JPH11315206A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyamide resin compsn. having such additional characteristics as strength under high humidity and good external surface appear ance, by adding to a polyamide resin a liquid crystalline resin having a carboxylic end group conc. of more than a specified quantity. SOLUTION: As the polyamide resin, nylon 6, 66, 610, 66/6T, 6T/6I, 6I/M5T, etc., are good examples. The polyamide resin has an amino end group conc. of pref. from 30×10<-6> equivalent/g to 1,000×10<-6> equivalent/g of the upper limit. The liquid crystalline resin is such a resin capable of forming an anisotropic melt phase as a liquid crystalline polyester, a liquid crystalline polyesteramide, etc., comprising a structural unit of an aromatic oxycarbonyl unit, an aromatic dioxy unit, ethylenedioxy unit and so on and also as having a carboxylic end group concn. of 75×10<-6> equivalent/g or more. The liquid crystalline resin used is added in an amt. of 0.01-10 pts.wt. to 100 pts.wt. of the polyamide resin. A blended is carried out by melt kneading.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyamide resin composition having excellent mechanical properties, surface appearance, moisture resistance, and chemical resistance, and particularly excellent rigidity and dimensional stability when placed in a high humidity environment. . More specifically, a polyamide resin composition that maintains excellent toughness, which is a characteristic of polyamide resin, and has high humidity resistance and extremely high dimensional stability with extremely small reduction in rigidity even after long-term exposure to a high humidity environment. The present invention relates to a polyamide resin composition which is used in molded articles, films, and textiles by making full use of its properties, and is particularly suitably used for automobiles and for resin connectors for circuit connection of electric / electronic devices.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for higher performance of plastics, and a number of polymers having various new properties have been developed and marketed. Among them, a polymer is characterized by a parallel arrangement of molecular chains. Optically anisotropic liquid crystalline polymers are attracting attention because of their excellent fluidity and mechanical properties.In particular, because of their high strength and rigidity, demand for small molded products in the fields of electric / electronics and office equipment is increasing. It is getting bigger.

Further, polyamide resins represented by nylon 6 and nylon 66 are widely used in the fields of automobiles, electric and electronic fields, and other fields of construction and miscellaneous goods, utilizing the excellent properties of engineering plastics. However, although the liquid crystalline polymer has high rigidity, it cannot be said that the toughness is sufficient compared to polyamide resin and the like.
Further, the price is higher than that of polyamide, polybutylene terephthalate, etc., so that it is currently limited to applications requiring high heat resistance and dimensional accuracy.

[0004] On the other hand, although polyamide resin has high toughness, its rigidity is reduced in use under high humidity, and when it is used for, for example, a connector, the connection function is impaired or its dimensional change is large depending on the use environment. There are problems such as poor stability, and improvement has been desired.

Attention has been paid to blends of a liquid crystalline resin and a thermoplastic resin in order to solve the drawbacks of both, and Japanese Patent Application Laid-Open Nos. 56-115357, 3-54222, and 9-12875 disclose. Publications and the like are disclosed.

[0006]

However, even if both polymers are simply blended, the compatibility is not sufficient, so that there is no significant improvement in physical properties, especially no improvement in rigidity under high humidity. Has the disadvantage of impairing toughness, which is a characteristic of In addition, it was found that foreign matters were easily generated due to poor compatibility, and the impact strength was reduced in molded products, and breakage in films or yarn breakage in yarn frequently occurred.

Therefore, the present invention solves the above-mentioned problems, and can be processed at the processing temperature of a conventional polyamide resin, and can newly provide rigidity and toughness under high humidity without deteriorating the conventional properties of the polyamide resin. Another object of the present invention is to obtain a polyamide resin composition in which properties such as chemical resistance, dimensional accuracy, and good surface appearance of the obtained molded article are added to a polyamide resin.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention relates to (1) (A) 100 parts by weight of a polyamide resin, and (B) a carboxyl end group concentration of 75 × 10 ^−6.
A polyamide resin composition obtained by adding 0.01 to 10 parts by weight of a liquid crystalline resin having an equivalent weight / g or more. 3
The polyamide resin composition according to the above (1), wherein (3) the polyamide resin composition is added at 40 ° C.
After immersion treatment in water for 10 days, ASTM method D790 (thickness 1 /
The flexural modulus measured at 8 inches) is improved by 10% or more compared to the flexural modulus similarly measured using the same polyamide resin (composition) except that the liquid crystalline resin (B) is not included. (4) The liquid crystal resin composition according to any one of the above (1) to (3), wherein the liquid crystal resin (B) contains an ethylenedioxy unit. A polyamide resin composition, (5) a molded article composed of the polyamide resin composition according to any one of the above (1) to (4), (6) a polyamide resin composition according to any one of the above (1) to (4) And (7) a fiber comprising the polyamide resin composition according to any one of the above (1) to (4).

[0009]

Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

The polyamide resin (A) used in the present invention
"Nylon" is a nylon made mainly of amino acids, lactams or diamines and dicarboxylic acids. Representative examples of the raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, lactams such as ε-aminocaprolactam, ω-laurolactam, tetramethylenediamine, Hexamethylenediamine, 2-methylpentamethylenediamine, nonanemethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,
2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (amino Methyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-
Aminocyclohexyl) methane, bis (3-methyl-4)
-Aminocyclohexyl) methane, 2,2-bis (4-
Aliphatic, alicyclic, aromatic diamines such as aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, and adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid;
Aliphatic, alicyclic, aromatic, such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid In the present invention, nylon homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.

In the present invention, a particularly useful nylon resin is a nylon resin having a melting point of 200 ° C. or more and excellent in heat resistance and strength. Specific examples include polycaproamide (nylon 6) and polyhexamethylene. Adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polynonamethylene methylene terephthalamide (nylon 9T), Polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66
/ 6T), polyhexamethylene terephthalamide / polycaproamide copolymer (nylon 6T / 6), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polydodecamide / polyhexamethylene terephthalamide copolymer (Nylon 12 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 /
6T / 6I), polyhexamethylene terephthalamide /
Polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / poly (2-methylpentamethylene terephthalamide) copolymer (nylon 6T / M5T), polyxylene adipamide (nylon XD6) and mixtures thereof Or a copolymer.

Particularly preferred are nylon 6, nylon 66, nylon 610, nylon 46, nylon 9T, nylon 6/66 copolymer, nylon 6
/ 12 copolymer, nylon 6T / 6 copolymer, nylon 66 / 6T copolymer, nylon 6T / 6I copolymer, nylon 66 / 6T / 6I, nylon 12/6
Examples of T, Nylon 6T / M5T copolymers and the like can be given, and it is also practically preferable to use these polyamide resins as a mixture depending on required properties such as moldability, heat resistance and low water absorption.

The degree of polymerization of the polyamide resin (A) is not particularly limited, and the relative viscosity measured at 25 ° C. in a 1% concentrated sulfuric acid solution is in the range of 1.5 to 5.0, especially 2.0. ~
Those having a range of 4.0 are preferred.

The amino terminal group concentration of the polyamide resin (A) used in the present invention is not particularly limited, but is preferably 30 × 10 ⁻⁶ equivalent / g or more, more preferably 35 × 10 ⁻⁶ equivalent / g or more. Particularly preferred is 45 × 10 ⁻⁶ equivalent / g or more. The upper limit is not particularly limited, but is preferably 1000 × 10 ⁻⁶ equivalent / g or less in view of the thermal stability of the polyamide resin.

The method for measuring the amino terminal group concentration of the polyamide resin (A) of the present invention is not particularly limited. For example, 20 mg of a sample is weighed in an NMR sample tube, and 0.6 ml of a solvent (hexafluoroisopropanol-d2) is added. After dissolution, measurement is performed using an NMR apparatus with an observation frequency of 599.9 MHz.

The liquid crystalline resin (B) of the present invention is a resin capable of forming an anisotropic molten phase, for example, an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic dicarbonyl unit, an ethylenedioxy unit and the like. A liquid crystalline polyester comprising a structural unit selected from and forming an anisotropic molten phase, or a structural unit selected from the above structural unit and an aromatic iminocarbonyl unit, an aromatic diimino unit, an aromatic iminooxy unit, etc. And a liquid crystalline polyesteramide or the like which forms an anisotropic molten phase and has a carboxyl terminal group concentration of 75 × 10 ⁻⁶ equivalent / g or more.

Examples of the aromatic oxycarbonyl unit include, for example, p-hydroxybenzoic acid, 6-hydroxy-2-
Examples of the structural unit and aromatic dioxy unit generated from naphthoic acid and the like include 4,4′-dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, t -Structural units formed from -butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl ether, and aromatics Examples of the dicarbonyl unit include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and 1,2-bis (phenoxy) ethane-4,4′-
Dicarboxylic acid, 1,2-bis (2-chlorophenoxy)
Structural units formed from ethane-4,4′-dicarboxylic acid and 4,4 ′ diphenyl ether dicarboxylic acid,
Examples of the aromatic iminooxy unit include a structural unit generated from 4-aminophenol and the like.

Specific examples of the liquid crystalline polyester include p
Liquid crystalline polyester comprising a structural unit formed from -hydroxybenzoic acid, a structural unit formed from 6-hydroxy-2-naphthoic acid, a structural unit formed from an aromatic dihydroxy compound and / or an aliphatic dicarboxylic acid, p
A structural unit formed from hydroxybenzoic acid, 4,4 ′
Liquid crystalline polyester comprising a structural unit formed from dihydroxybiphenyl, a structural unit formed from terephthalic acid and adipic acid, a structural unit formed from p-hydroxybenzoic acid, a structural unit formed from ethylene glycol, from terephthalic acid and isophthalic acid Liquid crystalline polyester composed of the generated structural units, structural unit generated from p-hydroxybenzoic acid, structural unit generated from ethylene glycol, structural unit generated from 4,4′-dihydroxybiphenyl, terephthalic acid and / or sebacic acid Liquid crystalline polyester composed of structural units produced from the produced structural units, structural units produced from p-hydroxybenzoic acid, structural units produced from ethylene glycol, structural units produced from aromatic dihydroxy compounds, terephthalic acid Liquid crystalline polyesters formed from one or more aromatic dicarboxylic acids such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, structural units formed from p-hydroxybenzoic acid, structural units formed from ethylene glycol, and terephthalic acid And liquid crystalline polyesters composed of the above structural units.

Preferred examples of the liquid crystalline polyester forming the anisotropic molten phase include the following (I), (II) and (III)
And a liquid crystalline polyester comprising the structural units of (IV),
Or, a liquid crystalline polyester comprising the structural units of (I), (III) and (IV) may be mentioned.

[0020]

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(Where R ₁ in the formula is

[0022]

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R ₂ represents one or more groups selected from

[0024]

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And at least one group selected from In the formula, X represents a hydrogen atom or a chlorine atom. )

The structural unit (I) is a structural unit formed from p-hydroxybenzoic acid, and the structural unit (II) is 4,
4'-dihydroxybiphenyl, 3,3 ', 5,5'-
Tetramethyl-4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene,
A structural unit generated from an aromatic dihydroxy compound selected from 2,2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether, a structural unit (III) is a structural unit generated from ethylene glycol, The structural unit (IV) is terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, And structural units formed from aromatic dicarboxylic acids selected from -bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,4'-diphenyletherdicarboxylic acid.

Of these, R ₁ is

[0028]

Embedded image

Is preferred. Also, as R ₂

[0030]

Embedded image

Is particularly preferred.

The liquid crystalline polyester which can be preferably used in the present invention is a copolymer comprising the above structural units (I), (III) and (IV) and / or the above structural units (I), (II) and (III) , (I
V) is a copolymer comprising the above structural units (I), (II),
The copolymerization amount of (III) and (IV) is optional. However, in order to exhibit the characteristics of the present invention, the following copolymerization amount is preferable.

That is, the structural units (I), (III) and (IV)
In the case of a copolymer consisting of (I), the structural unit (I) is (I), (II)
30-80 mol% is preferable with respect to the total of I) and (IV),
45-75 mol% is more preferred.

The structural units (I), (II), (III) and (I)
In the case of a copolymer consisting of V), the above structural unit (I) and
The total of (II) is preferably from 30 to 95 mol%, more preferably from 40 to 85 mol%, based on the total of the structural units (I), (II) and (III). Further, the structural unit (III) is the structural unit (I), (I
It is preferably from 70 to 10 mol%, more preferably from 60 to 15 mol%, based on the total of I) and (III). The molar ratio [(I) / (II)] of the structural units (I) and (II) is preferably 75 /
25 to 95/5, more preferably 78/22 to 9
3/7. Further, it is preferable that the structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III).

The term "substantially equimolar" means that the units constituting the polymer main chain excluding the terminal are equimolar, but the units constituting the terminal are not necessarily equimolar. This is because when the carboxy terminal group of the polyester is in a specific range, the ratio of the unit derived from the dicarboxylic acid at the polymer terminal is not completely equal to the ratio of the unit derived from the dihydroxy compound at the polymer terminal.

As the liquid crystalline polyesteramide,
Polyesteramides that form an anisotropic molten phase containing p-iminophenoxy units formed from p-aminophenol in addition to the structural units (I) to (IV) are preferred.

The liquid crystalline polyesters and liquid crystalline polyesteramides which can be preferably used include, in addition to the components constituting the structural units (I) to (IV), 3,3'-diphenyldicarboxylic acid and 2,2'-diphenyl Aromatic dicarboxylic acids such as dicarboxylic acid, adipic acid, azelaic acid,
Aliphatic dicarboxylic acids such as sebacic acid and dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylsulfone, 4,4'- Dihydroxydiphenyl sulfide,
Aromatic diols such as 4,4'-dihydroxybenzophenone and 3,4'-dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, Liquid crystalline properties of aliphatic, alicyclic diols such as 1,4-cyclohexanedimethanol, aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, and p-aminobenzoic acid are not impaired. Can be further copolymerized in the range described above.

The basic method for producing the liquid crystalline resin used in the present invention is not particularly limited, and can be basically produced according to a known polyester polycondensation method.

For example, in the production of the liquid crystal polyester, the following production method is preferably mentioned. (1) Polyester obtained from only the components excluding p-hydroxybenzoic acid and p-acetoxybenzoic acid are heated and melted in a dry nitrogen stream, a copolymerized polyester fragment is generated by an acidolysis reaction, and then the pressure is reduced to increase the viscosity. (2) p-acetoxybenzoic acid and diacylated aromatic dihydroxy compounds such as 4,4′-diacetoxybiphenyl and diacetoxybenzene, and 2,6-naphthalenedicarboxylic acid, terephthalic acid, A method for producing a liquid crystal polyester from an aromatic dicarboxylic acid such as isophthalic acid by a deacetic acid condensation polymerization reaction. (3) Reaction of aromatic dihydroxy compounds such as p-hydroxybenzoic acid and 4,4'-dihydroxybiphenyl and hydroquinone with aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, and acetic anhydride. A phenolic hydroxyl group is acylated, and then a liquid crystal polyester is produced by a deacetic acid polycondensation reaction. (4) Phenyl esters of p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4'-dihydroxybiphenyl and hydroquinone and diphenyl esters of aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid Of producing liquid crystalline polyester from phenol by a dephenol polycondensation reaction. (5) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and an aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, or isophthalic acid to form diphenyl esters, respectively.
A method in which an aromatic dihydroxy compound such as 4,4'-dihydroxybiphenyl or hydroquinone is added, and a liquid crystal polyester is produced by a phenol-free polycondensation reaction. (6) In the presence of bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as a polymer or oligomer of a polyester such as polyethylene terephthalate or an aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate, the liquid crystal is prepared by the method of (2) or (3). A method for producing polyester.

Although the polycondensation reaction of the liquid crystalline resin proceeds without a catalyst, metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and metal magnesium can also be used.

The liquid crystalline resin (B) used in the present invention must have a carboxyl terminal group concentration of 75 × 10 ⁻⁶ equivalent / g or more, preferably 100 × 10 ⁻⁶ equivalent / g.
The amount is more preferably 120 × 10 ⁻⁶ equivalent / g or more. If the carboxyl end group concentration is too low, the compatibility with the polyamide is poor and the effect as an improver cannot be exhibited.
The upper limit is not particularly limited, but is preferably 1000 × 10 ⁻⁶ equivalent / g or less in view of the thermal stability of the liquid crystalline resin.

The preferred methods for controlling the amount of terminal carboxyl groups of the liquid crystalline resin (B) used in the present invention to 75 × 10 ⁻⁶ equivalent / g or more are (1) to (6).
The acid component is added in an excessive amount in the range of 0.01 to 1 mol% by the method of (1) or the polymerization degree is set higher than the desired degree of polymerization by the method of (1) to (6), and water or water is added to the obtained polymer. The glycol component is added in an amount of 0.01 to 5 parts by weight, and the kneader, a single-screw or twin-screw extruder is used to add 180 to 38 parts.
A method of forming a melt pellet at a temperature of 0 ° C. is exemplified.

The method for measuring the carboxyl terminal group concentration of the liquid crystalline resin (B) of the present invention is not particularly limited.
The sample is dissolved in a solvent such as dioxane and titrated with a potassium hydroxide solution using cresol red as an indicator, or dissolved in a solvent such as pentafluoroisopropanol, pentafluorophenol / chloroform = 35/65 (weight ratio) and analyzed by NMR. Measurements are made, the latter being preferred.

The number average molecular weight of the liquid crystalline resin (B) of the present invention is not particularly limited, but is preferably 15,000 or less.
400 to 10000 is more preferable, and especially 500 to 50
00 is more preferred. The molecular weight can be measured by a GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which the liquid crystalline resin is soluble.

Some liquid crystal resins (B) used in the present invention can measure the logarithmic viscosity in pentafluorophenol.
It is preferably 0.03 dl / g or more as measured at 0 ° C.
0.05 to 10.0 dl / g is particularly preferred.

The melting point of the liquid crystalline resin (B) used in the present invention is not particularly limited, but is preferably not more than the melting point of the polyamide resin to be mixed so as not to impair the toughness of the polyamide resin (A). C. or lower is more preferable. Here, the melting point (Tm) refers to an endothermic peak temperature (Tm1) observed when a polymer that has been polymerized is measured from room temperature under a heating condition of 20 ° C./min in differential calorimetry.
), After holding at a temperature of Tm1 + 20 ° C. for 5 minutes, and once cooling to room temperature under a cooling condition of 20 ° C./min,
It refers to the endothermic peak temperature (Tm2) observed when the temperature is measured again at a temperature rising condition of 20 ° C./min.

The compounding amount of the liquid crystalline resin (B) of the present invention to the polyamide resin (A) is such that the inherent properties of the polyamide resin are not impaired, and the polyamide resin is newly placed in an environment of chemical resistance and high humidity. 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the polyamide resin (A), from the viewpoint of imparting properties such as rigidity and dimensional stability of the resulting molded article and good surface appearance of the obtained molded article. Parts by weight, more preferably 0.1
-5 parts by weight.

The method of blending the polyamide resin (A) and the liquid crystalline resin (B) of the present invention is not particularly limited, but usually it is preferable to perform melt kneading, and a known method can be used for melt kneading. For example, the composition can be melt-kneaded at a temperature of 180 to 380 ° C. using a Banbury mixer, a rubber roll machine, a kneader, a single-screw or twin-screw extruder, or the like to obtain a composition.

In the present invention, a filler can be used for imparting mechanical strength and other properties to the polyamide resin composition. The filler is not particularly limited, but may be a fibrous, plate-like, powder-like, Granular or other fillers can be used. Specifically, for example, glass fiber, PAN-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia Fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker,
Fibrous such as aluminum borate whisker, silicon nitride whisker, whisker-like filler, mica, talc,
Powdered form of kaolin, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastenite, titanium oxide, zinc oxide, calcium polyphosphate, graphite, etc.
Granular or plate-like fillers may be mentioned. Among the above fillers, glass fibers are preferably used. The type of the glass fiber is not particularly limited as long as it is generally used for reinforcing a resin. For example, a long fiber type or a short fiber type chopped strand, a milled fiber or the like can be used. Further, two or more of the above fillers can be used in combination. The filler used in the present invention has a surface with a known coupling agent (for example,
(A silane-based coupling agent, a titanate-based coupling agent, etc.) and other surface treatment agents.

The glass fiber may be covered or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

The above filler is added in an amount of 0.1 part by weight based on 100 parts by weight of a polyamide resin composition obtained by adding a liquid crystal resin (B) to a polyamide resin (A) (that is, a total of (A) and (B)). The amount is preferably 5 to 300 parts by weight, more preferably 10 to 250 parts by weight, and particularly preferably 20 to 150 parts by weight.

Further, the polyamide resin composition of the present invention contains an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and the like) and an ultraviolet absorber (for example, resorcinol, salicylate, Anti-coloring agents such as benzotriazole and benzophenone), phosphites and hypophosphites, lubricants and release agents (montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax, etc.) ),
Colorants including dyes (eg, nigrosine) and pigments (eg, cadmium sulfide, phthalocyanine, etc.),
Carbon black, a nucleating agent, a plasticizer, a flame retardant (for example, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, red phosphorus, magnesium hydroxide, melamine and cyanuric acid or a salt thereof) as a conductive agent or a coloring agent, Ordinary additives such as a flame retardant aid (antimony compound, fluorine resin, silicone resin, etc.) and antistatic agent can be added to further impart predetermined characteristics.

Further, as the need for further property improvement is required, olefin polymers such as polypropylene, polyethylene and polystyrene, acid-modified olefin polymers such as maleic anhydride, ethylene / propylene copolymers,
Ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer and 1 selected from ethylene / propylene-g-maleic anhydride copolymer, olefin copolymer such as ABS, and elastomer such as polyester polyether elastomer and polyester polyester elastomer
Species or mixtures of two or more can be added to further impart predetermined properties.

The method of adding these is preferably melt kneading, and a known method can be used for melt kneading. For example, Banbury mixer, rubber roll machine,
Using a kneader, single screw or twin screw extruder,
The composition can be melt-kneaded at a temperature of about 380 ° C to obtain a composition. In this case, even in a batch kneading method of the polyamide resin (A), the liquid crystal resin (B), and the filler, the polyamide resin (A) and the liquid crystal resin (B) are once kneaded, and then the filler and other additives are added. Either kneading method may be used.

In many cases, the polyamide resin composition thus obtained is immersed in water at 40 ° C. for 10 days to absorb water, and has a flexural modulus measured by ASTM method D790 (1/8 inch thickness) of the liquid crystalline resin (B). Can be improved by 10% or more as compared to the flexural modulus measured in the same manner using the same polyamide resin (composition) except that the resin does not contain the same.

The molding method for molding the molded article may be a usual molding method (injection molding, extrusion molding, blow molding, press molding, injection press molding, etc.) to form a three-dimensional molded article, sheet, container pipe or the like. It can be processed, in particular, into a molded article having a portion having a thickness of 1.5 mm or less by injection molding or an injection press, more preferably to a molded product having a portion having a thickness of 1.2 mm or less, still more preferably a portion having a thickness of 1.0 mm or less. Is effective for molded articles having The film can be formed by an existing method such as a T-die method or a ring die method, and may be an unstretched or unoriented film. It is preferable in terms of modulus, toughness, heat resistance and the like. These films may be a single film, or another film such as polyester, polyolefin, polyamide, polyvinylidene chloride, or acrylic polymer may be laminated thereon. Furthermore, the spinning method for spinning the fiber may be any of known methods such as a two-step method of spinning and drawing, a spin draw method in which the steps are continuously performed, and a draw spin method in which high-speed spinning is performed and the drawing step is omitted. May be used, spinning, the presence or absence of a method of distributing the degree of orientation in the stretching process and relaxation treatment,
The temperature step and the like do not need to be particularly limited. Needless to say, the total fineness, the number of filaments, and the cross-sectional shape are not limited.

The polyamide resin composition of the present invention does not impair the inherent properties of the polyamide resin (A), and has new chemical resistance and rigidity and dimensional stability when placed in a high humidity environment. Utilizing characteristics such as good surface appearance of molded products, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, and various terminals Board, transformer, plug, printed wiring board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FDD carriage, FDD chassis, HDD parts, motor brush holder, Parabolic antenna, computer Electrical and electronic parts typified by over-related parts; VTR parts, TV parts, iron,
Home and office represented by hair dryers, rice cooker parts, microwave parts, audio parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, washing jigs, oilless bearings, stern bearings, underwater bearings, etc., various bearings, motor parts, lighters, typewriters, etc. Related parts, optical equipment such as microscopes, binoculars, cameras, clocks, etc., precision machinery related parts; alternator terminals, alternator connectors, IC regulators, various valves such as exhaust gas valves, fuel related exhaust systems, etc. Various intake systems , Air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, parts for ignition coil, throttle position sensor, crankshaft position sensor , Air flow meter, Brake butt wear sensor, Thermostat base for air conditioner, Heating hot air flow control valve, Brush holder for radiator motor, Water pump impeller, Turbine vane, Wiper motor related parts, Distributor, Starter switch, Starter relay , Transmission wire harness, window washer nozzle, air conditioner panel switch Ji substrate, coil of magnetic valve for fuel supply, connectors for fuses, horn terminals, insulating plates for electric equipment, step motor rotor,
Lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, automotive and vehicle-related parts such as ignition device cases, and other various applications, especially connectors that require rigidity when absorbing water When used as a film, it is useful as a film for magnetic recording media, a film for photography, a film for capacitors, a film for electrical insulation, a film for packaging, a film for drafting, a film for ribbons, and when used as a fiber. Is useful in a wide variety of fields such as rubber reinforcements such as tire cords, conveyor belts, hoses, ropes, cables, speaker cones, tension members, safety clothing, bulletproof vests, space suits, and submarine workwear.

[0058]

EXAMPLES Reference Example 1 The following polyamide was polymerized and used in Examples. The amino terminal group concentration of the polyamide was measured by weighing out 20 mg of a sample into an NMR sample tube, dissolving with 0.6 ml of a solvent (hexafluoroisopropanol-d2), and using an NMR apparatus having an observation frequency of 599.9 MHz. Was.

A-1: ε-caprolactam was polymerized by a conventional method to obtain nylon 6 pellets. When the relative viscosity of this polyamide was measured, it was 2.70 and the amino terminal group concentration was 6.0 × 10 ⁻⁶ equivalent / g.

A-2: An equimolar salt of hexamethylenediamine-adipic acid was polymerized by a conventional method to obtain nylon 66 pellets. The relative viscosity of this polyamide was measured to be 2.75, and the amino terminal group concentration was 5.5 × 10 ⁻⁶ equivalent / g.

A-3: A mixed aqueous solution of hexamethylene diammonium terephthalate (6T salt) and aminododecanoic acid adjusted to have 60 mol% of hexamethylene terephthalamide units and 40 mol% of dodecamide units (solid raw material concentration: 60% by weight) ) Was charged into a pressure polymerization vessel, the temperature was increased with stirring, the reaction was carried out at a steam pressure of 19 kg / cm ² for 1.5 hours, and then the pressure was gradually released over about 2 hours. The mixture was reacted for 2 minutes to obtain a polyamide resin having a relative viscosity of 2.45 and an amino terminal group concentration of 7.5 × 10 ⁻⁶ eq / g.

Reference Example 2 (B-1) 1135 parts by weight of acetoxybenzoic acid having an intrinsic viscosity of about 0.5
6 dl / g of 519 parts by weight of polyethylene terephthalate and 3 parts by weight of terephthalic acid were charged into a reaction vessel equipped with a stirring blade and a distilling tube, and reacted at 250 to 300 ° C. for 2.0 hours. Reduce the pressure to 0.5 mmHg in 1.5 hours,
The mixture was further reacted for 1 hour and subjected to polycondensation. As a result, a melting point of 70 mol equivalents of aromatic oxycarbonyl units, 30 mol equivalents of ethylenedioxy units, and 30.2 mol equivalents of aromatic dicarboxylic acid units was 220 ° C., and the concentration of carboxyl end groups was 12
A liquid crystalline resin having 0 × 10 ⁻⁶ equivalent / g, logarithmic viscosity of 0.70 dl / g (measured using pentafluorophenol as a solvent), and a number average molecular weight of about 4,500 was obtained.

Reference Example 3 (B-2) 973 parts by weight of acetoxybenzoic acid, 3 parts by weight of terephthalic acid, 692 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g were stirred with a stirring blade and a distillation tube. The mixture was charged into a reaction vessel equipped with the reaction vessel, and reacted at 250 to 300 ° C. for 2.0 hours. Then, the pressure was reduced to 0.5 mmHg at 280 ° C. and 1.5 hours, and further reacted for 1 hour to perform polycondensation. 60 molar equivalents of oxycarbonyl units, 40 ethylenedioxy units
Molar equivalent, melting point 206 ° C. consisting of 40.2 molar equivalents of aromatic dicarboxylic acid unit, carboxyl end group concentration 165 ×
A liquid crystalline resin having 10 ^-6 equivalents / g, a logarithmic viscosity of 0.52 dl / g (measured using pentafluorophenol as a solvent) and a number average molecular weight of about 3500 was obtained.

Reference Example 4 (B-5) 901 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4'-dihydroxybiphenyl, 115 terephthalic acid
Parts by weight, 346 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 884 parts by weight of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distilling tube.
After reacting at 50 ° C. for 5 hours and at 250 to 300 ° C. for 1.5 hours, the pressure was reduced to 0.5 mmHg at 280 ° C. for 1.5 hours.
The mixture was further reacted for 1 hour and subjected to polycondensation. As a result, 72.5 mole equivalents of aromatic oxycarbonyl units, 7.5 mole equivalents of aromatic dioxy units, 20 mole equivalents of ethylenedioxy units, and 27.7 moles of aromatic dicarboxylic acid units Equivalent melting point 256 ° C, carboxyl end group concentration 120 × 10 ^-6
Equivalent / g, logarithmic viscosity 0.70 dl / g (measured using pentafluorophenol as a solvent), number average molecular weight of about 4
500 liquid crystalline resins were obtained.

Reference Example 5 (B-3) 1297 parts by weight of p-hydroxybenzoic acid and 346 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g A reaction vessel equipped with stirring blades and a distillation tube 25
After reacting at 0 to 300 ° C for 2.0 hours, 280 ° C,
The pressure was reduced to 0.5 mmHg in 1.5 hours, and the mixture was reacted for 0.5 hour to perform polycondensation. As a result, aromatic oxycarbonyl unit 80 molar equivalent, ethylenedioxy unit 20 molar equivalent,
Melting point 28 consisting of 20 molar equivalents of aromatic dicarboxylic acid units
3 ° C., carboxyl end group concentration of 50 × 10 ⁻⁶ equivalent / g or less, logarithmic viscosity of 1.2 dl / g (measured using pentafluorophenol as a solvent), number average molecular weight of about 12,000
Was obtained.

Reference Example 6 (B-4) 1135 parts by weight of acetoxybenzoic acid having an intrinsic viscosity of about 0.1
519 parts by weight of 6 dl / g of polyethylene terephthalate were charged into a reaction vessel equipped with a stirring blade and a distilling tube, and
After reacting at 300 ° C for 2.0 hours, 280 ° C, 1.5 hours
The pressure was reduced to 0.5 mmHg over a period of time, and polycondensation was carried out by further reacting for 1 hour. ^-6 equivalents /
g, a liquid crystal resin having a logarithmic viscosity of 1.0 dl / g (measured using pentafluorophenol as a solvent) and a number average molecular weight of about 8800 was obtained.

The carboxyl terminal group concentration of the liquid crystalline resin was pentafluorophenol / chloroform = 35/6.
5 (weight ratio) and measured by NMR. The number average molecular weight was pentafluorophenol / chloroform = 35/6.
5 (weight ratio) was used as a solvent and measured by GPC-LS (gel permeation chromatography-light scattering).

Examples 1 to 6 and Comparative Examples 1 to 7 The polyamide resin (A-1 to A-3) and the liquid crystalline polyester resin (B-1 to B-5) obtained in Reference Examples and 9 μm
As shown in Table 1, predetermined amounts of glass fibers having a diameter of 3 mm and a length of 3 mm were weighed and dry-blended. The temperature of the cylinder was set to the melting point of the polyamide resin + 30 ° C. using a 30 mmφ single screw extruder, and the mixture was melt-kneaded under the conditions of a screw rotation of 30 to 100 rpm to form pellets. After vacuum drying, the pellets are subjected to IS55EPN (manufactured by Toshiba Machine Co., Ltd.), the cylinder temperature is set to the melting point of the polyamide resin + 30 ° C., the mold temperature is set to 80 ° C., and the test pieces for measurement shown below are injection molded. I got it. The measuring method is described below. (1) Rigidity upon water absorption A bending test piece (1/8 inch thick) of 127 × 12.7 × 3.2 mm was immersed in water at 40 ° C. for 10 days in an incubator, and subjected to ASTM.
The flexural modulus was measured according to D790. (2) Tensile elongation An ASTM No. 1 tensile test piece was molded, and the test piece in the absolutely dry state was designated as A.
The tensile elongation was determined according to STM D638. (3) Dimensional stability A film gate square plate (70 × 70 × 2 mm) is formed at a molding minimum pressure (minimum filling pressure of the mold) +3 kgf / cm ² , and is formed with an incubator.
It was immersed in water at 0 ° C. for 10 days, and the dimensional change in the flow direction with respect to the time of absolute drying was evaluated. (4) Chemical resistance Molded product (127 × 1) used in the rigidity test during water absorption in (1)
A 2.7 × 3.2 mm bending test piece was placed in an incubator at 40 ° C. × 10
A 50% strength aqueous solution of calcium chloride was added at 10 points to the surface with a dropper at each temperature (80, 100, 1).
(30 ° C.) for 30 minutes. The evaluation was as follows: ×: crack generation, ：: no crack generation.

[0069]

[Table 1]

Example 7 The polyamide resin composition of Example 1 was press-molded at 255 ° C., and a 100 μm unstretched film was simultaneously biaxially stretched three times both vertically and horizontally at 90 ° C. using a film stretcher manufactured by TM Long. Then, it was immersed in water at 40 ° C. for 10 days in an incubator. The obtained sample was put on a Tensilon-type tensile tester (manufactured by Orientec) at a width of 10 mm and a length between chucks of 100 mm.
Set the sample so that the tensile speed is 200mm / m
As a result of calculating the breaking strength in, it was 1 MPa. Comparative Example 8 The breaking strength of the polyamide resin composition of Comparative Example 1 measured under the same conditions as in Example 7 was 0.5 MPa. Comparative Example 9 The polyamide resin composition of Comparative Example 4 was press-molded at 255 ° C., and an unstretched film of 100 μm was simultaneously biaxially stretched three times vertically and horizontally at 90 ° C. using a film stretcher manufactured by TM Long. Breakage occurred and a good film could not be obtained. Example 8 The polyamide resin composition of Example 1 was subjected to 40 mmφ single screw extruder.
0.4mmφ, spinning temperature 255 ° C using a 6-hole die,
Melt spinning was carried out at a take-up speed of 70 m / min, and immersed in water at 40 ° C. for 10 days in an incubator. The obtained sample was set on a Tensilon-type tensile tester (manufactured by Orientec) so that the chuck-to-chuck length was 100 mm, and the tensile strength was determined at a tensile speed of 200 mm / min. As a result, it was 3 g / d. . Comparative Example 10 The tensile strength of the polyamide resin composition of Comparative Example 1 measured under the same conditions as in Example 8 was 2.2 d / g. Comparative Example 11 The polyamide resin composition of Comparative Example 4 was subjected to 40 mmφ single screw extruder.
0.4mmφ, spinning temperature 255 ° C using a 6-hole die,
As a result of melt spinning at a take-up speed of 70 m / min, yarn breakage occurred.

Table 1 and Examples 7, 8 and Comparative Examples 8 to 11
The results show that the polyamide resin composition of the present invention is excellent in mechanical properties, surface appearance, moisture resistance, and chemical resistance, and is particularly excellent in rigidity and dimensional stability when placed in a high-humidity environment. Products, films, fibers).

[0072]

EFFECT OF THE INVENTION The polyamide resin composition of the present invention is a polyamide resin which is a molded article (molded article, film,
Fiber) can be obtained, and in particular, molded products are suitable for various other uses such as electric / electronic related parts, precision machine related parts, office equipment parts, and automobile / vehicle related parts.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 77/00 101: 12)

Claims (7)

[Claims] 1. A carboxyl terminal group concentration of ^{75.times.10.sup.-6} equivalents / g based on 100 parts by weight of a polyamide resin.
A polyamide resin composition obtained by adding 0.01 to 10 parts by weight of the above liquid crystalline resin. 2. The polyamide resin composition according to claim 1, wherein 0.5 to 300 parts by weight of a filler is added to 100 parts by weight of the total of (A) and (B). 3. The polyamide resin composition is immersed in water at 40 ° C. for 10 days and then subjected to ASTM method D790 (thickness 1/8 inch).
Characterized in that the flexural modulus measured by the method is improved by 10% or more as compared with the flexural modulus similarly measured using the same polyamide resin (composition) except that the liquid crystalline resin (B) is not included. The liquid crystalline resin composition according to claim 1 or 2, wherein 4. The polyamide resin composition according to claim 1, wherein the liquid crystalline resin (B) contains an ethylenedioxy unit. 5. A molded article comprising the polyamide resin composition according to claim 1. 6. A film comprising the polyamide resin composition according to claim 1. 7. A fiber comprising the polyamide resin composition according to claim 1.