JP2000191771A - Polyamide and its composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyamide improved in low water absorbability, chemical resistance, melt stability, heat deterioration resistance and toughness compared to conventional semiaromatic polyamides such as PA6-T and excellent in lightweightness and melt flowability as well, and to obtain a polyamide composition containing the above polyamide. SOLUTION: This polyamide is such one as to be composed of a dicarboxylic acid component containing 60-100 mol% of terephthalic acid and a diamine component containing 60-100 mol% of 1,6-hexanediamine and 1,9-nonanediamine and/or 2-methyl-1,8-octanediamine, wherein the diamine component contains 30-60 mol% of 1,9-nonanediamine plus 2-methyl-1,8-octanediamine, and this polyamide has an intrinsic viscosity [η] measured in concentrated sulfuric acid at 30 deg.C of 0.4-3.0 dL/g. The other objective polyamide composition is obtained by compounding 100 pts.wt. of the above polyamide with 0.1-200 pts.wt. of a filler. Molded products can be afforded using the above polyamide or polyamide composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel semi-aromatic polyamide, a composition obtained by mixing a filler with the polyamide, and a molded article thereof. The polyamide and the polyamide composition provided by the present invention have excellent low water absorption, chemical resistance, melt stability, heat aging resistance, and toughness, and are also excellent in light weight, melt fluidity, and the like.
Polyamide and polyamide composition of the present invention, not only various applications of ordinary engineering plastics,
It can be suitably used as a molding material for various mechanical parts, automobile parts, electric / electronic parts, household goods and the like.

[0002]

2. Description of the Related Art Crystalline polyamides such as nylon 6 and nylon 66 have been widely used as fibers for clothing and industrial materials, general-purpose engineering plastics, etc. due to their excellent properties and ease of melt molding. Used. 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 the fields of electric / electronic parts, automobile parts, engineering plastics and the like have been required to have high performance. For example, in the case of electric / electronic parts, the surface mount technology (SMT) has been developed. Accordingly, 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. Thus, as a copolymer component of PA6-T, dicarboxylic acid components such as adipic acid and isophthalic acid are mainly used, and the number of amide groups per unit weight of polyamide is as high as that of conventional nylon 6, nylon 66. does not change. Therefore, the PA6-T copolymer has improved heat resistance and reduced water absorption due to the introduction of aromatic components as compared with conventional nylon 66, but the level is not sufficient.
Further, at present, various physical properties such as chemical resistance, melt stability and heat aging resistance are not sufficient.

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. It is described. Also, JP-A-3-28
No. 1532 discloses a dicarboxylic acid unit composed of 50 to 60 mol% of a terephthalic acid unit and 40 to 50 mol% of an aliphatic dicarboxylic acid unit and 100 parts by weight of a semi-aromatic polyamide composed of an aliphatic alkylenediamine unit.
The polyamide composition containing 0.5 to 200 parts by weight of a fibrous filler has a wider moldable temperature range than a semi-aromatic polyamide containing 60 mol% or more of an aromatic dicarboxylic acid unit as a dicarboxylic acid unit. Have been. However, these polyamide compositions have not yet reached levels such as low water absorption, chemical resistance, melt stability, heat aging resistance and the like that satisfy market requirements.

[0005]

An object of the present invention is to provide a PA
Compared to conventional semi-aromatic polyamides such as 6-T, it has significantly improved low water absorption, chemical resistance, melt stability, heat aging resistance, toughness, light weight, melt fluidity, etc. Another object of the present invention is to provide an excellent polyamide and a composition thereof.

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a dicarboxylic acid component mainly composed of terephthalic acid, 1,6-hexanediamine and a fatty acid having 9 carbon atoms. Semi-aromatic polyamide comprising a diamine component mainly composed of an aromatic diamine has excellent low water absorption, chemical resistance, melt stability, heat aging resistance, toughness, light weight, and melt fluidity. The present invention has been completed by finding that a polyamide composition obtained by blending a filler with an aromatic polyamide has improved mechanical properties while maintaining the above-mentioned performance.

[0007] That is, the present invention relates to terephthalic acid of 60
A dicarboxylic acid component containing from 100 to 100 mol%;
Hexanediamine and 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine are added in an amount of 60 to 1
00 mol%, and 1,9-nonanediamine and 2-
30 to 60 mol% of methyl-1,8-octanediamine
A polyamide comprising a diamine component,
The intrinsic viscosity [η] measured at 30 ° C. in concentrated sulfuric acid is 0.4 to
For a polyamide that is 3.0 dl / g. The present invention also relates to a polyamide composition comprising 0.1 to 200 parts by weight of a filler with respect to 100 parts by weight of the above polyamide. Furthermore, the present invention relates to a molded article comprising the above polyamide or polyamide composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the polyamide of the present invention, 60 to 100 mol% of the dicarboxylic acid component is composed of terephthalic acid, and the ratio is preferably 70 mol% or more.
When the amount of terephthalic acid in the dicarboxylic acid component is within this range, the obtained polyamide is excellent in heat resistance, chemical resistance, mechanical properties and the like. Examples of the dicarboxylic acid component other than terephthalic acid include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, Aliphatic dicarboxylic acids such as 1,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid and dimer acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; isophthalic acid Acid, 2,6-naphthalenedicarboxylic 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, Examples thereof include aromatic dicarboxylic acids such as diphenylsulfone-4,4'-dicarboxylic acid and 4,4'-biphenyldicarboxylic acid, and these can be used alone or in combination of two or more. Among these, isophthalic acid, adipic acid, azelaic acid and sebacic acid are preferably used. further,
Polyvalent carboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can also be used within a range where the resulting polyamide can be melt-molded.

In the polyamide of the present invention, 60 to 100 mol% of the diamine component is composed of 1,6-hexanediamine, 1,9-nonanediamine and / or 2-methyl-diamine.
It is composed of 1,8-octanediamine, and its ratio is preferably at least 75 mol%, more preferably at least 90 mol%. When the total amount of the diamine in the diamine component is within this range, the obtained polyamide has excellent heat resistance, mechanical properties, and the like. Further, 30 to 60 mol% of the diamine component is composed of 1,9-nonanediamine and / or 2-methyl-diamine.
Consists of 1,8-octanediamine. When these conditions are satisfied, the obtained polyamide is excellent in various properties such as chemical resistance and melt stability, and the above conditions are also important from the viewpoint of economical efficiency of the raw material diamine.

The diamine components other than 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine constituting the polyamide of the present invention include, for example, 1,4-butanediamine, , 7-heptanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,1
Linear aliphatic diamines such as 2-dodecanediamine;
Methyl-1,5-pentanediamine, 3-methyl-1,
5-pentanediamine, 2,2,4-trimethyl-1,
6-hexanediamine, 2,4,4-trimethyl-1,
Branched aliphatic diamines such as 6-hexanediamine and 5-methyl-1,9-nonanediamine; cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, bis (4-aminocyclohexyl) methane,
Alicyclic diamines such as norbornane dimethylamine and tricyclodecane dimethylamine; p-phenylenediamine, m-phenylenediamine, xylenediamine, 4,
Examples thereof include aromatic diamines such as 4'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl ether, and these can be used alone or in combination of two or more. Among these, 1,7-heptanediamine, 1,1,
8-octanediamine, 1,10-decanediamine,
1,11-undecanediamine and 1,12-dodecanediamine are preferred.

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. The encapsulation rate of the group is more preferably 40% or more, still more preferably 60% or more.
% Is particularly preferable. When determining the capping rate of the terminal group, the number of carboxyl group terminals, amino group terminals and the number of terminals capped by the terminal capping agent present in the polyamide are measured, respectively, by ¹ H-NMR, It is preferable to obtain from the integrated value of the characteristic signal corresponding to the terminal 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 terminal of the polyamide, 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 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).

[0016]

Embedded image

(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 blocking agent is not particularly limited as long as it has reactivity with a carboxyl group. Examples thereof include methylamine, ethylamine, propylamine, butylamine, hexylamine and 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. Among these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are particularly preferable in terms of reactivity, high 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).

[0020]

Embedded image

[0021] (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.If the polymerization temperature is in the range of 200 to 250 ° C., the polymerization rate is large and the productivity is excellent, 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.

As the filler compounded in 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 compounding amount of these fillers is 0.1 to 200 parts by weight based on 100 parts by weight of the polyamide. When the amount is within the range, the polyamide composition can effectively exhibit the above excellent performance. The compounding amount of the filler is more preferably 0.1 to 150 parts by weight based on 100 parts by weight of the polyamide. 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, nucleating agents or other polymers can also be used as additives.

As a method of blending the above-mentioned fillers or additives 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.

The polyamide and the polyamide composition of the present invention have good moldability, and it is possible to use molding methods such as injection molding, blow molding, extrusion molding, compression molding, stretching, vacuum molding, etc. A shaped article 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 mounts, fans, oil filter brackets, oil strainers, oil pans, cylinder head covers, fuel filters, inlet manifolds, air ducts, wire harness connectors, junction boxes, starter coil bobbins, lamp reflectors and other automotive parts, connectors, switches, and volumes , Bobbins, relay bases, electric and electronic parts such as condenser base materials, and household goods.

[0032]

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],
Measuring methods of tensile strength, strength retention after steam treatment, strength retention after alcohol treatment and IZOD impact strength,
A test method for evaluating the coloring of the copper foil by outgas during melting is 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.

[0034]

[Table 1]

Intrinsic viscosity [η]: The polyamide is dissolved in concentrated sulfuric acid, and the concentrations are 0.05, 0.1, 0.2 and 0.1.
A sample solution of 4 dl / g was prepared, the intrinsic viscosity η _inh at 30 ° C. was measured, and the extrapolated value to a concentration of 0 was defined as the intrinsic viscosity [η].

Presence / absence of coloring of copper foil due to outgas 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 the 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.

Strength retention after steam treatment: JIS No. 1 dumbbell type test piece was prepared using polyamide, and the test piece was used in a pressure 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.

Example 1 3272.76 g (19.70 mol) of terephthalic acid,
1162.1 g (10.0 mol) of 1,6-hexanediamine, 1582.9 g of 1,9-nonanediamine (10.
00 mol), 73.27 g (0.60 mol) of benzoic acid, 6.0 g (0.1% by weight based on the raw material) of sodium hypophosphite monohydrate and 2.2 liters of distilled water
It was placed in a 0 liter autoclave and purged with nitrogen. 2
The internal temperature was raised to 210 ° C. over time. At this time, the pressure in the autoclave was increased to 22 kg / cm ² . After the reaction was continued for 1 hour, the temperature was raised to 230 ° C., and thereafter, the temperature was maintained at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and maintaining the pressure at 22 kg / cm ² . Next, the pressure was reduced to 10 kg / cm ² over 30 minutes, and the reaction was further performed for 1 hour, so that the intrinsic viscosity [η] was 0.25 dl / g.
Was obtained. This is heated at 100 ° C. under reduced pressure for 12 hours.
Dry for hours and pulverize to a size of 2 mm or less. This was subjected to solid-phase polymerization at 230 ° C. and 0.1 mmHg for 10 hours to obtain a polyamide having a terminal blocking rate of 90% and an intrinsic viscosity [η] of 1.22 dl / g. Cylinder temperature 3
Pellets were formed using a twin screw extruder at 30 ° C., and an outgassing test during melting was performed. Table 2 shows the obtained results. The pellet obtained by the above method, the cylinder temperature 330 ℃,
Injection molding was performed at a mold temperature of 140 ° C., and the obtained molded product was measured for tensile strength, strength retention after steam treatment, strength retention after alcohol treatment, and IZOD impact strength.
Table 2 shows the obtained results.

Example 2 1,6-hexanediamine was added as a diamine component to 116
2.1 g (10.0 mol), 1,345-47 g (8.50 mol) of 1,9-nonanediamine, 2-methyl-1,
A polyamide having a terminal blocking rate of 92% and an intrinsic viscosity [η] of 1.21 dl / g was obtained in the same manner as in Example 1 except that 237.44 g (1.50 mol) of 8-octanediamine 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 330 ° C. and a mold temperature of 140 ° C. Using the obtained molded product, tensile strength, strength retention after steam treatment, strength retention after alcohol treatment rate,
IZOD impact strength was measured. Table 2 shows the obtained results.

Example 3 2781.8 g of terephthalic acid as a dicarboxylic acid component
(16.745 mol), 490.9 g of isophthalic acid
(2.955 mol) In the same manner as in Example 1 except that the terminal blocking ratio was 89% and the intrinsic viscosity [η] was 1.2.
3 dl / g of polyamide 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 pellet obtained by the above method is injection-molded at a cylinder temperature of 330 ° C. and a mold temperature of 140 ° C. Using the obtained molded product, tensile strength, strength retention after steam treatment, strength retention after alcohol treatment Rate and IZOD impact strength were measured. Table 2 shows the obtained results.

Example 4 2454.6 g of terephthalic acid as a dicarboxylic acid component
(14.775 mol), 719.7 g of adipic acid
(4.925 mol) in the same manner as in Example 1 except that terminal blocking ratio was 91% and intrinsic viscosity [η] was 1.
21 dl / g of polyamide 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 pellet obtained by the above method is injection-molded at a cylinder temperature of 330 ° C. and a mold temperature of 140 ° C. Using the obtained molded product, tensile strength, strength retention after steam treatment, strength retention after alcohol treatment Rate and IZOD impact strength were measured. Table 2 shows the obtained results.

Example 5 100 parts by weight of the polyamide obtained according to the method of Example 1 were mixed with 50 parts by weight of glass fiber (3540, manufactured by PPG) using a twin-screw extruder at a cylinder temperature of 330 ° C., and pelletized. Shaped. Using this pellet, an outgassing test during melting was performed. Table 2 shows the obtained results.
The pellets obtained by the above method were placed at a cylinder temperature of 330.
Injection molding was performed at 140 ° C. and a mold temperature of 140 ° C., and the obtained molded product was measured for tensile strength, strength retention after steam treatment, strength retention after alcohol treatment, and IZOD impact strength. Table 2 shows the obtained results.

[0046]

[Table 2]

Each symbol in Table 2 is described below. 1) TA: terephthalic acid IA: isophthalic acid AdA: adipic acid HMDA: 1,6-hexanediamine NMDA: 1,9-nonanediamine MODA: 2-methyl-1,8-octanediamine 2) GF: glass fiber

Comparative Example 1 1,6-hexanediamine was used as a diamine component at 185
End sealing was carried out in the same manner as in Example 1 except that 9.36 g (16.0 mol), 633.16 g (4.00 mol) of 1,9-nonanediamine and 5.8 g of sodium hypophosphite were used. Retention 88%, intrinsic viscosity [η] 1.08d
1 / g of polyamide was obtained. The melting point of this polyamide is 3
It was 50 ° C. Pelletization was attempted using a twin-screw extruder with a cylinder temperature of 370 ° C. However, the polyamide was remarkably decomposed thermally, and foaming, coloring, and a decrease in viscosity were observed.

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 terminal blocking rate is 8
A polyamide having an intrinsic viscosity [η] of 1% and 1.00 dl / g was obtained. This polyamide was used in a cylinder at 330 ° C.
Pelletization was performed using a screw extruder, and an outgassing test during melting was performed. Table 3 shows the obtained results. The pellet obtained by the above method was subjected to a cylinder temperature of 330 ° C. and a mold temperature of 1
Injection molding was performed at 40 ° C., and the obtained molded product was measured for tensile strength, strength retention after steam treatment, strength retention after alcohol treatment, and IZOD impact strength. 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 above method, a polyamide having a terminal blocking rate of 81% and an intrinsic viscosity [η] of 1.03 dl / g 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 was heated at a cylinder temperature of 330 ° C. and a mold temperature of 140 ° C.
The tensile strength, the strength retention after the steam treatment, the strength retention after the alcohol treatment, and the IZOD impact strength were measured using the obtained molded article. Table 3 shows the obtained results.

[0051]

[Table 3]

Each symbol in Table 3 is described below. 1) TA, IA, AdA, NMDA and HMDA are as described above. 2)-: Foaming, coloring and viscosity decrease are severe during pelletization, and pellet molding is not possible.

[0053]

Industrial Applicability The polyamide and the polyamide composition of the present invention have excellent low water absorption, chemical resistance, melt stability, heat aging resistance, and toughness. Because of its superiority, it is suitably used as a molding material not only for various applications of ordinary engineering plastics but also for various mechanical parts, automobile parts, electric / electronic parts, household goods, and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J001 DA01 DB01 DB02 DC15 DD07 EB05 EB06 EB07 EB08 EB09 EB37 EB46 EB71 EC08 EC09 EC15 EC16 EC45 EC46 EC47 EC48 HA01 JA02 JA05 JA07 JB04 JB17 JB18 JB21 JB32 4J002 BD162BE032CF1623 DA036 DE106 DE136 DE146 DE186 DJ026 DJ036 DJ046 DK006 DL006 FA042 FA066 FD012 FD016 GM00 GN00 GQ00

Claims (4)

[Claims] 1. A dicarboxylic acid component containing 60 to 100 mol% of terephthalic acid, 1,6-hexanediamine, 1,9-nonanediamine and / or 2-methyl-diamine.
It contains 60 to 100 mol% of 1,8-octanediamine, and 1,9-nonanediamine and 2-methyl-1,8
A polyamide comprising a diamine component containing 30 to 60 mol% of octanediamine, wherein the polyamide is composed of
A polyamide having an intrinsic viscosity [η] of 0.4 to 3.0 dl / g measured in the above. 2. The polyamide according to claim 1, wherein at least 10% of the terminal groups are blocked. 3. Polyamide 10 according to claim 1 or 2
A polyamide composition comprising 0.1 to 200 parts by weight of a filler based on 0 part by weight. 4. A molded article comprising the polyamide according to claim 1 or the polyamide composition according to claim 3.