JPWO2011074536A1 - Copolyamide - Google Patents

Abstract

In addition to extremely low water absorption, the present invention provides a novel polyamide highly satisfying moldability and impact resistance. (A) 50-98 mol% of structural units obtained from an equimolar molar salt of decanediamine and terephthalic acid, and (b) 11-aminoundecanoic acid, 12-aminododecanoic acid, undecane lactam, lauryllactam, and mixtures thereof A copolyamide comprising 50 to 2 mol% of a structural unit selected from the group consisting of:

Description

  The present invention relates to a novel copolyamide which has a very high moldability and impact resistance 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, 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-pentanediamine, etc. are copolymerized. By doing so, the modified polyamide 6T is used which has a melting point lowered from 330 ° C. to 270 ° C. 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. Compared with 11 nylon and 12 nylon, which are polyamides with low water absorption, 6T component has high water absorption because it contains many amide bonds in the skeleton, and in the reflow soldering process performed in electrical and electronic applications for surface mounting. It is not preferable that the surface of the component is swollen or that it is resistant to chemicals such as a coolant used in a cooling component of an automobile component. 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 a polycondensation reaction of 1,10-decanediamine (10) and terephthalic acid (T) as a polyamide having crystallinity and excellent low water absorption. ing. These 10T nylons have good crystallinity, but because of their high crystallinity, they crystallize very quickly, freeze in the nozzle during injection molding, or do not have sufficient fluidity In addition, there are problems such as poor weld strength and impact resistance in molded products.

  Patent Documents 3 and 4 disclose polyamides obtained by copolymerizing 10T nylon with other components. The polyamide implemented in these documents is a copolymer of 10T nylon and 6T nylon, which not only has no impact resistance improvement effect, but also has the inherent low water absorption property of 10T nylon. It has fallen by superposition | polymerization (refer FIG. 2 of patent document 4).

  As described above, none of the conventionally known 10T nylons have a high level of moldability and impact resistance while maintaining an extremely low water absorption rate.

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 and impact resistance 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, by copolymerizing 11 nylon and / or 12 nylon at a specific ratio, The present inventors have found that it is possible to provide a copolyamide having a high degree of moldability and impact resistance in addition to a low water absorption rate, and have completed the present invention.

That is, the present invention has the following configurations (1) to (6).
(1) (a) 50 to 98 mol% of structural units obtained from an equimolar molar salt of decanediamine and terephthalic acid, and (b) 11-aminoundecanoic acid, 12-aminododecanoic acid, undecane lactam, lauryllactam and A copolymerized polyamide comprising 50 to 2 mol% of a structural unit selected from the group consisting of these mixtures.
(2) (a) 75-98 mol% of structural units obtained from an equimolar molar salt of decanediamine and terephthalic acid, and (b) 11-aminoundecanoic acid, 12-aminododecanoic acid, undecane lactam, lauryllactam and The copolyamide according to (1), comprising 25 to 2 mol% of a structural unit selected from the group consisting of these mixtures.
(3) Copolyamide is (c) a structural unit obtained from an equivalent molar 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) The copolyamide according to (1) or (2), which comprises up to 30 mol% of structural units obtained from
(4) The melting point (Tm) of the copolymerized polyamide is 240 to 315 ° C., and the glass transition temperature (Tg) is 70 to 120 ° C. Copolyamide.
(5) A copolymerized polyamide resin composition, wherein a fibrous reinforcing material is blended at a maximum of 250 parts by weight with respect to 100 parts by weight of the copolymerized polyamide according to any one of (1) to (4).
(6) The copolymerized polyamide resin composition as described in (5), which is used as a molding material for automobile parts or electronic parts.

  The copolymerized polyamide of the present invention has the characteristics of 10T nylon such as high melting point, slidability, and low water absorption because 11Nylon and / or 12nylon are copolymerized at a specific ratio to the main component 10T nylon. While being utilized, the moldability and impact resistance can be highly satisfied.

  Hereinafter, the copolymerized polyamide of the present invention will be described in detail. The copolymerized polyamide of the present invention contains (a) component corresponding to 10T nylon and (b) component corresponding to 11 nylon and / or 12 nylon in a specific ratio, and is a drawback of 10T nylon. In addition to improved properties and impact resistance, it also has a feature that low water absorption is highly satisfactory.

  The component (a) corresponds to 10T nylon obtained by co-condensation polymerization of equimolar amounts of 1,10-decanediamine (10) and terephthalic acid (T). It is represented by (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 75 to 98 mol%, more preferably 80 to 95 mol%. When the blending ratio of the component (a) is less than the above lower limit, 10T nylon which is a crystal component is subject to crystal inhibition by the copolymer component, which may lead to a decrease in moldability and heat resistance. This is not preferable because workability and impact resistance are significantly reduced.

  The component (b) corresponds to 11 nylon or 12 nylon obtained by polycondensation of 11-aminoundecanoic acid, 12-aminododecanoic acid, undecane lactam, or lauryl lactam. Those represented by formulas (II) and (III). These may be used alone or in a mixture.

  The component (b) is for improving the drawbacks of the component (a) and has a role of improving all of the impact resistance, workability and low water absorption of the copolymerized polyamide. The blending ratio of the component (b) in the copolymerized polyamide is 50 to 2 mol%, preferably 25 to 2 mol%, more preferably 20 to 5 mol%. When the blending ratio of the component (b) is less than the above lower limit, the impact resistance of the copolymer polyamide is not improved, and the effect of reducing water absorption is insufficient. When the above upper limit is exceeded, the crystallinity of the copolymerized polyamide is greatly lowered, the crystallization rate is slowed, the moldability is deteriorated, and the impact resistance may be deteriorated. Further, the amount of the component (a) corresponding to 10T nylon is decreased, and heat resistance and slidability may be insufficient.

  The copolymerized polyamide of the present invention comprises (c) a structural unit obtained from an equivalent molar salt of diamine and dicarboxylic acid other than the structural unit of (a) above, in addition to the above components (a) and (b), or the above A structural unit obtained from aminocarboxylic acid or lactam other than the structural unit of (b) may be copolymerized at a maximum of 30 mol%. Here, the copolymerization amount of the component (c) is an amount when the total of (a), (b) and (c) is 100 mol%. Component (c) is added to give other characteristics not obtainable with 10T nylon, 11 nylon, and 12 nylon to copolymer polyamide, and to further improve the characteristics obtained with 10T nylon, 11 nylon, and 12 nylon. Is done.

Specific examples of the copolymer component used as the component (c) include the following copolymer components. As the diamine component, 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 2-methyl-1,5-pentamethylenediamine, 1,6 -Hexamethylenediamine, 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-hexadecamethylenediamine, 1,18-octadecamethylenediamine, 2,2,4 (or 2,4,4) -aliphatic diamines such as trimethylhexamethylenediamine, piperazi Cyclohexanediamine, bis (3-methyl-4-aminohexyl) methane, bis- (4,4′-aminocyclohexyl) methane, cycloaliphatic diamines such as isophoronediamine, metaxylylenediamine, paraxylylenediamine, Examples thereof include aromatic diamines such as paraphenylenediamine and metaphenylenediamine, and hydrogenated products thereof.
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-cyclohexanedi Carboxylic acids, such as aliphatic or alicyclic dicarboxylic acids such as dimer acid. In addition, lactams such as ε-caprolactam and aminocarboxylic acids having a ring-opened structure are exemplified.

  Specific examples of the component (c) include polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyundecamethylene adipamide (nylon 116). ), Polymetaxylylene adipamide (nylon MXD6), polyparaxylylene adipamide (nylon PXD6), polytetramethylene sebacamide (nylon 410), polyhexamethylene sebacamide (nylon 610), polydecamethylene Adipamide (nylon 106), polydecamethylene sebamide (nylon 1010), polyhexamethylene dodecamide (nylon 612), polydecamethylene dodecamide (nylon 1012), polyhexamethylene isophthalamide (nylon 6I), poly Tetramethylene terephthalate Amide (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 terephthalate Amide (nylon PACMT), polybis (3-methyl-4-aminohexyl) methane isophthalamide (nylon PACMI), polybis (3-methyl-4-aminohexyl) methandecamide (Nai Down 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 polydodecamethylene terephthalamide (nylon 12T) and polydecamethylene sebacamide (nylon 1010) for improving processability, low water absorption, and impact resistance. And polydecamethylene dodecamide (nylon 1012). 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 small, the effect of the component (c) may not be sufficiently exhibited. When the above upper limit is exceeded, the amount of the essential component (a) or component (b) is reduced. The originally intended effect of the copolymerized polyamide of the invention may not be sufficiently exhibited, which is not preferable.

  The copolymerized polyamide of the present invention preferably uses plant-derived raw materials in order to achieve a low carbon society and environmental harmony. As a plant-derived raw material, it is preferable to use a castor oil-derived raw material that does not compete with food, decanediamine in the component (a) of the copolymerized polyamide of the present invention, (b) aminoundecanoic acid in the component, (c) Sebacic acid as a component is preferably a plant-derived material. Preferable compositions of the copolymerized polyamide of the present invention include nylon 10T / 11 and nylon PA10T / 1010/11 using these plant-derived raw materials in a high ratio.

  The melting point of the copolymerized polyamide of the present invention is preferably 240 to 315 ° C, more preferably 280 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 lower limit, the crystallization rate is slow, and in any case, molding may be difficult. The glass transition temperature (Tg) is preferably 70 ° C to 120 ° C, more preferably 85 ° C to 110 ° C. When Tg exceeds the above upper limit, when molding a copolymerized polyamide by injection molding or the like, not only the mold temperature required 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 may 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 and impact resistance. 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 described above, a resin having a high melting point, low water absorption, and easy moldability is required. In the copolymerized polyamide of the present invention, a specific amount of 11 nylon and / or 12 nylon is copolymerized with 10T nylon. By doing so, not only the impact resistance can be improved, but 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, the high melting point copolymerized polyamide is required for use in electronic parts and for deployment in an automobile engine room, and easy processability. In addition, low water absorption and impact resistance are all highly satisfied. The high-melting point copolymerized polyamide should have a component (a) of 75 to 98 mol%, a component (b) of 25 to 2 mol%, and a copolymer (c) up to 30 mol% as necessary. Is obtained.

  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. 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 preferably 0.4 to 4.0, more preferably 1.0 to 3.5, still more preferably. 1.5-3.0. 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, and 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 may be caused even 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 50 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 optimum amount of the fibrous reinforcing material may be selected, but a maximum of 250 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight is added to 100 parts by weight of the copolymer polyamide. Is possible.

  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, hydroxyapatite, graphite, carbon nanotube, fullerene, zinc oxide, indium oxide, tin oxide, iron oxide, titanium oxide, magnesium oxide, aluminum hydroxide, water Magnesium oxide, red phosphorus, calcium carbonate, potassium titanate, lead zirconate titanate, barium titanate, aluminum nitride, boron nitride, zinc borate, aluminum borate, barium sulfate, magnesium sulfate, zinc sulfide, iron, aluminum, Copper, silver And the like. These fillers may be used not only alone but also in combination of several kinds. Although it does not specifically limit as a shape, A needle shape, spherical shape, plate shape, an indeterminate form, etc. can be used. An optimum amount of filler may be selected, but a maximum of 250 parts by weight, preferably 20 to 150 parts by weight of filler can be added to 100 parts by weight of the copolyamide. 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. An optimum amount of the stabilizer may be selected, but a maximum of 5 parts by weight can be added to 100 parts by weight of the copolyamide.

  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-amino) Hexyl) methanetetradecamide (nylon PACM14), 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 copolymerized polyamide of the present invention may be selected, but a maximum of 50 parts by weight can be added to 100 parts by weight of the copolymerized 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. Polymers other than polyamide include 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), polyether sulfone (PES), polysulfone (PSU), polyarylate (PAR), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene Phthalate, polycarbonate (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethylpentene (TPX), polystyrene ( S), polymethyl methacrylate, acrylonitrile-styrene copolymer (AS), and acrylonitrile-butadiene-styrene copolymer (ABS). If the compatibility is poor, compatibilization of reactive compounds, block polymers, etc. It is important to add an agent 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 a maximum of 50 parts by weight can be added to 100 parts by weight of the copolymer polyamide.

  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 a maximum of 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. Since the thermoplastic resin having a reactive group that reacts with the polyamide resin is finely dispersed in the polyamide, the distance between the particles is shortened, and the impact resistance is greatly improved.

  As a flame retardant, a combination of a halogen flame retardant and a flame retardant aid is good. As a halogen flame retardant, brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, brominated styrene maleic anhydride Polymers, brominated epoxy resins, brominated phenoxy resins, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perchlorocyclopentadecane, brominated cross-linked aromatic polymers, etc. are preferred. Antimony compounds such as antimony, antimony pentoxide, and sodium antimonate, and zinc stannate are preferred. Among these, a combination of dibromopolystyrene and sodium antimonate and / or zinc stannate 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 or a melamine condensate such as melam and melon and polyphosphoric acid reactive organisms or Including mixtures thereof. At that time, it is preferable to add a hydrotalcite-based compound in order to prevent metal corrosion of a mold or the like. Other flame retardants and flame retardant aids include zinc borate, zinc sulfide, molybdenum compounds, iron oxide, aluminum hydroxide, magnesium hydroxide, silicone resin, fluororesin, montmorillonite, silica, metal carbonate, etc. . The optimum amount of the flame retardant may be selected, but a maximum of 50 parts by weight can be added to 100 parts by weight of the copolyamide.

  Examples of the release agent include long chain fatty acids or esters thereof, metal salts, amide compounds, polyethylene wax, silicone, 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. An optimum amount of the release material may be selected, but a maximum of 5 parts by weight can be added to 100 parts by weight of the copolyamide.

  Examples of the sliding property improving material include high molecular weight polyethylene, acid-modified high molecular weight polyethylene, fluororesin powder, molybdenum disulfide, silicone resin, silicone oil, zinc, graphite, mineral oil, and the like. The resin slidability improving material can be added up to 3 parts by weight with respect to 100 parts by weight of the copolymerized polyamide.

  The copolymerized polyamide of the present invention can be produced by a conventionally known method. For example, decanediamine, terephthalic acid, which is a raw material monomer of component (a), and 11-aminoundecanoic acid, which is component (b), A raw material monomer selected from the group consisting of 12-aminododecanoic acid, undecane lactam, lauryl lactam, and mixtures thereof, and (c) an equimolar molar salt of a diamine other than the structural unit of (a) and dicarboxylic acid if necessary, Or it can synthesize | combine easily by carrying out the cocondensation reaction of the raw material monomer obtained from aminocarboxylic acid or lactam other than the structural unit of said (b). 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. The polymerization method is not particularly limited, but from raw material charging to polymer production may proceed in a continuous process, and after producing an oligomer 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) Relative viscosity 0.25 g of 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) and sealed with an aluminum lid (TA Instruments, product number 900794.901). 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., molding was performed at an injection speed of 50 mm / sec, 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.
○: No decomposition of the resin is observed, and a molded product can be obtained without problems.
(Triangle | delta): The sign of decomposition | disassembly, such as foaming and an external appearance defect, is seen at the time of molding.
X: 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 when saturated water absorption−weight when dried) / weight when dried} × 100

(5) Charpy impact strength Charpy impact strength was evaluated according to ISO 179 at 23 ° C and with a notch. The test piece was an injection molding machine EC-100 manufactured by Toshiba Machine, and the cylinder temperature was set to the melting point of the resin + 20 ° C. Molding was performed at a mold temperature of 140 ° C., an injection speed of 50 mm / sec, a holding pressure of 30 MPa, an injection time of 10 seconds, and a cooling time of 16 seconds.

[Example 1]
Decamethylenediamine (12.38 kg), terephthalic acid (11.95 kg), 11-aminoundecanoic acid (1.61 kg), sodium diphosphite (9 g), terminal conditioner (40 g) acetic acid and ion-exchanged water (17.52 kg) in a 50 liter autoclave The pressure was charged with N ₂ from normal pressure to 0.05 MPa, the pressure was released, and the pressure was 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, and the resin temperature is 330 ° C. while water is being removed from three vents. Polycondensation proceeded under melting to obtain a copolymerized polyamide. Table 1 shows the charging ratio and characteristics of the raw monomer of the non-reinforced copolyamide and the evaluation results of the molded product obtained from the copolyamide. Next, glass fibers were added to the obtained copolymer polyamide to prepare a reinforced copolymer polyamide resin composition. 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 2 shows the composition ratio of the reinforced copolymerized polyamide resin composition, moldability, and evaluation results of molded products obtained from the copolymerized polyamide resin composition.

[Example 2]
In the same manner as in Example 1, except that the amount of decamethylenediamine was changed to 8.26 kg, the amount of terephthalic acid was changed to 7.97 kg, and the amount of 11-aminoundecanoic acid was changed to 6.43 kg. Polymerized polyamide was synthesized. Table 1 shows the charging ratio and characteristics of the raw monomer of the non-reinforced copolyamide and the evaluation results of the molded product obtained from the copolyamide. Next, glass fiber was added to the obtained copolyamide to obtain a reinforced copolyamide resin composition in the same manner as in Example 1. Table 2 shows the composition ratio of the reinforced copolymerized polyamide resin composition, moldability, and evaluation results of molded products obtained from the copolymerized polyamide resin composition.

Example 3
In the same manner as in Example 1, except that the amount of decamethylenediamine was changed to 11.01 kg, the amount of terephthalic acid was changed to 10.62 kg, and the amount of 11-aminoundecanoic acid was changed to 3.22 kg. Polymerized polyamide was synthesized. Table 2 shows the charging ratio and characteristics of the raw material monomers of this copolymerized polyamide. Next, glass fiber was added to the obtained copolyamide to obtain a reinforced copolyamide resin composition in the same manner as in Example 1. Table 2 shows the composition ratio of the reinforced copolymerized polyamide resin composition, moldability, and evaluation results of molded products obtained from the copolymerized polyamide resin composition.

Example 4
A copolymer polyamide was synthesized in the same manner as in Example 3 except that 3.22 kg of 11-aminoundecanoic acid was changed to 2.93 kg of undecane lactam. Table 2 shows the charging ratio and characteristics of the raw material monomers of this copolymerized polyamide. Next, glass fiber was added to the obtained copolyamide to obtain a reinforced copolyamide resin composition in the same manner as in Example 1. Table 2 shows the composition ratio of the reinforced copolymerized polyamide resin composition, moldability, and evaluation results of molded products obtained from the copolymerized polyamide resin composition.

Example 5
A copolymer polyamide was synthesized in the same manner as in Example 3 except that 3.22 kg of 11-aminoundecanoic acid was changed to 3.44 kg of 12-aminododecanoic acid. Table 2 shows the charging ratio and characteristics of the raw material monomers of this copolymerized polyamide. Next, glass fiber was added to the obtained copolyamide to obtain a reinforced copolyamide resin composition in the same manner as in Example 1. Table 2 shows the composition ratio of the reinforced copolymerized polyamide resin composition, moldability, and evaluation results of molded products obtained from the copolymerized polyamide resin composition.

Example 6
A copolymerized polyamide was synthesized in the same manner as in Example 3 except that 3.22 kg of 11-aminoundecanoic acid was changed to 3.15 kg of lauryl lactam. Table 2 shows the charging ratio and characteristics of the raw material monomers of this copolymerized polyamide. Next, glass fiber was added to the obtained copolyamide to obtain a reinforced copolyamide resin composition in the same manner as in Example 1. Table 2 shows the composition ratio of the reinforced copolymerized polyamide resin composition, moldability, and evaluation results of molded products obtained from the copolymerized polyamide resin composition.

Example 7
Copolyamide was synthesized in the same manner as in Example 1 except that 11.95 kg of terephthalic acid was changed to 10.62 kg of terephthalic acid and 1.62 kg of sebacic acid. Table 2 shows the charging ratio and characteristics of the raw material monomers of this copolymerized polyamide. Next, glass fiber was added to the obtained copolyamide to obtain a reinforced copolyamide resin composition in the same manner as in Example 1. Table 2 shows the composition ratio of the reinforced copolymerized polyamide resin composition, moldability, and evaluation results of molded products obtained from the copolymerized polyamide resin composition.

Example 8
In the same manner as in Example 1, except that the amount of decamethylenediamine was changed to 13.07 kg, the amount of terephthalic acid was changed to 12.62 kg, and the amount of 11-aminoundecanoic acid was changed to 0.80 kg. Polymerized polyamide was synthesized. Table 2 shows the charging ratio and characteristics of the raw material monomers of this copolymerized polyamide. Next, glass fiber was added to the obtained copolyamide to obtain a reinforced copolyamide resin composition in the same manner as in Example 1. Table 2 shows the composition ratio of the reinforced copolymerized polyamide resin composition, moldability, and evaluation results of molded products obtained from the copolymerized polyamide resin composition.

[Comparative Example 1]
11-aminoundecanoic acid was not used, the amount of decamethylenediamine was changed to 13.76 kg, and the amount of terephthalic acid was changed to 13.28 kg. It was. Table 1 shows the charging ratio and characteristics of the raw monomer of the non-reinforced copolyamide and the evaluation results of the molded product obtained from the copolyamide. Next, glass fiber was added to the obtained copolyamide to obtain a reinforced copolyamide resin composition in the same manner as in Example 1. Table 2 shows the composition ratio of the reinforced copolymerized polyamide resin composition, moldability, and evaluation results of molded products obtained from the copolymerized polyamide resin composition.

[Comparative Example 2]
Example 1 except that 11-aminoundecanoic acid was not used, 12.38 kg of decamethylenediamine was changed to 8.26 kg of decamethylenediamine and 3.71 kg of hexamethylenediamine, and the amount of terephthalic acid was changed to 13.28 kg. In the same manner as above, a copolymerized polyamide was obtained. Table 1 shows the charging ratio and characteristics of the raw monomer of the non-reinforced copolyamide and the evaluation results of the molded product obtained from the copolyamide. Next, glass fiber was added to the obtained copolyamide to obtain a reinforced copolyamide resin composition in the same manner as in Example 1. Table 2 shows the composition ratio of the reinforced copolymerized polyamide resin composition, moldability, and evaluation results of molded products obtained from the copolymerized polyamide resin composition.

[Comparative Example 3]
In the same manner as in Example 1, except that the amount of decamethylenediamine was changed to 5.50 kg, the amount of terephthalic acid was changed to 5.31 kg, and the amount of 11-aminoundecanoic acid was changed to 9.65 kg. Polymerized polyamide was synthesized. Table 2 shows the charging ratio and characteristics of the raw material monomers of this copolymerized polyamide. Next, glass fiber was added to the obtained copolyamide to obtain a reinforced copolyamide resin composition in the same manner as in Example 1. Table 2 shows the composition ratio of the reinforced copolymerized polyamide resin composition, moldability, and evaluation results of molded products obtained from the copolymerized polyamide resin composition.

[Comparative Example 4]
A copolymerized polyamide was synthesized in the same manner as in Example 3 except that 3.22 kg of 11-aminoundecanoic acid was changed to 1.81 kg of ε-caprolactam. Table 2 shows the charging ratio and characteristics of the raw material monomers of this copolymerized polyamide. Next, glass fiber was added to the obtained copolyamide to obtain a reinforced copolyamide resin composition in the same manner as in Example 1. Table 2 shows the composition ratio of the reinforced copolymerized polyamide resin composition, moldability, and evaluation results of molded products obtained from the copolymerized polyamide resin composition.

  As is clear from Tables 1 and 2, the copolymerized polyamides and glass fiber reinforced resins of Examples 1 to 8 are highly satisfied with all three properties of moldability, low water absorption, and impact resistance. . On the other hand, the copolymerized polyamide of Comparative Example 1 in which the 11 nylon or 12 nylon components are not copolymerized not only causes molding failure due to foaming during molding, but also has a high water absorption rate. It becomes brittle. In addition, the copolymerized polyamide of Comparative Example 2 in which hexamethylene was copolymerized with a part of decanediamine had a glass transition temperature that was too high, so that crystallization did not proceed sufficiently and deformation occurred during mold release. Moreover, since hexamethylenediamine was copolymerized, the water absorption rate increased significantly. The copolymerized polyamide of Comparative Example 3 in which the amount of aminoundecanoic acid was increased showed extremely good low water absorption and impact resistance due to the increase in the 11 nylon component, but the 10T component, which is a crystal component, was crystallized. Was hindered, resulting in poor mold release during molding. The copolymerized polyamide of Comparative Example 4 in which ε-caprolactam, which is also an aminocarboxylic acid instead of aminoundecanoic acid, was copolymerized, not only had no effect of impact improvement, but also caused a significant deterioration in water absorption.

  The copolymerized polyamide of the present invention is molded while 11 nylon and / or 12 nylon is copolymerized in a specific ratio with 10T nylon as a main component, while utilizing the characteristics of 10T nylon such as high melting point and slidability. Therefore, it can be suitably used as a molding material or a sliding material for automobiles and electronic parts.

Claims (6)

  (A) 50-98 mol% of structural units obtained from an equimolar molar salt of decanediamine and terephthalic acid, and (b) 11-aminoundecanoic acid, 12-aminododecanoic acid, undecane lactam, lauryllactam, and mixtures thereof A copolyamide comprising 50 to 2 mol% of a structural unit selected from the group consisting of:   (A) 75-98 mol% of structural units obtained from an equimolar molar salt of decanediamine and terephthalic acid, and (b) 11-aminoundecanoic acid, 12-aminododecanoic acid, undecane lactam, lauryllactam, and mixtures thereof The copolymerized polyamide according to claim 1, comprising 25 to 2 mol% of a structural unit selected from the group consisting of:   The copolymerized polyamide is obtained from (c) a structural unit obtained from an equivalent molar 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). The copolyamide according to claim 1 or 2, which comprises up to 30 mol% of structural units.   The copolymer polyamide according to any one of claims 1 to 3, wherein the copolymer polyamide has a melting point (Tm) of 240 to 315 ° C and a glass transition temperature (Tg) of 70 to 120 ° C.   A copolymerized polyamide resin composition, wherein a fibrous reinforcing material is blended at a maximum of 250 parts by weight with respect to 100 parts by weight of the copolymerized polyamide according to any one of claims 1 to 4.   The copolymerized polyamide resin composition according to claim 5, which is used as a molding material for automobile parts or electronic parts.