JP2000086759A - Polyamide and its composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide having excellent toughness, hot water resis tance, chemical resistance, mechanical characteristics, melt stability, light weight, heat resistance, low water absorption, etc., and further having remarkably improved moldability due to a short molding cycle time and the employment of a hot water-heating mold which can be cooled at low temperature, in compari son with semi-aromatic polyamides such as a conventional PA6-T type polyam ide, and to provide a composition containing the polyamide. SOLUTION: This polyamide is produced from a dicarboxylic acid component whose 60-100 mol.% comprises terephthalic acid and a 4-40C aliphatic dicarboxylic acid in a terephthalic acid/4-40C aliphatic dicarboxylic acid weight ratio of 50/50 to 90/10, and a diamine component whose 60-100 mol.% is a 9C aliphatic diamine, and has an intrinsic viscosity [η] of 0.4-3.0 dl/g in concentrated sulfuric acid at 30 deg.C. A polyamide composition is obtained by adding 0.01-10 pts.wt. of a nucleating agent and/or 0.1-200 pts.wt. of a filler to the polyamide. A molded product comprises the polyamide or the polyamide composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel semi-aromatic polyamide, a composition comprising the polyamide and a nucleating agent and / or a filler, and molded articles thereof. The polyamide and the polyamide composition provided by the present invention have excellent toughness, hot water resistance, chemical resistance, mechanical properties, melt stability, and extremely excellent moldability (use of a low-temperature mold, short molding Cycle, etc.), and is also excellent in lightness, heat resistance, low water absorption, and the like. Polyamide and polyamide composition of the present invention,
For example, it can be suitably used as a molding material for industrial materials, industrial materials, household goods and the like.

[0002]

2. Description of the Related Art Crystalline polyamides represented by nylon 6, nylon 66 and the like have been widely used for clothing, industrial materials, engineering plastics, etc. because of their excellent properties and ease of melt molding. I have. However, on the other hand, it has been pointed out that these general-purpose polyamides have problems in points such as insufficient heat resistance and poor dimensional stability due to water absorption. In particular, in recent years, polyamides used in fields such as electric / electronic parts, automobile parts, and engineering plastics have been required to have high performance. For example, in electric / electronic parts, surface mount technology (SMT) has been required. With the development, high heat resistance such as reflow soldering heat resistance has been required, and polyamides having even higher heat resistance than before have been demanded for automobile parts such as engine room parts. Moreover, in conjunction with the expanding use of polyamides, not only in electric / electronic parts and automobile parts, but also in other fields of application, polyamides with even better physical properties and functions are required. At the same time, there is a demand for the development of polyamides having excellent dimensional stability, mechanical properties, chemical resistance and the like.

[0003] In response to the above requirements, polyamides comprising terephthalic acid and 1,6-hexanediamine (hereinafter referred to as "polyamides")
Various types of semi-aromatic polyamides whose main component is PA6-T) have been proposed. Since PA6-T has a melting point near 370 ° C., which is higher than the decomposition temperature of the polymer, melt polymerization and melt molding are difficult and are not practical. Therefore, by actually copolymerizing a dicarboxylic acid component such as adipic acid and isophthalic acid, or an aliphatic polyamide such as nylon 6 by 30 to 50 mol%,
At present, it is used in a temperature range where the melting point can be reduced to a practically usable temperature range, that is, about 280 to 320 ° C. Copolymerizing such a large amount of the third component, and possibly the fourth component in some cases, is certainly effective in lowering the melting point of the polymer, but on the other hand, it lowers the crystallinity, lowers the ultimate crystallinity, and reduces the heat resistance. As a result, not only performance such as rigidity at high temperature, chemical resistance, dimensional stability, melt stability, etc., but also the extension of molding cycle In some cases, productivity may be reduced.

Japanese Patent Publication No. 64-11073 discloses a semi-aromatic polyamide comprising an aromatic dicarboxylic acid unit containing 60 to 100 mol% of a terephthalic acid unit and a linear aliphatic alkylenediamine unit having 6 to 18 carbon atoms. A polyamide composition obtained by blending 0.5 to 200 parts by weight of a filler with respect to 100 parts by weight has excellent performance in all of heat resistance, mechanical properties, chemical physical properties and molding properties. However, the moldability, toughness, light weight, low water absorption, chemical resistance, heat resistance, melt stability and the like of the polyamide composition are not at a sufficient level.

JP-A-3-281532 discloses a semi-aromatic composition comprising a dicarboxylic acid unit composed of 50 to 60 mol% of terephthalic acid units and 40 to 50 mol% of aliphatic dicarboxylic acid units and an aliphatic alkylenediamine unit. The polyamide composition obtained by adding 0.5 to 200 parts by weight of a fibrous filler to 100 parts by weight of an aromatic polyamide contains 60 mol% of an aromatic dicarboxylic acid unit as a dicarboxylic acid unit.
Although it is described that the moldable temperature range is wider than that of the semi-aromatic polyamide included above, the mold temperature during injection molding is actually set to a high temperature of 120 ° C., and ordinary steam or hot water It is difficult to use a warm mold.

Further, JP-A-3-17156 discloses that a composition obtained by blending a thermotropic liquid crystal polymer with a glass fiber reinforced PA6-T copolymerized polyamide is heated to a temperature lower than the glass transition point of the polyamide component. Even when molded using a mold, it shows excellent thermal properties including a high heat deflection temperature, and is described as often facilitating molding using a mold heated with steam or hot water. The above compositions do not have sufficient levels of lightness, low water absorption, chemical resistance, heat resistance, melt stability, and the like.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to make it possible to cool a mold at a low temperature using a hot water heating mold as compared with a conventional semi-aromatic polyamide such as PA6-T type polyamide. Yes, and with significantly improved formability that the molding cycle time is shortened, toughness,
An object of the present invention is to provide a polyamide excellent in hot water resistance, chemical resistance, mechanical properties, melt stability, light weight, heat resistance, low water absorption and the like, and a composition thereof.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a dicarboxylic acid component containing terephthalic acid and an aliphatic dicarboxylic acid as main components, and a C9 fatty acid. Polyamide composed of a diamine component containing an aromatic diamine as a main component has excellent toughness, hot water resistance, chemical resistance, mechanical properties, melt stability, and extremely excellent moldability (low-temperature molds can be used. Short molding cycle, etc.), and also excellent in light weight, heat resistance, low water absorption, etc., and the polyamide composition obtained by blending a crystal nucleating agent and / or a filler with such polyamide has the above-mentioned performance. The present invention was found to improve the crystallization rate and / or to have improved mechanical properties, particularly excellent mechanical properties at high temperatures, while maintaining the present invention.

That is, according to the present invention, 60 to 100 mol% of the dicarboxylic acid component contains terephthalic acid and 4 to 4 carbon atoms.
A dicarboxylic acid component consisting of an aliphatic dicarboxylic acid of 0 and having a weight ratio of terephthalic acid to an aliphatic dicarboxylic acid having 4 to 40 carbon atoms of 50:50 to 90:10, and 60 to 100 mol of a diamine component % Of an aliphatic diamine and a diamine component having an intrinsic viscosity [η] of 0.4 to 3.0 d measured at 30 ° C. in concentrated sulfuric acid.
1 / g. The present invention also relates to a polyamide composition comprising 100 parts by weight of the above polyamide and 0.01 to 10 parts by weight of a nucleating agent and / or 0.1 to 200 parts by weight of a filler. Furthermore, the present invention relates to a molded article comprising the above polyamide or polyamide composition.

[0010]

DETAILED DESCRIPTION OF THE INVENTION In the polyamide of the present invention, 60 to 100 mol% of the dicarboxylic acid component is composed of terephthalic acid and an aliphatic dicarboxylic acid having 4 to 40 carbon atoms, and terephthalic acid and a fatty acid having 4 to 40 carbon atoms. The proportion of group dicarboxylic acid must be 50:50 to 90:10 by weight. When the total amount of terephthalic acid and the aliphatic dicarboxylic acid is less than 60 mol% of the dicarboxylic acid component,
The resulting polyamide has reduced physical properties such as heat resistance and chemical resistance. The total amount of terephthalic acid and the aliphatic dicarboxylic acid is 75 to 10 of the dicarboxylic acid component.
It is preferably 0 mol%, more preferably 90 to 100 mol%. The ratio of terephthalic acid to the above aliphatic dicarboxylic acid is 50:50 to 90:10 by weight.
Within this range, even when a hot water heating mold is used at the time of injection molding, not only the crystallization of the molded product proceeds sufficiently, but also a molded product excellent in melt fluidity and toughness can be obtained. The ratio of terephthalic acid to the aliphatic dicarboxylic acid is preferably in the range of 65:35 to 85:15 by weight.

The aliphatic dicarboxylic acids having 4 to 40 carbon atoms include, for example, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid,
Trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid, dimer acid, etc., and one of these aliphatic dicarboxylic acids Alternatively, two or more kinds can be used. Among these aliphatic dicarboxylic acids, adipic acid, azelaic acid and sebacic acid are preferred.

Other dicarboxylic acid components in the polyamide of the present invention include, for example, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; isophthalic acid, 2,6-naphthalenedicarboxylic acid Acid, 2,7-naphthalenedicarboxylic acid,
1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid,
Diphenic acid, dibenzoic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-
Examples thereof include aromatic dicarboxylic acids such as biphenyldicarboxylic acid, and these can be used alone or in combination of two or more. Among these, aromatic dicarboxylic acids such as isophthalic acid are preferably used. Furthermore, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used as long as the obtained polyamide can be melt-molded.

In the polyamide of the present invention, 60 to 100 mol% of the diamine component must be an aliphatic diamine having 9 carbon atoms. When the proportion is less than 60 mol%, the polyamide becomes unsatisfactory in any of toughness, light weight, low water absorption, chemical resistance, heat resistance and melt stability. The above ratio is preferably from 75 to 100 mol%, more preferably from 90 to 100 mol%. Examples of the aliphatic diamine having 9 carbon atoms include 1,9-nonanediamine (hereinafter sometimes abbreviated as NMDA) and 2-methyl-1,8-octanediamine (hereinafter abbreviated as MODA). A)). As other diamine components in the polyamide of the present invention, for example, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,10-diamine
Decanediamine, 1,11-undecanediamine, 1,
Linear aliphatic diamines such as 12-dodecanediamine; 2
-Methyl-1,5-pentanediamine, 3-methyl-
1,5-pentanediamine, 2,2,4-trimethyl-
1,6-hexanediamine, 2,4,4-trimethyl-
Branched aliphatic diamines such as 1,6-hexanediamine and 5-methyl-1,9-nonanediamine; cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, bis (4-aminocyclohexyl) methane, norbornanedimethylamine, tricyclo Alicyclic diamines such as decane dimethylamine; p-phenylenediamine, m-phenylenediamine, xylenediamine;
Examples thereof include aromatic diamines such as 4,4'-diaminodiphenylsulfone and 4,4'-diaminodiphenylether, and these can be used alone or in combination of two or more. Of these, 1,6-hexanediamine,
1,7-heptanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine are preferred. N
The ratio between MDA and MODA is preferably such that the molar ratio of the former to the latter is 100: 0 to 10:90, and more preferably the ratio is 100: 0 to 20:80. preferable.

In the polyamide of the present invention, from the viewpoint of stabilizing the molecular weight and improving the melt stability, it is preferable that at least 10% of the terminal groups of the molecular chain are blocked with a terminal blocking agent. Is more preferably 40% or more, more preferably 60% or more of the terminal group is sealed, and particularly preferably 70% or more of the terminal group is sealed. In determining the terminal blocking ratio of the carboxyl group-terminated present in the polyamide, although each measuring the number of ends sealed by amino-terminal and terminal blocking agent, the ¹ H-NMR, each end It is preferable to obtain from the integrated value of the characteristic signal corresponding to the group in terms of accuracy and simplicity. When the characteristic signal of the terminal capped by the terminal blocking agent cannot be identified, the intrinsic viscosity [η] of the polyamide is measured, and Mn = 21900 [η] -7900 (Mn represents a number average molecular weight) The total number of molecular chain terminal groups is calculated using the relationship of total number of terminal groups (eq / g) = 2 / Mn. further,
By titration, the number of carboxyl group terminals of the polyamide (eq
/ G) [0.1% solution of polyamide in benzyl alcohol
N with sodium hydroxide] and the number of amino groups (eq / g) [0.1 N phenol solution of polyamide
Titration with hydrochloric acid], and the terminal sealing ratio can be determined by the following equation (1).

Sealing ratio (%) = [(AB) ÷ A] × 100 (1) [wherein A is the total number of molecular chain terminal groups (this is usually twice the number of polyamide molecules) And B represents the total number of carboxyl and amino groups.

The terminal blocking agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the polyamide terminal, but from the viewpoints of reactivity and stability of the blocked terminal. , Monocarboxylic acids or monoamines are preferred, and monocarboxylic acids are more preferred from the viewpoint of easy handling. In addition, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols can also be used.

The monocarboxylic acid that can be used as a terminal blocking agent is not particularly limited as long as it has reactivity with an amino group. Examples thereof include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, and caprylic acid. Aliphatic monocarboxylic acids such as acids, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutylic acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α- Naphthalene carboxylic acid, β-naphthalene carboxylic acid, methyl naphthalene carboxylic acid, aromatic monocarboxylic acids such as phenylacetic acid,
Alternatively, an arbitrary mixture thereof can be mentioned.
Among them, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid are considered from the viewpoints of reactivity, sealed terminal stability, and price. And benzoic acid are particularly preferred.

The amino group terminal of the polyamide of the present invention is blocked with these monocarboxylic acids to form a blocked terminal represented by the following general formula (I).

[0019]

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(In the formula, R is a residue obtained by removing a carboxyl group from the above monocarboxylic acid, and is preferably an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.)

The monoamine used as the terminal capping agent is not particularly limited as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine Aliphatic monoamines such as decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; cycloaliphatic monoamines such as cyclohexylamine and dicyclohexylamine; aniline, toluidine, diphenylamine,
An aromatic monoamine such as naphthylamine, or an arbitrary mixture thereof can be mentioned. Of these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are particularly preferred from the viewpoints of reactivity, boiling point, stability of the sealed terminal, and price.

The carboxyl group terminal of the polyamide of the present invention is blocked with these monoamines to form a blocked terminal represented by the following general formula (II).

[0023]

Embedded image

[0024] (In the formula, R ¹ is a residue obtained by removing the amino groups from the above monoamines, preferably alkyl group, a cycloalkyl group, an aryl group, an aralkyl group .R ²
Is a hydrogen atom or a residue obtained by removing the amino group from the above monoamine, and is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. )

The polyamide of the present invention can be produced by any method known as a method for producing a crystalline polyamide. For example, a solution polymerization method or an interfacial polymerization method using acid chloride and diamine as raw materials; a melt polymerization method using dicarboxylic acid and diamine as raw materials, a solid state polymerization method,
It can be produced by a method such as a melt extruder polymerization method. In the production of polyamides, phosphoric acid, phosphorous acid, hypophosphorous acid, or salts thereof, and esters thereof, for the purpose of increasing the rate of polycondensation and preventing the polyamide formed during polymerization from deteriorating. It is preferable to add a phosphorus-based catalyst such as a catalyst to the reaction system. Of these, a hypophosphorous acid derivative is preferred from the viewpoint of the quality of the produced polyamide, and particularly, sodium hypophosphite is preferred from the viewpoint of cost and ease of handling. The addition amount of these phosphorus-based catalysts is preferably 0.01 to 5% by weight based on the total weight of dicarboxylic acid and diamine, and 0.05 to 2% by weight.
%, More preferably 0.07 to 1% by weight. The amount of the terminal blocking agent varies depending on the reactivity of the terminal blocking agent used, the boiling point, the reaction apparatus, the reaction conditions, and the like, but is usually 0 to the total number of moles of the dicarboxylic acid and the diamine. It can be used within a range of 0.1 to 15 mol%.

The following is an example of a method for producing a polyamide. If necessary, a catalyst and a terminal blocking agent are first added to the diamine and the dicarboxylic acid at once, to produce a nylon salt, and then, once at a temperature of 200 to 250 ° C, the intrinsic viscosity at 30 ° C in concentrated sulfuric acid [η] ] Is 0.15 to 0.2
A polyamide can be easily obtained by forming a prepolymer of 5 dl / g and further performing solid phase polymerization or performing polymerization using a melt extruder. When the intrinsic viscosity [η] of the prepolymer is in the range of 0.15 to 0.25 dl / g, a shift in the molar balance between carboxyl groups and amino groups and a decrease in the polymerization rate in the post-polymerization stage are small, and the molecular weight is further reduced. A polyamide having a small distribution and excellent in various performances and moldability can be obtained. When the final stage of the polymerization is carried out by solid phase polymerization, it is preferable to carry out under reduced pressure or under an inert gas flow. It is preferable because coloring and gelation can be effectively suppressed. When the final stage of the polymerization is carried out by a melt extruder, the polymerization temperature is 370
When the temperature is lower than or equal to ° C., polyamide is hardly decomposed and a polyamide without deterioration is obtained.

The polyamide of the present invention has an intrinsic viscosity [η] measured in concentrated sulfuric acid at 30 ° C. in the range of 0.4 to 3.0 dl / g, and in the range of 0.6 to 2.0 dl / g. Are preferable, and those in the range of 0.8 to 1.8 dl / g are more preferable. When the intrinsic viscosity [η] is within the above range, the mechanical properties and moldability of the polyamide become good.

The nucleating agent blended in the polyamide of the present invention is not particularly limited as long as it is generally used as a nucleating agent for polyamide.
Silica, graphite, magnesium oxide, aluminum oxide, calcium stearate, aluminum stearate, barium stearate, zinc stearate, partially saponified calcium salts of montanic acid esters, or any mixture thereof. Of these,
Talc is preferred because it has a large effect of increasing the crystallization speed of the polyamide. The nucleating agent may be treated with a silane coupler or a titanium coupler for the purpose of improving the compatibility with the polyamide. The amount of the crystal nucleating agent is preferably in the range of 0.01 to 10 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the polyamide. The crystal nucleating agent can be added at any stage from polymerization of the polyamide to molding.

As the filler to be added to the polyamide of the present invention, conventionally known fillers having various forms such as powder, fiber, cloth and the like can be used. As the powdery filler, for example, talc, silica,
Silica alumina, alumina, titanium oxide, zinc oxide, boron nitride, potassium titanate, calcium silicate, magnesium sulfate, aluminum borate, asbestos, wollastonite, potassium titanate whisker, calcium carbonate whisker, aluminum borate whisker, glass Examples include beads, carbon black, graphite, molybdenum disulfide, and polytetrafluoroethylene. When a powdery filler is blended, a molded article obtained from the polyamide composition has excellent dimensional stability, heat resistance, chemical and physical properties, sliding properties and the like.

Examples of the fibrous filler include polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaphenylene isophthalamide fiber, polymetaphenylene isophthalamide fiber, diaminodiphenyl ether and terephthalic acid or isophthalic acid. Organic fiber fibrous fillers such as wholly aromatic polyamide fibers such as fibers obtained from condensates of the above, or wholly aromatic liquid crystal polyester fibers and vinylon fibers; or glass fibers, carbon fibers, alumina fibers, metal fibers, and boron fibers And inorganic fibrous fillers. When such a fibrous filler is compounded, a molded article obtained from the polyamide composition is preferable because it not only has excellent sliding properties, but also has excellent mechanical properties, heat resistance properties, and chemical physical properties. . These fibrous fillers are
Those having an average length in the range of 0.05 to 50 mm are preferred. Furthermore, it is more preferable to use those having an average length in the range of 1 to 10 mm in that the moldability is good and the obtained molded product has more excellent sliding properties, heat resistance properties, and mechanical properties. These fibrous fillers may be subjected to secondary processing such as cloth.

The above-mentioned fillers can be used alone or in combination of two or more. The amount of these fillers is preferably in the range of 0.1 to 200 parts by weight, and more preferably 0.1 to 150 parts by weight, based on 100 parts by weight of polyamide or a composition obtained by blending a crystal nucleating agent with polyamide. More preferably, it is within the range. If it is within the range of this compounding amount,
The polyamide composition can effectively exhibit the above excellent performance. The above filler may be treated with a silane coupler, a titanium coupler, or the like.

When the polyamide or the polyamide composition of the present invention is used in the electric or electronic field, a brominated polymer such as polytribromostyrene, polydibromostyrene, brominated polyphenylene ether, antimony oxide, metal hydroxide, etc. It is preferable to add a flame retardant. In addition, if necessary, hindered phenol-based, hindered amine-based, phosphorus-based, thio-based antioxidants, coloring agents, ultraviolet absorbers, light stabilizers, antistatic agents, plasticizers,
Lubricants or other types of polymers can also be used as additives.

As a method of blending the above-mentioned filler or an additive used as necessary with the polyamide, a method of adding during the polycondensation reaction, a method of dry blending, a method of melt-kneading using an extruder, and the like are employed. Is done.

As a mold for injection molding the polyamide or polyamide composition of the present invention, steam or steam which has been difficult to use since conventional semi-aromatic polyamides require a higher mold temperature. A hot water heating mold can be used. The polyamide and the polyamide composition of the present invention are sufficiently crystallized and exhibit a sufficiently high load deflection temperature even when a steam or hot water heating mold, whose temperature can usually be set only up to about 120 ° C., is used. In addition, the molded product is sufficiently crystallized even in a mold cooling time shorter than that of the conventional semi-aromatic polyamide, which leads to a high cycle of molding.

The polyamide and the polyamide composition of the present invention have good moldability. In addition to the above-described injection molding, molding methods such as blow molding, extrusion molding, compression molding, stretching, and vacuum molding can be used. Yes, a molded article having a desired shape can be manufactured. Specifically, molded articles of various shapes such as sheets, films, bottles, and fibers can be obtained.

The above molded products include not only various applications of ordinary engineering plastics, but also mechanical parts such as bearing retainers, belt chains, clampers, pulleys, gears, cases, washers, bolts, nuts, travelers, and radiator tanks. , Engine mount, fan, oil filter bracket, oil strainer, oil pan, cylinder head cover, fuel filter, inlet manifold, air duct, wire harneus connector, junction box,
Examples include automotive parts such as starter coil bobbins and lamp reflectors, electrical and electronic parts such as connectors, switches, volumes, bobbins, relay bases, condenser base materials, and household goods.

[0037]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited by these examples. In the examples, the terminal sealing ratio, intrinsic viscosity [η], water absorption, tensile strength, strength retention after steam treatment, strength retention after alcohol treatment, IZOD impact strength, and crystallization heat after quenching And the test method for evaluating the coloring of the copper foil by outgassing during melting are shown below.

Terminal blocking ratio: ¹ H-NMR (500 MH
z, measured in deuterated trifluoroacetic acid at 50 ° C.), the number of carboxyl group ends, amino group ends and sealed ends was measured from the integrated value of the characteristic signal for each terminal group, and the above formula was used. The terminal blocking rate was determined from (1). Table 1 shows chemical shift values of typical signals used in the measurement.

[0039]

[Table 1]

Intrinsic viscosity [η]: The polyamide is dissolved in concentrated sulfuric acid and the concentrations are 0.05, 0.1, 0.2 and 0.4.
A sample solution of dl / g was prepared, and the intrinsic viscosity η _inh at 30 ° C. was measured.
[η].

Presence or absence of coloring of copper foil due to outgassing during melting: 10 g of polyamide pellets were placed in a 100 cc flask, and a 1 cm square copper foil was hung from above in a space of the flask. Next, while the flask was immersed in a bath at 340 ° C. for 120 minutes while flowing nitrogen at a flow rate of 50 cc / min, the presence or absence of coloring of the copper foil was visually evaluated (hereinafter, this is referred to as an outgas test during melting). The case where no coloring was observed was evaluated as ○, the case where a part was colored was evaluated as △, and the case where the entire color was colored was evaluated as x.

Tensile strength: JIS 1 using polyamide
No. dumbbell type test piece (thickness: 3 mm) was prepared, and the tensile strength was measured using the test piece according to JIS K-7113.

Water absorption: JIS 1 using polyamide
No. 2 dumbbell-shaped test piece was prepared, and
The ratio (%) of the weight increase when immersed in water at 3 ° C. for one day to the weight before immersion was measured.

Strength retention after steam treatment: A JIS No. 1 dumbbell-type test piece was prepared using polyamide, and the test piece was used in a pressure-resistant autoclave at 120 ° C.
Steam treatment was performed at 2 atm for 60 hours, and the ratio (%) of the tensile strength of the test piece after the treatment to the tensile strength before the treatment was measured.

Strength retention after alcohol treatment: JIS No. 1 dumbbell type test piece was prepared using polyamide,
The ratio (%) of the tensile strength after the test piece was immersed in methanol at 23 ° C. for one week to the tensile strength before the treatment was measured.

IZOD impact strength: Using polyamide,
A test piece of 63.5 mm × 13 m × 3 mm was prepared, and the test piece was used to make an IZOD according to ASTM D256.
The impact strength was measured.

Heat value of crystallization after quenching: A 10 mm × 50 mm × 0.2 mm press film was press-formed using a polyamide pellet at a cooling press temperature of 100 ° C. The obtained press film was subjected to DSC measurement (3.
(The temperature is raised from 0 ° C to 350 ° C at a rate of 10 ° C / min.)
Then, the heat of crystallization appearing near the temperature exceeding the glass transition temperature was measured. The smaller this value is, the more the press film is crystallized.

Example 1 2229.93 g (13.79 mol) of terephthalic acid, 863.69 g (5.91 mol) of adipic acid, 3165.8 g (20.00 mol) of 1,9-nonanediamine, 73.27 g of benzoic acid (0.60 mol), 6.4 g of sodium hypophosphite monohydrate (0.1% by weight based on the raw material), and 2.2 liters of distilled water were put into an autoclave having an inner volume of 20 liters, and the inside of the autoclave was purged with nitrogen. . The internal temperature was raised to 210 ° C. over 2 hours. At this time, the autoclave is 22k
g / cm ² . After the reaction was continued for 1 hour, the temperature was raised to 230 ° C., and then maintained at 230 ° C. for 2 hours.
^The reaction was carried out while keeping at ² . Next, the pressure is increased to 1 over 30 minutes.
The pressure was lowered to 0 kg / cm ^2, and the mixture was further reacted for 1 hour to obtain a prepolymer having an intrinsic viscosity [η] of 0.25 dl / g. This was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This is 230 ° C, 0.1 mmHg
Under the solid state polymerization for 10 hours, intrinsic viscosity [η] is 1.22 dl
/ G of polyamide was obtained. This polyamide was pelletized using a twin-screw extruder with a cylinder temperature of 310 ° C., and an outgassing test during melting was performed. Table 2 shows the obtained results. The pellets obtained by the above method were heated at a cylinder temperature of 3
Injection molding was performed at 10 ° C. and a mold temperature of 80 ° C., and the obtained molded product was measured for water absorption, tensile strength, strength retention after steam treatment, strength retention after alcohol treatment, and IZOD impact strength. . Table 2 shows the obtained results. Further, the pellets obtained by the above method were press-formed at 310 ° C., and the crystallization heat after quenching was measured using the obtained press film. Table 2 shows the obtained results.

Example 2 Terephthalic acid was 2781.85 as a dicarboxylic acid component.
g (16.745 mol), 597.65 g of sebacic acid
(2.955 mol) A polyamide having an intrinsic viscosity [η] of 1.21 dl / g was obtained in the same manner as in Example 1 except that the polyamide was used. This polyamide was pelletized according to the method of Example 1, and an outgassing test during melting was performed. Table 2 shows the obtained results. The pellet obtained by the above method is injection molded at a cylinder temperature of 310 ° C. and a mold temperature of 80 ° C.
Using the obtained molded product, water absorption, tensile strength, strength retention after steam treatment, strength retention after alcohol treatment,
IZOD impact strength was measured. Table 2 shows the obtained results. Further, using the pellet obtained by the above method, 310
Press molding was performed at ℃, and the crystallization calorific value after quenching was measured using the obtained press film. Table 2 shows the obtained results.

Example 3 As a diamine component, 1,9-nonanediamine was added to 269
0.93 g (17.00 mol), 2-methyl-1,8-
According to the same method as that of Example 1 except that 474.87 g (3.00 mol) of octanediamine was used, the limiting viscosity was determined.
A polyamide having [η] of 1.21 dl / g was obtained. This polyamide was pelletized according to the method of Example 1, and an outgassing test during melting was performed. Table 2 shows the obtained results.
The pellets obtained by the above method were subjected to a cylinder temperature of 310.
Injection molding was performed at 80 ° C. and a mold temperature of 80 ° C., and the obtained molded product was measured for water absorption, tensile strength, strength retention after steam treatment, strength retention after alcohol treatment, and IZOD impact strength. Table 2 shows the obtained results. Further, the pellets obtained by the above method were press-formed at 310 ° C., and the crystallization calorific value after quenching was measured using the obtained press film. Table 2 shows the obtained results.

Example 4 180.02 terephthalic acid as a dicarboxylic acid component
g (10.84 mol), 1296.26 g of adipic acid
(8.87 g), sodium hypophosphite monohydrate.
A polyamide having an intrinsic viscosity [η] of 1.21 dl / g was obtained in the same manner as in Example 1 except that 3 g was used. This polyamide was pelletized according to the method of Example 1, and an outgassing test during melting was performed. Table 2 shows the obtained results. The pellets obtained by the above method were heated at a cylinder temperature of 3
Injection molding was performed at 10 ° C. and a mold temperature of 80 ° C., and the obtained molded product was measured for water absorption, tensile strength, strength retention after steam treatment, strength retention after alcohol treatment, and IZOD impact strength. . Table 2 shows the obtained results. Further, the pellets obtained by the above method were press-formed at 310 ° C., and the crystallization calorific value after quenching was measured using the obtained press film. Table 2 shows the obtained results.

Example 5 0.2 part by weight of talc [PKP-80 aminosilane-treated product, manufactured by Fuji Talc Kogyo Co., Ltd.] was mixed with 100 parts by weight of the polyamide obtained according to the method of Example 1. Pellets were obtained according to the same method as described above. Using this pellet, an outgassing test during melting was performed. Table 2 shows the obtained results. The pellet obtained by the above method is injection-molded at a cylinder temperature of 310 ° C. and a mold temperature of 80 ° C. Using the obtained molded product, water absorption, tensile strength, strength retention after steam treatment, after alcohol treatment Strength retention, IZ
The OD impact strength was measured. Table 2 shows the obtained results.
Further, the pellets obtained by the above method were press-formed at 310 ° C., and the crystallization calorific value after quenching was measured using the obtained press film. Table 2 shows the obtained results.

Example 6 To 100 parts by weight of the polyamide obtained according to the method of Example 1, 0.2 part by weight of talc [PKP-80 aminosilane-treated product, manufactured by Fuji Talc Kogyo KK] and glass fiber [3540, manufactured by PPG And 50 parts by weight thereof, and pellets were obtained in the same manner as in Example 1. Using this pellet, an outgassing test during melting was performed. Table 2 shows the obtained results. The pellet obtained by the above method is injection-molded at a cylinder temperature of 310 ° C. and a mold temperature of 80 ° C. Using the obtained molded product, water absorption, tensile strength, strength retention after steam treatment, after alcohol treatment Strength retention, IZ
The OD impact strength was measured. Table 2 shows the obtained results.
Further, the pellets obtained by the above method were press-formed at 310 ° C., and the crystallization calorific value after quenching was measured using the obtained press film. Table 2 shows the obtained results.

[0054]

[Table 2]

Comparative Example 1 Terephthalic acid was 3272.76 as a dicarboxylic acid component.
g (19.7 mol), and a polyamide having an intrinsic viscosity [η] of 1.22 dl / g was obtained in the same manner as in Example 1 except that g (19.7 mol) was used. This polyamide was pelletized using a twin-screw extruder with a cylinder temperature of 330 ° C., and an outgassing test during melting was performed. Table 3 shows the obtained results. The pellet obtained by the above method is injection-molded at a cylinder temperature of 330 ° C. and a mold temperature of 80 ° C. Using the obtained molded product, water absorption, tensile strength, strength retention after steam treatment, after alcohol treatment Was measured for its strength retention and IZOD impact strength.
Table 3 shows the obtained results. Further, the pellets obtained by the above method were press-formed at 330 ° C., and the crystallization heat after quenching was measured using the obtained press film. Table 3 shows the obtained results.

Comparative Example 2 2290.9 g of terephthalic acid as a dicarboxylic acid component
(13.79 mol), 981.8 g of isophthalic acid
Example 1 (5.91 mol), except that 2324.2 g (20.00 mol) of 1,6-hexanediamine and 6.5 g of sodium hypophosphite monohydrate were used as diamine components. According to the same method as described above, the intrinsic viscosity [η]
Was 1.00 dl / g. This polyamide was pelletized using a twin-screw extruder with a cylinder temperature of 330 ° C., and an outgassing test during melting was performed. Table 3 shows the obtained results. The pellet obtained by the above method is injection-molded at a cylinder temperature of 330 ° C. and a mold temperature of 80 ° C. Using the obtained molded product, water absorption, tensile strength, strength retention after steam treatment, after alcohol treatment Strength retention, I
The ZOD impact strength was measured. Table 3 shows the obtained results. Further, using the pellet obtained by the above method, 330
Press molding was performed at ℃, and the crystallization calorific value after quenching was measured using the obtained press film. Table 3 shows the obtained results.

Comparative Example 3 180.02 terephthalic acid as a dicarboxylic acid component
g (10.84 mol), 1296.26 g of adipic acid
(8.87 mol), the same as Example 1 except that 2324.2 g (20.00 mol) of 1,6-hexanediamine and 5.5 g of sodium hypophosphite monohydrate were used as diamine components. According to the method described above, the intrinsic viscosity [η] is 1.0
3 dl / g of polyamide was obtained. This polyamide was pelletized using a twin-screw extruder with a cylinder temperature of 330 ° C., and an outgassing test during melting was performed. Table 3 shows the obtained results. The pellet obtained by the above method is injection-molded at a cylinder temperature of 330 ° C. and a mold temperature of 80 ° C. Using the obtained molded product, water absorption, tensile strength, strength retention after steam treatment, after alcohol treatment Strength retention, IZOD
The impact strength was measured. Table 3 shows the obtained results. Further, the pellets obtained by the above method were press-formed at 330 ° C., and the crystallization heat after quenching was measured using the obtained press film. Table 3 shows the obtained results.

[0058]

[Table 3]

[0059]

The polyamide and the composition of the present invention are excellent in toughness, hot water resistance, chemical resistance, mechanical properties, melt stability and extremely excellent moldability (use of a low-temperature mold, Short molding cycle) and excellent light weight, heat resistance, low water absorption, etc., not only for various applications of ordinary engineering plastics, but also for various mechanical parts, automobile parts, electric -It is suitably used for electronic parts and household goods.

Continued on the front page F-term (reference) 4J001 DA01 DB04 DC14 EB05 EB06 EB07 EB08 EB09 EB13 EB37 EB71 EC08 EC09 EC13 EC14 EC16 EC45 EC46 EC47 EC67 EC70 EE08E EE18E EE27E FA01 FB05 FC03 FC05 FD01 JA01 JB021DE0 DA142 DE187 DG027 DG047 DJ007 DJ016 DJ017 DJ027 DJ046 DJ047 DK007 DL007 EG016 FA067 FA087 FD012 FD017 FD206

Claims (4)

[Claims] 1. 60 to 100 mol% of a dicarboxylic acid component
Is composed of terephthalic acid and an aliphatic dicarboxylic acid having 4 to 40 carbon atoms, and the ratio of terephthalic acid to the aliphatic dicarboxylic acid having 4 to 40 carbon atoms is 50:50 to 90:
A dicarboxylic acid component of 10 and a diamine component of 60 to
A polyamide comprising a diamine component in which 100 mol% is an aliphatic diamine having 9 carbon atoms.
A polyamide having an intrinsic viscosity [η] of 0.4 to 3.0 dl / g measured in the above. 2. A polyamide composition comprising 0.01 to 10 parts by weight of a nucleating agent per 100 parts by weight of the polyamide according to claim 1. 3. A polyamide composition obtained by mixing 0.1 to 200 parts by weight of a filler with respect to 100 parts by weight of the polyamide of claim 1 or the polyamide composition of claim 2. 4. The polyamide according to claim 1 or claim 2.
Or a molded article comprising the polyamide composition according to 3.