthalic acid is copolymerized is inhibited from crystallization of the 10T component, which is a crystalline component, I was not satisfied with the sex. The copolymerized polyamide of Comparative Example 4 having an increased number of structural units obtained from an equimolar salt of an aliphatic diamine having a methylene chain number of 5 or less and terephthalic acid is composed of an aliphatic diamine having a methylene chain number of 5 or less and terephthalic acid. Due to the increase in structural units obtained from equimolar salts, crystallization of the 10T component, which is a crystalline component, was inhibited, and low water absorption was not satisfactory. Moreover, moldability was not satisfied. The copolymerized polyamide of Comparative Example 5 in which the structural unit obtained from an equimolar salt of an aliphatic diamine having a methylene chain number of 5 or less and terephthalic acid was reduced was obtained from an aliphatic diamine having a methylene chain number of 5 or less and terephthalic acid. Due to the decrease in structural units obtained from equimolar salts, moldability could not be satisfied.

  The copolymer polyamide of the present invention has a high melting point, because a structural unit composed of an equimolar salt of an aliphatic diamine having 5 or less methylene chains and terephthalic acid is copolymerized at a specific ratio to 10T nylon as a main component. In addition, while utilizing the properties of 10T nylon such as slidability, the moldability and low water absorption can be highly satisfied, so it can be suitably used as a molding material or sliding material for automobiles and electronic parts. .

Claims (4)

  (A) 50 to 98 mol% of structural units obtained from an equimolar salt of 1,10-decamethylenediamine and terephthalic acid, and (b) equimolar of an aliphatic diamine having 5 or less methylene chains and terephthalic acid A copolymerized polyamide comprising 50 to 2 mol% of a structural unit obtained from a salt.   The copolymer polyamide according to claim 1, wherein the aliphatic diamine having 5 or less methylene chains is 1,5-pentamethylenediamine.   Copolyamide has a maximum of 30 moles of structural units obtained from (c) equimolar salts of diamine and dicarboxylic acid other than the structural units of (a) or (b) above, or structural units obtained from aminocarboxylic acids or lactams. The copolymerized polyamide according to claim 1, wherein the copolymerized polyamide is contained up to 5%.   The copolymer polyamide according to any one of claims 1 to 5, wherein the copolymer polyamide has a melting point (Tm) of 285 to 315 ° C and a glass transition temperature (Tg) of 90 to 120 ° C.