JP3466331B2 - Polyamide, polyamide composition and use thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a specific semi-aromatic polyamide, a polyamide composition obtained by blending the polyamide with a filler, and its use. The polyamide and the polyamide composition of the present invention have extremely excellent moldability, and have excellent dimensional stability, hot water resistance, surface beauty, heat resistance, mechanical properties, low water absorption, chemical resistance, and the like, Parts for engineering use, fibers, films obtained from these polyamides and polyamide compositions,
Molded articles of various shapes such as sheets and bottles can be suitably used for applications such as industrial materials, industrial materials and household products.

[0002]

2. Description of the Related Art Conventionally, crystalline polyamides such as nylon 6 and nylon 66 have been widely used as fibers for clothes, industrial materials or general-purpose engineering plastics because of their excellent properties and ease of melt molding. However, on the other hand, problems such as insufficient heat resistance and poor dimensional stability due to water absorption have been pointed out. Especially in the electric and electronic fields that require heat resistance of reflow solder due to the recent progress of surface mounting technology (SMT), or in the engine room parts of automobiles where the demand for heat resistance is increasing year by year, the use of conventional polyamide is not recommended. It is difficult, and there is an increasing demand for polyamides having more excellent heat resistance, dimensional stability, mechanical properties and physicochemical properties.

To meet such requirements, adipic acid and 1,
Various all-aliphatic polyamides composed of 4-butanediamine and semi-aromatic polyamides containing terephthalic acid and 1,6-hexanediamine as main components have been proposed and some of them have been put into practical use. However, a polyamide composed of adipic acid and 1,4-butanediamine (hereinafter abbreviated as PA4-6)
Has a low melt viscosity and has better moldability than semi-aromatic polyamide containing terephthalic acid and 1,6-hexanediamine as the main components, but has a high water absorption rate and is suitable for practical use such as dimensional stability. Changes in various physical properties are regarded as problems.

On the other hand, a polyamide composed of terephthalic acid and 1,6-hexanediamine (hereinafter, abbreviated as PA6-T) has a melting point near 370 ° C., which is higher than the decomposition temperature of the polymer, so that it is not suitable for melt polymerization or melt molding. It is difficult and not practical. Therefore, in practice, a dicarboxylic acid component such as adipic acid or isophthalic acid, or an aliphatic polyamide such as nylon 6 is copolymerized in an amount of 30 to 40 mol% so that the temperature can be practically used, that is, 2
At present, it is used in a composition having a low melting point of about 80 to 320 ° C. Copolymerization of such a large amount of the third component (in some cases, the fourth component) is effective for lowering the melting point of the polymer, but on the other hand, it is accompanied by a decrease in crystallization rate and ultimate crystallinity. As a result, not only the physical properties such as rigidity at high temperature, chemical resistance, and dimensional stability are deteriorated, but also the productivity is deteriorated as the molding cycle is extended. In addition, with regard to changes in various physical properties such as dimensional stability due to water absorption, although it is somewhat improved by introducing an aromatic group as compared with conventional aliphatic polyamides, it has reached a level of practical problem solving. Not not.

Japanese Patent Publication No. 64-11073, JP-A-6-6
As a diamine component of semi-aromatic polyamide, Japanese Patent Publication No. 2-36459, Japanese Patent Publication No. 1-19809, etc.
In addition to 1,6-hexanediamine, it is mentioned that longer chain linear aliphatic diamines can be used. In British Patent No. 1070416, a nylon salt composed of terephthalic acid and 1,9-nonanediamine is subjected to polycondensation in the presence of 3.1 to 4.0 mol% of terephthalic acid based on the diamine component. Polyamide with intrinsic viscosity (ηinh) of 0.67 to 1.03 dl / g (hereinafter referred to as PA
9-T) is manufactured and fiberized. Further, in JP-A-59-155427 and US Pat. No. 4,617,342, terephthalic acid and 1,6-hexanediamine which is a linear aliphatic diamine and 2,2,4 which is a branched aliphatic diamine are disclosed. -(2,4
4-) Polyamides consisting of trimethylhexanediamine are described. However, in these prior documents, the use of 2-methyl-1,8-octanediamine, which is a branched chain aliphatic diamine, as the diamine component,
Alternatively, there is no specific disclosure of using 2-methyl-1,8-octanediamine and 1,9-nonanediamine, which is a linear aliphatic diamine, in a specific ratio.

[0006]

DISCLOSURE OF THE INVENTION According to the research conducted by the present inventors, terephthalic acid and 1,9-nonanediamine, which are obtained by supplementing the method described in British Patent No. 1070416, are used. Polyamide in which is not sealed (that is, having a carboxyl group at the end) has a tendency to be colored or foamed during melt molding, and the surface beauty of the resulting molded article is insufficient, and the hot water resistance is also high. There is a problem that it is inferior. Further, JP-A-59-15
Copolymerization of a branched chain aliphatic diamine, 2,2,4- (2,4,4-) trimethylhexamethylenediamine, with a PA6-T polyamide described in Japanese Patent No. 5427 and US Pat. No. 4,617,342. The resulting polyamide has a problem that the molded product is inferior in rigidity at high temperature, chemical resistance, dimensional stability when absorbing water, and the like.

The object of the present invention is to have molding processability which is remarkably improved as compared with conventional semi-aromatic polyamides, and is excellent in heat resistance, low water absorption, chemical resistance and the like, and has dimensional stability. Another object is to provide a polyamide having excellent hot water resistance and mechanical properties. Another object of the present invention is to provide a polyamide composition having excellent moldability, low water absorption, chemical resistance and high heat distortion temperature. Further, the present invention has an object to provide a molded article made of the above polyamide or polyamide composition, which is excellent in surface beauty and chemical resistance, has a small water absorption dimensional change, and has a small performance deterioration at high temperatures. .

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a semi-aromatic polyamide mainly composed of a terephthalic acid unit and a 2-methyl-1,8-octanediamine unit. In order to obtain a polyamide having excellent properties such as melt moldability, surface beauty, and hot water resistance, it is necessary to control the intrinsic viscosity [η] and the terminal sealing rate within specific ranges. Acid unit and 2-methyl-1,8-
By copolymerizing a semi-aromatic polyamide mainly composed of octanediamine units with a specific amount of 1,9-nonanediamine, a polyamide having more excellent melt moldability and surface beauty can be obtained without impairing the characteristics of the polyamide. By blending a specific amount of a filler with these polyamides, a polyamide composition having excellent moldability, low water absorption, chemical resistance, and high heat distortion temperature can be obtained; Or, by molding a polyamide composition by a usual melt molding method, it has been found that a molded article having excellent surface beauty, chemical resistance, small water absorption dimensional change, and small performance deterioration at high temperature can be obtained. Was completed.

That is, in the present invention, 60 to 100 mol% of the dicarboxylic acid unit is composed of a terephthalic acid unit, and 60 to 100 mol% of the diamine unit is 2-methyl-1,8-.
A polyamide composed of octanediamine units, which has an intrinsic viscosity [η] measured in concentrated sulfuric acid at 30 ° C. of 0.4 to 3.
A polyamide having a terminal group of 0 dl / g and 10% or more of which terminal groups are sealed [hereinafter, may be referred to as polyamide (A)]; or 60 to 100 mol% of dicarboxylic acid units are terephthalic acid units. , 60 of diamine units
~ 100 mol% consists of 2-methyl-1,8-octanediamine units and 1,9-nonanediamine units, and 2-methyl-1,8-octanediamine units and 1,9
The molar ratio with the nonanediamine unit is 61:39 to 99:
A polyamide which is 1 mol% and has an intrinsic viscosity [η] measured in concentrated sulfuric acid at 30 ° C. of 0.4 to 3.0 dl / g [may be referred to as polyamide (B) hereinafter]. . The present invention also provides the above polyamide 10
It is a polyamide composition obtained by blending 0 part by weight of a filler with 1 to 200 parts by weight. Furthermore, the present invention is a molded article made of the above polyamide or polyamide composition.

The present invention will be described in detail below. The polyamide of the present invention consists essentially of dicarboxylic acid units and diamine units. As the dicarboxylic acid unit, it is necessary to contain a terephthalic acid unit in an amount of 60 mol% or more, preferably 75 mol% or more.
It is more preferable that the content is at least mol%. When the content of the terephthalic acid unit is less than 60 mol%, various properties such as heat resistance and chemical resistance of the obtained polyamide are deteriorated, which is not preferable.

Examples of the dicarboxylic acid unit other than the terephthalic acid unit include malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid and 2,2-
Aliphatic dicarboxylic acids such as dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid; 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid Alicyclic dicarboxylic acids such as acids;
Isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,
7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3
-Phenylenedioxydiacetic acid, diphenic acid, 4,4'-
Examples thereof include units derived from aromatic dicarboxylic acids such as oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid and 4,4'-biphenyldicarboxylic acid, One or more of these may be included. From the viewpoint of heat resistance and the like, it is preferable to include an aromatic dicarboxylic acid unit among the above dicarboxylic acid units. Further, a unit derived from a polyvalent carboxylic acid having three or more functional groups such as trimellitic acid, trimesic acid, and pyromellitic acid can be included within the range where melt molding is possible.

[0012] In the polyamide (A), as the diamine units, it is necessary to contain 2-methyl-1,8-octane diamine units 60 mol% or more, 75
It is preferably contained in an amount of not less than mol%, more preferably not less than 90% by mol. 2-methyl-1,
When the content of the 8-octanediamine unit is less than 60 mol%, the obtained polyamide has moldability, heat resistance,
It is not preferable because physical properties such as chemical resistance are deteriorated.

Examples of the diamine unit other than the 2-methyl-1,8-octanediamine unit include, for example, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine. 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2-methyl-1,
5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl- 1,9 aliphatic diamines such as nonanediamine; cyclohexane diamine, methylcyclohexane diamine, alicyclic diamine such as isophorone diamine; p-phenylenediamine, m- phenylenediamine, xylylenediamine, 4, 4'-diaminodiphenylmethane, 4 , 4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether and other units derived from an aromatic diamine can be mentioned, and one or more of these can be included.

When the diamine unit contains a diamine unit other than the 2-methyl-1,8-octanediamine unit, not only the moldability of the obtained polyamide is extremely excellent but also the crystallinity, The 1,9-nonanediamine unit is preferable because it is also excellent in mechanical properties, chemical resistance, low water absorption and the like. And the smell of polyamide (B)
The diamine unit contains a 2 -methyl-1,8-octanediamine unit and a 1,9-nonanediamine unit, but 60 to 100 mol% of the diamine unit contains 2-methyl-1,8-octanediamine unit and It is preferably composed of 1,9-nonanediamine units, and the molar ratio of 2-methyl-1,8-octanediamine units to 1,9-nonanediamine units is preferably 61:40 to 99: 1, and 7
It is more preferably 0:30 to 98: 2, and 80:
It is more preferably 20 to 95: 5.

In the polyamide (A) of the present invention, it is necessary that 10% or more of the terminal groups of its molecular chain be capped with a terminal capping agent, and 40% or more of the terminal groups are capped. Is preferred, and it is more preferred that 60% or more of the terminal groups are sealed. Further, in the polyamide (B), 10% or more of the terminal groups of its molecular chain are preferably capped with an end cap, more preferably 40% or more of the terminal groups are capped, More preferably, 60% or more of the terminal groups are capped. By sealing the terminal group of the polyamide, a polyamide having more excellent hot water resistance can be obtained.

To determine the terminal blocking ratio, the number of carboxyl group terminals, amino group terminals and terminals blocked by the terminal blocking agent, which are present in the polyamide, are measured, respectively, and calculated by the following formula (1). The terminal sealing rate can be obtained. The number of each terminal group is preferably determined by ¹ H-NMR from the integrated value of the characteristic signal corresponding to each terminal group in terms of accuracy and simplicity. When the characteristic signal of the terminal blocked 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) molecular chain The total number of end groups of the molecular chain is calculated using the relationship of the total number of end groups (eq / g) = 2 / Mn. further,
The number of carboxyl group terminals of the polyamide by titration (eq
/ G) [0.1% benzyl alcohol solution of polyamide
Titration with N sodium hydroxide] and the number of amino group terminals (eq / g) [0.1% polyamide solution in phenol]
The titration ratio with N hydrochloric acid] can be measured, and the terminal sealing rate can be determined by the following formula (1).

End capping rate (%) = [(A−B) ÷ A] × 100 (1) [In the formula, A is the total number of end groups of molecular chain (this is usually 2 of the number of polyamide molecules). And B represents the total number of carboxyl group terminals and amino group terminals.)

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

The monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it has reactivity with an amino group, and examples thereof include acetic acid, propionic acid, butyric acid, valeric acid and caproic acid. Aliphatic monocarboxylic acids such as caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α -Aromatic monocarboxylic acids such as naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and phenylacetic acid,
Alternatively, mention may be made of any mixture thereof.
Among these, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid from the viewpoints of reactivity, stability of the capped end, price, etc. Benzoic acid is particularly preferred.

When the end groups of the polyamide are sealed with a monocarboxylic acid, the number of moles of the diamine component to the dicarboxylic acid component used in the production of the polyamide is slightly increased so that both ends of the polyamide are amino groups. ,
It is advisable to add monocarboxylic acids as endcapping agents.

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).

[0022]

[Chemical 1] (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, and examples thereof include methylamine, ethylamine, propylamine, butylamine, hexylamine and octylamine. , Aliphatic monoamines such as decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine; cycloaliphatic monoamines such as cyclohexylamine and dicyclohexylamine; aniline, toluidine, diphenylamine,
Mention may be made of aromatic monoamines such as naphthylamine or any mixtures thereof. Of these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are particularly preferable from the viewpoints of reactivity, boiling point, stability of capped terminal, price, and the like.

When the end groups of the polyamide are sealed with monoamine, the number of moles of the diamine component to the dicarboxylic acid component used in the production of the polyamide is slightly reduced so that both ends of the polyamide are carboxyl groups. Is preferably added as an end-capping agent.

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

[0026]

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

The amount of the end-capping agent used in the production of polyamide depends on the reactivity, boiling point,
Although it varies depending on the reaction apparatus, reaction conditions, etc., it is usually 0.1 to 15 relative to the total number of moles of dicarboxylic acid and diamine.
It is preferably used in the range of mol%.

The polyamide of the present invention can be produced by a conventionally known method for producing a polyamide, such as a melt polymerization method, a solution polymerization method, or a polymerization method using a reactive extruder. . According to the research conducted by the present inventors, a catalyst and, if necessary, an end-capping agent were first added all at once to a diamine and a dicarboxylic acid to prepare a nylon salt, which was once concentrated at a temperature of 280 ° C. or lower. The intrinsic viscosity [η] at 30 ° C in sulfuric acid is 0.10 to 0.
The polyamide of the present invention can be easily obtained by using a prepolymer of 60 dl / g and further subjecting it to solid phase polymerization or polymerization using a melt extruder. The intrinsic viscosity [η] of the prepolymer is 0.10 to 0.60 dl
Within the range of / g, there is little deviation in the molar balance between the carboxyl group and the amino group and the decrease in the polymerization rate in the post-polymerization stage, and a polyamide having a small molecular weight distribution and excellent performance and moldability can be obtained. . When the final step of the polymerization is carried out by solid phase polymerization, it is preferably carried out under reduced pressure or under the flow of an inert gas, and if the polymerization temperature is in the range of 180 to 280 ° C., the polymerization rate is high 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, it is preferable that the polymerization temperature is 370 ° C. or less, because the polyamide is hardly decomposed and the polyamide can be obtained without deterioration.

As the catalyst that can be used in the production of polyamide, phosphoric acid, phosphorous acid, hypophosphorous acid or their ammonium salts, their metal salts (potassium, sodium, magnesium, vanadium, calcium, Metal salts of zinc, cobalt, manganese, tin, tungsten, germanium, titanium, antimony, etc., and their esters (ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester) , Phenyl ester) and the like. In addition, if necessary, stabilizers such as copper compounds, colorants, ultraviolet absorbers, light stabilizers, antioxidants such as hindered phenols, thios, phosphorus, amines, antistatic agents, brominated Polymer, antimony oxide, flame retardant such as metal hydroxide, crystal nucleating agent, plasticizer, release agent,
Other additives such as lubricants can be added during or after the polycondensation reaction.

The polyamide of the present invention has an intrinsic viscosity [η] measured in concentrated sulfuric acid at 30 ° C. of 0.4 to 3.0 dl / g and 0.6 to 2.0 dl / g. Those of 0.8 to 1.6 dl / g are more preferable. When the intrinsic viscosity [η] of the polyamide is within the above range, not only excellent moldability but also excellent mechanical properties and heat resistance can be obtained.

In the polyamide of the present invention, the intrinsic viscosity [η]
Is in the range of 0.4 to 3.0 dl / g, the intrinsic viscosity [η]
And the melt viscosity (MV) measured at a shear rate of 1000 s ⁻¹ , the relationship represented by the following formula (2) is established. logMV = 1.9 [η] + A (2) (where A is a number that changes with temperature)

In the case of the preferred polyamides according to the invention, 34
A value at 0 ° C is 0.5 to 0.9, and A value at 330 ° C
The difference between the value and the A value at 350 ° C. is 0.1 to 0.6.
On the other hand, in the case of the conventional PA6-T type polyamide, the coefficient of intrinsic viscosity [η] is almost the same as that of the polyamide of the present invention, but the A value at 340 ° C is 1.3 to 1.7, and 330
The difference between the A value at 0 ° C and the A value at 350 ° C is 0.7 to 1.1.
Is. Thus, the preferable molding temperature is 330 to
At 350 ° C., the polyamide of the present invention is
Compared with -T polyamide, the melt viscosity is small even with the same intrinsic viscosity [η], and the change in melt viscosity with the change in molding temperature is also small. Further, the polyamide of the present invention also has a characteristic that the change in melt viscosity during the residence time during molding is small, and the moldability is significantly improved as compared with the conventional PA6-T based polyamide. There is.

The polyamide of the present invention includes polyamide 10
The filler can be blended in an amount of 1 to 200 parts by weight with respect to 0 parts by weight. By blending the filler in such a ratio, a polyamide composition having further improved properties such as mechanical properties and heat distortion temperature can be obtained. The blending ratio of the filler is
The amount is preferably 1 to 150 parts by weight, more preferably 2 to 100 parts by weight, based on 100 parts by weight of the polyamide.

As the filler, conventionally known fillers having various forms such as powder, fiber and cloth can be used.

As the powdery filler, silica, silica alumina, alumina, titanium oxide, zinc oxide, boron nitride, talc, mica, potassium titanate, calcium silicate, magnesium sulfate, aluminum borate, asbestos, glass beads, Examples thereof include carbon black, graphite, molybdenum disulfide, polytetrafluoroethylene and the like. As such a powdery filler, it is usually preferable to use one having an average particle size of 0.1 μm to 200 μm, and more preferably one having an average particle size of 1 μm to 100 μm. Use of these fillers improves the dimensional stability, mechanical properties, heat resistance properties, physicochemical properties, sliding properties and the like of molded articles obtained from the polyamide composition.

As the fibrous filler, polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaphenylene isophthalamide fiber, polymetaphenylene isophthalamide fiber, condensate of diaminodiphenyl ether and terephthalic acid or isophthalic acid. Examples thereof include wholly aromatic polyamide fibers such as fibers obtained from the above, organic fibrous fillers such as wholly aromatic liquid crystal polyester fibers; and inorganic fibrous fillers such as glass fibers, carbon fibers or boron fibers. The use of such a fibrous filler not only improves the sliding characteristics of the molded article obtained from the polyamide composition, but also
It is preferable because mechanical properties, heat resistance properties, physicochemical properties, etc. are improved. As such a fibrous filler, usually,
It is preferable to use one having an average length of 0.05 to 50 mm. Further, it is more preferable to use one having an average length in the range of 1 to 10 mm from the viewpoint that the moldability is good and the sliding properties, heat resistance and mechanical properties of the obtained molded product are further improved. These fibrous fillers may be secondarily processed into a cloth shape or the like.

These fillers may be used either individually or in combination of two or more. In particular, it is preferable to use a combination of the above fibrous filler and powdered filler because it is possible to obtain a composition having more excellent moldability, surface beauty, mechanical properties, and heat resistance. . Further, as these fillers, those surface-treated with a silane coupling agent or a titanium coupling agent may be used. It is preferable to use a filler whose surface is treated with these coupling agents, because the resulting molded article has excellent mechanical properties. Among the silane coupling agents, it is more preferable to use an aminosilane coupling agent because the resulting molded product has particularly excellent mechanical properties.

The method of blending the above-mentioned filler with the polyamide is not particularly limited, but for example, a method of adding during the polycondensation reaction of the polyamide, a method of dry blending, a method of melt-kneading using an extruder. And so on.

Using the polyamide or polyamide composition prepared as described above, a molded article having a desired shape can be formed by a usual melt molding method such as compression molding method, injection molding method, extrusion molding method or blow molding method. Can be manufactured.

For example, the polyamide or polyamide composition of the present invention is melted in a cylinder of an injection molding machine in which the cylinder temperature is adjusted to 300 to 350 ° C., and introduced (injected) into a mold having a predetermined shape. By doing so, a molded product can be manufactured. In addition, the resin can be melted in the extruder adjusted to the cylinder temperature and spun from the spinneret nozzle to produce the fiber. Further, the film can be produced by melting the resin in the extruder adjusted to the cylinder temperature and extruding the resin from the T die. Further, a molded product such as a film or a bottle can be obtained by inflation molding or blow molding.

The molded product as described above can be used in a state where the surface is further coated with a paint, a metal layer, another kind of polymer or the like.

Molded articles made of the polyamide or polyamide composition of the present invention include, for example, electric tools, general industrial parts, mechanical parts such as gears and cams, connectors, switches, relays, MIDs, printed wiring boards, electronic parts. Examples thereof include electronic parts such as housings, films, sheets, fibers, and various shaped articles. In particular, it can be suitably used for molded articles for automobiles, for example, interior / exterior parts of automobiles, parts in the engine room of automobiles, and electrical components of automobiles.

[0043]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following examples, the end-capping rate of polyamide, intrinsic viscosity, melting point, melt viscosity; heat distortion temperature of molded article,
Tensile strength, water absorption dimensional change rate, heating dimensional change rate, chemical resistance, hot water resistance, surface beauty, water absorption rate, solder heat resistance, alcohol resistance; fiber strength, elastic modulus, water absorption rate, chemical resistance, It was measured or evaluated by the following method.

End capping ratio : ¹ H-NMR (500 MH
z, measured in deuterated trifluoroacetic acid at 50 ° C.) to measure the number of carboxyl group end, amino group end and capping end respectively from the integrated value of the characteristic signal for each end group, The terminal sealing rate was calculated from (1). The chemical shift values of typical signals used for measurement are shown below.

[0045]

[Table 1]

Intrinsic viscosity [η] : in concentrated sulfuric acid at 30 ° C.
The intrinsic viscosity (ηinh) of the samples having the concentrations of 0.05, 0.1, 0.2 and 0.4 g / dl was measured, and the value obtained by extrapolating this to the concentration of 0 was defined as the intrinsic viscosity [η]. ηinh = [ln (t ₁ / t ₀ )] / c [wherein, ηinh is an intrinsic viscosity (dl / g), t ₀ is a solvent flowing time (seconds), t ₁ is a sample solution flowing time (seconds) , C
Represents the concentration (g / dl) of the sample in the solution. ]

Melting point : Differential scanning calorimeter ("D" manufactured by METTLER CORPORATION)
SC30 ") to raise the temperature of the sample at a rate of 100 ° C / min to completely melt the sample, and then 5 at a rate of temperature decrease of 10 ° C / min.
The temperature at the position of the endothermic peak that appeared when the temperature was cooled to 0 ° C. and the temperature was raised again at a rate of 10 ° C./min, was taken as the melting point.

Melt viscosity : KAYNESS "capillary rheometer, GALAXYV MODEL 805
2 "(die diameter 1 mm, L / D = 10)
Melt viscosity at 0 ° C. at a shear rate of 1000 s ⁻¹ (p
oise) was measured and used as an index of moldability.

Heat distortion temperature : 127 × 14 × 6.4 mm injection-molded article was prepared according to ASTM D648.
It was measured with a load of 6 kg / cm ² .

Tensile strength : Measured according to JIS K 7113 using a JIS No. 1 dumbbell type injection molded product.

Water absorption dimensional change rate : An injection molded article of 80 × 80 × 3 mm was immersed in water at 23 ° C. for 48 hours and then taken out, and the dimensional change rate of the molded article before and after immersion (in the machine axis direction) ( %) Was measured.

Rate of dimensional change by heating : An injection-molded article of 80 × 80 × 3 mm was heated in a gear oven at 200 ° C. for 2 hours and cooled in a vacuum desiccator to room temperature over 1 hour. The dimensional change rate (%) in the MD direction (machine axis direction) of the molded product before and after the heat treatment was measured.

Chemical resistance : JIS No. 2 dumbbell type injection-molded products were placed in gasoline or engine oil at 120 ° C for 7 days.
Soaked for a day. Measure the tensile strength of the molded product before and after immersion,
The retention rate (%) of tensile strength was determined.

Hot water resistance : JIS No. 2 dumbbell type injection molded product was steam treated in a pressure resistant autoclave (120
℃, 2 atmospheres for 120 hours), then the sample at 120 ℃
And dried in vacuum for 120 hours. The tensile strength of the molded product before and after the treatment was measured to determine the retention rate (%) of the tensile strength.

Surface beauty : The polyamide composition was injection molded at a cylinder temperature of 340 ° C. to obtain 80 × 80 ×.
The surface of the 3 mm injection-molded article was visually observed.

Water absorption : An injection-molded article of 80 × 80 × 3 mm was immersed in water at 23 ° C. for 24 hours. The water absorption rate (%) was determined from the weight change of the molded product before and after immersion.

Solder heat resistance : 40 × 40 × 1 mm injection-molded product was left in a desiccator at 23 ° C. and 50% RH for 96 hours, and then the injection-molded product was floated in a solder bath at a temperature of 260 ° C. for 60 seconds. After that, the state of the surface was observed. When no change was observed on the surface of the injection-molded piece, it was marked with O, and when blisters were found, it was marked with X.

Alcohol resistance : A JIS No. 2 dumbbell type injection molded article was immersed in a 50% ethylene glycol aqueous solution in a pressure resistant autoclave and treated at a temperature of 130 ° C. for 100 hours. The tensile strength of the molded product before and after the treatment was measured to determine the retention rate (%) of the tensile strength.

Fiber strength and elastic modulus : JIS L 101
It measured according to 3.

Water absorption of fiber : About 2 g of drawn yarn was dried in a vacuum dryer (60 ° C. for 6 hours) and then conditioned (23 ° C.,
It was left for 1 week in a desiccator (95% RH).
The water absorption rate (%) was determined from the weight change before and after humidity control.

Chemical resistance of fiber : The drawn yarn was immersed in various chemicals (10% hydrochloric acid, methanol) at 70 ° C. for 10 hours.
The strength of the fiber before and after the immersion was measured to determine the strength retention rate (%).

Reference Example 1 3272.9 g (19.7 mol) of terephthalic acid, 3165.8 g of 2-methyl-1,8-octanediamine (2
0.0 mol), 73.27 g (0.60 mol) of benzoic acid, 6.5 g of sodium hypophosphite monohydrate (0.1% by weight based on the raw material) and 2.2 liters of distilled water. It was placed in an autoclave having a volume of 20 liters and purged with nitrogen. After stirring at 100 ° C for 30 minutes, the internal temperature was raised to 210 ° C over 2 hours. At this time, the pressure in the autoclave was increased to 22 kg / cm ² . After continuing the reaction for 1 hour as it is, the temperature was raised to 230 ° C., and then the temperature was kept at 230 ° C. for 2 hours, and steam was gradually discharged to a pressure of 22 kg / c.
The reaction was carried out while maintaining m ² . Next, the pressure is reduced to 10 kg / cm ² over 30 minutes, and the reaction is continued for 1 hour.
A prepolymer having an intrinsic viscosity [η] of 0.25 dl / g was obtained. This was dried at a temperature of 100 ° C. under reduced pressure for 12 hours and then pulverized to a size of 2 mm or less. This is solid-state polymerized under conditions of a temperature of 230 ° C. and a pressure of 0.1 mmHg for 10 hours, and has a melting point of 285 ° C. and an intrinsic viscosity [η] of 1.30 d.
A white polyamide having a l / g and a terminal sealing rate of 91% was obtained.

Reference Examples 2 to 10 Except that the dicarboxylic acid component, diamine component and end-capping agent (benzoic acid) were used in the proportions shown in Table 2 below,
A polyamide was obtained by the same procedure as in Reference Example 1. The intrinsic viscosity [η], end capping ratio and melting point of the obtained polyamide are shown together in Table 2 below.

[0064]

[Table 2]

Examples 1 to 6 and Comparative Examples 1 to 4 The polyamides obtained in Reference Examples 1 to 10 were used, using an injection molding machine "FS80S12ASE" manufactured by NISSEI PLASTIC INDUSTRIAL CO., LTD. Injection molding was performed by setting the mold temperature to 150 ° C and the mold temperature to -40 ° C higher. Table 3 below shows the results of evaluation of the obtained molded products.

[0066]

[Table 3]

Examples 7 to 9 and Comparative Examples 5 and 6 Uniaxial extruder "UT-40" manufactured by Plastic Engineering Laboratory
"H", and the cylinder temperature is 20
A polyamide composition was obtained by extruding the filler and polyamide described in Table 4 below in a molten state by setting the temperature to be higher by -40 ° C. The obtained polyamide composition was applied to an injection molding machine "FS80S12A" manufactured by Nissei Plastic Industry Co., Ltd.
SE ”, and the cylinder temperature is 2
Injection molding was performed by setting the mold temperature to 150 ° C and the temperature higher from 0 to 40 ° C. Table 4 below shows the results of evaluation of the obtained molded products.

[0068]

[Table 4]

Example 10, Comparative Examples 7 and 8 Using "Flow Tester CFT-500" (base: 0.3 mmφ) manufactured by Shimadzu Corporation, the polyamides shown in Table 5 below were discharged at the spinning temperatures shown in Table 5. A monofilament was produced by spinning under conditions such that the ratio of the speed to the winding speed (draft ratio) was around 15. This was continuously stretched at 200 ° C. at a maximum stretch ratio of 0.9 to 0.95. Here, the maximum draw ratio is the draw ratio of the yarn when the first roller speed is fixed at 50 m / min and the second roller speed is adjusted and the yarn is not broken for 5 minutes. The evaluation results of the obtained fibers are shown in Table 5 below.
Shown in.

[0070]

[Table 5]

[0071]

EFFECT OF THE INVENTION The polyamide and the polyamide composition of the present invention have excellent moldability and excellent hot water resistance, surface beauty, heat resistance, mechanical properties, low water absorption and chemical resistance. , Molded articles of various shapes such as parts for engineering use, fibers, films, sheets, bottles obtained from these polyamides and polyamide compositions should be suitably used for applications such as industrial materials, industrial materials and household products. You can

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI D01F 6/60 361 D01F 6/60 361 (56) Reference JP-A-7-53715 (JP, A) Patent 3242781 (JP, B2) ) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 69/00-69/50

Claims (6)

(57) [Claims] 1. 60 to 100 mol% of dicarboxylic acid units
Is a terephthalic acid unit, and is a diamine unit of 60 to 1
A polyamide having 00 mol% of 2-methyl-1,8-octanediamine units, having an intrinsic viscosity [η] measured at 30 ° C. in concentrated sulfuric acid of 0.4 to 3.0 dl / g and having its terminal end. A polyamide in which 10% or more of the base is sealed. 2. 60 to 100 mol% of dicarboxylic acid units
Is a terephthalic acid unit, and is a diamine unit of 60 to 1
00 mol% consists of 2-methyl-1,8-octanediamine units and 1,9-nonanediamine units, and 2
A polyamide having a molar ratio of -methyl-1,8-octanediamine unit and 1,9-nonanediamine unit of 61:39 to 99: 1 mol% and having an intrinsic viscosity [η ] Is 0.4-3.0 dl / g. 3. The polyamide 10 according to claim 1 or 2.
A polyamide composition comprising 1 to 200 parts by weight of a filler in 0 parts by weight. 4. A molded article made of the polyamide according to claim 1 or 2. 5. A molded article made of the polyamide composition according to claim 3. 6. A fiber comprising the polyamide according to claim 1 or 2.