JP2001115014A - Polyamide resin and polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both an aromatic ring-containing polyamide resin and a reinforced aromatic ring-containing polyamide resin composition capable of providing a molding product having a slight yellowing and maintaining excellent surface gloss even under a use condition exposed to ultraviolet rays indoors and outdoors. SOLUTION: This polyamide resin composition comprises a polyamide resin having a sulfuric acid relative viscosity (ηr) in a range of 1.5-2.8, a carboxyl end group ratio in a range of 55-85% and containing 3-90 mol% aromatic ring- containing polymer unit at least in the structure, an inorganic filler, a triazine derivative and a phosphite compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition suitable for exterior and interior parts of automobiles and houses, and more particularly to a composition suitable for exterior and interior parts of automobiles and houses.
The present invention relates to a polyamide resin and a polyamide resin composition capable of obtaining a molded article with less yellowing even in an environment exposed to ultraviolet rays.

[0002]

2. Description of the Related Art Polyamide resins are widely used for parts such as automobiles and electric / electronic products because of their excellent mechanical and thermal properties and oil resistance. In recent years, a reinforced polyamide resin in which a semi-aromatic polyamide resin containing an aromatic ring in its constituent unit, or a blend of an aliphatic polyamide resin and a semi-aromatic polyamide resin and an inorganic filler such as glass fiber is blended, The mechanical properties, heat resistance, chemical resistance, etc. are greatly improved compared to the polyamide resin alone, so parts that were conventionally made of metal will be made of reinforced polyamide resin from the viewpoint of weight reduction and streamlining of processes. Has become possible, and its use has been actively promoted in recent years.

However, when a molded article obtained from a polyamide resin or a reinforced polyamide resin composition is used outdoors or indoors in an environment where ultraviolet rays are irradiated, the stability to ultraviolet rays is not sufficient, and the discoloration of the molded article may be reduced. And its use is restricted. In particular, when a composition containing a polyamide containing an aromatic ring in its structural unit is used, discoloration, particularly yellowing, is remarkable, and its use is further restricted.

As a method for solving these problems, Japanese Patent Application Laid-Open No. 1-156364 discloses a method of discoloring a polyamide resin by using a composition comprising an inorganic colorant, zinc sulfide, copper halide, potassium halide, and a triazine derivative. It is disclosed that a colored molded article having excellent properties can be obtained. However, there is no disclosure of an example in which a polyamide resin containing an aromatic ring is used as a structural unit.

In Japanese Patent Application Laid-Open No. 3-181561, a polyamide resin composition containing a nylon resin, a hindered phenolic antioxidant, a phosphite compound, a hindered amine light stabilizer, and a benzotriazole ultraviolet absorber is excellent in ultraviolet light stability. Is disclosed. Also in this example, nothing is disclosed about an example in which a polyamide resin containing an aromatic ring is used as a structural unit. Even in a reinforced polyamide resin using a polyamide containing an aromatic ring in its constituent unit, development of a technique capable of suppressing fading due to ultraviolet rays has been desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic ring-containing polyamide resin and a reinforced polyamide resin composition which can provide a molded article with less yellowing even under the use conditions of being exposed to ultraviolet light outdoors and indoors. Is to provide.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, the terminal carboxyl group ratio in a polyamide resin containing an aromatic ring in its structural unit is within a specific range. The present inventors have further found that the above problem can be solved by using a specific triazine derivative and a phosphite compound in combination, and have completed the present invention. That is, the present invention is as follows.

1) Relative viscosity of sulfuric acid (ηr) is 1.5-2.
8 and the terminal carboxyl group ratio is 55 to 85.
% Of the polyamide resin containing at least 3 to 90 mol% of an aromatic ring-containing polymer unit in its structure, and the triazine derivative 0.05 to 100 parts by weight.
0.5 parts by weight and a phosphite compound 0.05 to 0.5
A polyamide resin composition characterized by containing by weight. 2) The polyamide resin composition according to the above item 2, wherein the phosphite compound is a pentaerythritol type phosphite.

3) The polyamide resin composition as described in 2 above, wherein the triazine derivative is a hydroxyphenyl triazine. 4) 30 to 70 parts by weight of the polyamide resin described in 1 above and 70 to 30 parts by weight of an inorganic filler, and 0.05 to 50 parts by weight of the triazine derivative per 100 parts by weight of the polyamide resin.
0.5 parts by weight and a phosphite compound 0.05 to 0.5
A polyamide resin composition characterized by containing by weight.

5) The polyamide resin composition as described in 4 above, wherein the phosphite compound is a pentaerythritol type phosphite. (6) The polyamide resin composition as described in (4) above, wherein the triazine derivative is a hydroxyphenyltriazine.

Hereinafter, the present invention will be described in detail. The polyamide resin used in the present invention has a sulfuric acid relative viscosity (ηr) in the range of 1.5 to 2.8, a terminal carboxyl group ratio in the range of 55 to 85%, and at least an aromatic ring in its structure. It is a polyamide resin containing 3 to 90 mol% of a contained polymer unit.

The relative viscosity of sulfuric acid (hereinafter referred to as ηr) used in the present invention is 95.5% sulfuric acid 100 g per 1 g of the polymer.
This is a value measured at 25 ° C. using 1.5 to 2.8, preferably 1.8 to 2.8.
2.5, more preferably 2.0 to 2.5. ηr
If the ratio is less than 1.5, the resin composition becomes brittle, and furthermore, the drawing from the nozzle tip of the cylinder becomes severe during molding, and molding may not be possible. When ηr is 2.
If it is higher than 8, the melt viscosity of the resin becomes too high, and the moldability decreases.

The term "terminal carboxyl group ratio of the polyamide resin used in the present invention" refers to the terminal carboxyl group concentration relative to the sum of the terminal carboxyl group concentration [COOH] and the terminal amino group concentration [NH2] of the polyamide. (Equivalents / kg polymer) is expressed as a percentage.

The carboxyl terminal group ratio is 55 to 85.
%, Preferably 60 to 75%, more preferably 60 to 7%.
Polyamide resins in the range of 0% can be used. If this ratio is less than 55%, the viscosity increases at the time of compounding or molding, and the moldability and the appearance of the molded article are greatly reduced. 8
If it exceeds 5%, discoloration upon irradiation with ultraviolet rays is extremely undesirable.

The terminal carboxyl group concentration of the polyamide resin used in the present invention can be controlled, for example, by adding a predetermined amount of monocarboxylic acid, dicarboxylic acid or monoamine during polymerization. Specific examples include acetic acid, caprylic acid, caproic acid, undecanoic acid, aliphatic monocarboxylic acids such as stearic acid, cyclohexanecarboxylic acid, alicyclic monocarboxylic acids such as methylcyclocarboxylic acid, and aromatic compounds such as benzoic acid. Aliphatic monocarboxylic acids, aliphatic dicarboxylic acids such as malonic acid, succinic acid and adipic acid, and aliphatic monoamines such as hexylamine, octylamine and decylamine can be used.

In the present invention, the terminal amino group concentration (unit:
Milliequivalent / kg) and terminal carboxyl group concentration (unit:
As a method of measuring the concentration of the terminal amino group, the concentration of the terminal amino group was calculated by dissolving a predetermined amount of the sample in 90% phenol and titrating at 25 ° C. with 1/50 N hydrochloric acid.
The terminal carboxyl group concentration was calculated by dissolving a predetermined amount of a sample in benzyl alcohol at 160 ° C. and titrating with a 1/10 N potassium hydroxide ethylene glycol solution using phenolphthalein as an indicator.

The aromatic ring-containing polymer unit in the polyamide in the present invention is a unit derived from an aminocarboxylic acid containing an aromatic ring, or a unit derived from a salt of a dicarboxylic acid and a diamine containing an aromatic ring in either dicarboxylic acid or diamine. Means the unit. For example, a semi-aromatic polyamide resin obtained by polymerizing a hexamethylene terephthalamide salt obtained from terephthalic acid and hexamethylene diamine alone is composed of only a repeating unit composed of hexamethylene terephthalamide. This is a value expressed as 100 mol% as a polymer unit concentration.

When the concentration of the aromatic ring-containing polymer unit is less than 3 mol%, a material satisfying properties such as mechanical strength and dimensional change which can be substituted for metal cannot be obtained. In many cases, the influence of deterioration due to the deterioration is large, which is not preferable. On the other hand, when it is more than 90 mol%, not only the yellowing resistance is not improved, but also the moldability and impact resistance are reduced, which is not preferable in many cases.

As a method for measuring the concentration of the aromatic ring-containing polymer unit in the polyamide, for example, a method of dissolving and measuring a polyamide as a sample by using NMR in a solvent such as bisulfuric acid or deuterated trifluoroacetic acid can be used. . Further, a method of chemically decomposing the polyamide component by hydrolysis or the like and identifying the obtained monomer by using an analytical means such as gas chromatography can also be used.

In the present invention, a sample concentration of 2% by weight, deuterated trifluoroacetic acid as a solvent, and a Brucker
1H-NMR using FT-NMR DPX400
Was measured. In determining the chemical shift value, tetramethylsilane was used as a reference substance.

The polyamide in the present invention may be a semi-aromatic polyamide alone, a mixture of a crystalline semi-aromatic polyamide and an amorphous semi-aromatic polyamide, or a mixture of a semi-aromatic polyamide and an aliphatic polyamide. If the aromatic ring-containing polymer unit concentration in the polyamide is within the range of the present invention, it can be used without any problem. Examples of the aliphatic polyamide that can be used in the present invention include nylon 6, nylon 66, nylon 610, and nylon 61.
2, nylon 11, nylon 12, nylon 46, or a copolymer thereof, or the like can be used.

Specific examples of the crystalline semi-aromatic polyamide include, for example, hexamethylene terephthalamide units (hereinafter referred to as 6T polymer units) obtained from terephthalic acid and hexamethylene diamine, and isophthalic acid and hexamethylene diamine. Hexamethylene isophthalamide unit (hereinafter referred to as 6I polymer unit), metaxylylene adipamide unit obtained from adipic acid and metaxylylenediamine (hereinafter referred to as MXD6 polymer unit), terephthalic acid and nonanediamine Examples thereof include nonanediamine terephthalamide units (hereinafter referred to as 9T polymer units) and the like, and at least one unit selected from these units and hexamethylene adipamide units (hereinafter referred to as 6T units) obtained from adipic acid and hexamethylenediamine.
6 polymer units) and caprolactam unit (hereinafter referred to as 6 polymer units).
Copolymer unit) and hexamethylene dodecamide unit (hereinafter, referred to as 612 polymer unit).

Examples of amorphous semi-aromatic polyamides include polyamides obtained from terephthalic acid and trimethylhexamethylenediamine, bis (4-amino-methylhexyl) methane, hexamethylenediamine, terephthalic acid, and isophthalic acid. , Polyamide obtained from caprolactam, bis (4-amino-3-methylcyclohexyl) methane, bis (4-amino-methyl-5-ethylcyclohexyl) methane, hexamethylenediamine, terephthalic acid, isophthalic acid, and non-polyamide obtained from caprolactam. Crystalline polyamide and the like.

In the present invention, particularly preferred polyamides having an aromatic ring-containing polymer unit include 66 components of 7
Polyamide 66 / 6I copolymer having 0 to 95% by weight and 6I component in 5 to 30% by weight, more preferably 72 to 93% by weight of 66 component and 7 to 28% by weight of 6I component. Is a copolymer.

If the content of the 6I component is less than 5% by weight, a molded article having excellent molded appearance and excellent weather resistance cannot be obtained.
If the I component is more than 30% by weight, a molded article having an excellent surface appearance cannot be obtained or the molded article becomes difficult to release from the mold unless sufficient cooling time is taken in the mold. There is concern that productivity will suffer.

The polyamide in the present invention is produced, for example, from a salt of adipic acid, isophthalic acid and hexamethylenediamine by a melt polymerization method, a solid phase polymerization method, a bulk polymerization method, a solution polymerization method, or a combination thereof. A method of performing polycondensation may be used. Further, for example, a method such as solution polymerization or interfacial polymerization from adipic acid chloride, isophthalic acid chloride and hexamethylenediamine may be used. Among these, a method based on melt polymerization or a combination of melt polymerization and solid phase polymerization is more preferably used in the present invention from an economic viewpoint.

As the triazine derivative used in the present invention, hydroxyphenyl triazines are preferable, and examples thereof include 2,4,6-tris (2-hydroxy-4-octyloxy-phenyl) -1,3,3 5-
Triazine, 2- (2-hydroxy-4-hexyloxy-phenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octyloxy-phenyl) -4,6- Bis (2,4-dimethylphenyl) -1,3,5-triazine,

2- (2,4-dihydroxyphenyl)-
4,6-bis (2,4-dimethylphenyl) -1,3
5-triazine, 2,4-bis (2-hydroxy-4-
Propyloxy-phenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxy-phenyl) -4,6-bis (4-methylphenyl ) -1,3,5-triazine,

2- (2-hydroxy-4-dodecyloxy-phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2 '-Hydroxy-4'-isopropyloxyphenyl) -1,3,5-triazine, 2,4,6-tris (2'-hydroxy-4'-n-hexyloxyphenyl) -1,3,5-triazine, And 2,4,6-tris (2'-hydroxy-4'-ethoxycarbonylmethoxyphenyl) -1,3,5-triazine.

The amount of the triazine derivative to be added is 0.05 to 0.5 part by weight, preferably 0.08 to 0.3 part by weight, based on 100 parts by weight of the polyamide resin. If the amount is less than 0.05 parts by weight, the effect may not be sufficient. If the amount exceeds 0.5 parts by weight, the effect of the compounding will be saturated, which is not economical and may impair the appearance of the molded article.

The phosphite compound used in the present invention is not particularly limited. For example, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, tris isodecyl phosphite, phenyl diisodecyl phosphite Phyte, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyltridecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl)
Phosphite,

Tris (2,4-di-tert-butyl-5-methylphenyl) phosphite, tri (butoxyethyl)
Phosphite, tetratridecyl-4,4'butylidenebis (3-methyl-6-tert-butylphenol) diphosphite, 4,4'-isopropylidenediphenol alkyl phosphite (where alkyl is one carbon atom)
About 2 to 15), 4,4'-isopropylidenebis (2
-T-butylphenol) di (nonylphenyl) phosphite,

Tris (biphenyl) phosphite, tetra (tridecyl) 1,1,3 tris (2-methyl-5
-T-butyl-4-hydroxyphenyl) butanediphosphite, tetra (tridecyl) -4,4'butylidenebis (3-methyl-6-tert-butylphenol) diphosphite, tetra (C1-C15 mixed alkyl) -4,4'-isopropylidene Diphenyl diphosphite,

Tris (mono- and di-mixed nonylphenyl) phosphite, 4,4'-isopropylidenebis (2-t
-Butylphenol) di (nonylphenyl) phosphite, 9,10-dihydro-9-oxa9-oxa10-phosphaphenanthrene-10-oxide,
Tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenyl polyphosphite, bis (octylphenyl) bis (4,4'butylidenebis (3-methyl- 6-t-butylphenol) ・ 1,6-hexaneoldiphosphite, hexatridecyl-1,1,3
Tris (2-methyl-4-hydroxy-5-tert-butylphenol) diphosphite, tris (4,4′-isopropylidenebis (2-tert-butylphenol)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite,

2,2-methylenebis (4,6-di-t-
Butylphenyl) octyl phosphite, 2,2-methylenebis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-tert-butyl-5-methylphenyl)-
4,4′-biphenylenediphosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphite.

Further, as a preferred phosphite compound, a pentaerythritol type phosphite compound can be mentioned. Specific examples of the pentaeristol type phosphite compound include 2,6-di-t-butyl-4-methylphenyl phenyl pentaerythritol diphosphite and 2,6-di-t-butyl-4-. Methylphenyl
Methyl pentaerythritol diphosphite, 2,6
-Di-t-butyl-4-methylphenyl-2-ethylhexyl pentaerythritol diphosphite, 2,6
-Di-t-butyl-4-methylphenyl isodecyl.
Pentaerythritol diphosphite,

2,6-di-t-butyl-4-methylphenyl lauryl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl isotridecyl pentaerythritol diphosphite,
2,6-di-t-butyl-4-methylphenyl stearyl pentaerythritol diphosphite, 2,6-
Di-t-butyl-4-methylphenyl cyclohexyl pentaerythritol diphosphite,

2,6-di-t-butyl-4-methylphenyl benzyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl ethyl cellosolve pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl butyl carbitol pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl octylphenyl pentaerythritol diphosphite, , 6-Di-t-butyl-4-methylphenyl nonylphenyl pentaerythritol diphosphite,

Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, , 6-di-t-
Butyl-4-methylphenyl 2,6-di-t-butylphenyl pentaerythritol diphosphite, 2,
6-di-t-butyl-4-methylphenyl 2,4-di-t-butylphenyl pentaerythritol diphosphite,

2,6-di-t-butyl-4-methylphenyl 2,4-di-t-octylphenyl pentaerythritol diphosphite, 2,6-di-t-butyl-
4-methylphenyl-2-cyclohexylphenyl pentaerythritol diphosphite, 2,6-di-t-
Amyl-4-methylphenyl phenyl pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t- (Octyl-4-methylphenyl) pentaerythritol diphosphite.

Among them, bis (2,6-di-t-butyl-
4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) ) Pentaerythritol diphosphite, bis (2,6-di-)
t-octyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is particularly preferred.

In the present invention, the sulfuric acid relative viscosity (ηr) is in the range of 1.5 to 2.8, the carboxyl terminal group ratio is in the range of 55 to 85%, and at least the aromatic ring-containing polymer is contained in the structure. In the case of a polyamide resin composition comprising a polyamide resin containing 3 to 90 mol% of units and an inorganic filler, the weight loss at 310 ° C. in a thermogravimetric analysis curve measured in air is less than 10% by weight. It is particularly preferred to use certain phosphite compounds.

The thermogravimetric analysis curve is a curve obtained by using a thermoanalyzer TG-DTA manufactured by Rigaku Denki Co., Ltd. at a heating rate of 20 ° C./min. The weight loss rate at 310 ° C. in the thermogravimetric analysis curve measured in the air means the weight loss rate at the time of reaching 310 ° C. when the temperature is raised from room temperature under the above conditions, and when this value exceeds 10% by weight. However, when the compound is prepared or the compound is decomposed by heating during the production of the molded product, a sufficient improvement effect cannot be obtained.

The phosphite compound is added in an amount of 0.05 to 0.5 with respect to 100 parts by weight of the polyamide resin.
Parts by weight, preferably 0.08 to 0.3 parts by weight. If the amount is less than 0.05 parts by weight, the effect may not be sufficient. If the amount exceeds 0.5 parts by weight, the effect of the compounding will be saturated, which is not economical and may impair the appearance of the molded article.

Next, the relative viscosity of sulfuric acid (ηr) is 1.5 to
2.8, and the carboxyl end group ratio is 55 to 55.
A polyamide resin composition comprising an inorganic filler and a polyamide resin which is in the range of 85% and contains at least 3 to 90 mol% of an aromatic ring-containing polymer unit in its structure will be described.

The polyamide resin is as described above. The inorganic filler used in the present invention is not particularly limited, for example, glass fiber, milled fiber, glass flake, glass beads, potassium titanate, magnesium sulfate, barium sulfate, magnesium hydroxide, hydroxyapatite, Calcium hydrogen phosphate,
Examples include inorganic fillers such as sepiolite, zonolite, aluminum borate, carbon fiber, kaolin, wollastonite, talc, montmorillonite, swellable fluoromica-based mineral, and mica.

Further, these can be used in combination of two or more kinds. Preferred examples of glass fibers include those commonly used for thermoplastic resins, and there are no particular restrictions on the fiber diameter or length.
Any of chopped strands, rovings, and milled fibers of ２５25 μm may be used. When using chopped strands, the length is 0.1 to 6 mm
Can be appropriately selected for use.

As the inorganic filler, those having a generally known silane coupling agent adhered to the surface thereof may be used.
Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, vinyltriethoxysilane, γ
-Glycidoxypropyltrimethoxysilane and the like can be used.

The amount of the polyamide in the composition of the present invention is 30 to 70 parts by weight, preferably 35 to 70 parts by weight.
It is in the range of 67 parts by weight. If the amount is less than 30 parts by weight, the fluidity of the resin will be poor, and it will be difficult to obtain a molded product having good surface gloss. On the other hand, if the amount is more than 70 parts by weight, strength and rigidity are insufficient as a material that can be replaced with metal.

The amount of the inorganic filler is 70 to 30 parts by weight, preferably 65 to 33 parts by weight. If the amount is more than 70 parts by weight, the fluidity of the resin deteriorates, and it becomes difficult to obtain a molded product having good surface gloss. On the other hand, if the amount is less than 30 parts by weight, strength and rigidity are insufficient as a material that can be substituted for metal.

The composition of the present invention may further preferably contain a copper compound. Examples thereof include, for example, copper chloride, copper bromide, copper fluoride, copper iodide, copper thiocyanate,
Copper nitrate, copper acetate, copper naphthenate, copper caprate, copper laurate, copper stearate, copper acetylacetone, copper (I) oxide, copper (II) oxide, and the like, and particularly preferred in the present invention, Copper halide such as copper iodide; and copper acetate.

The amount of the copper compound to be added is 10 to 1000 p with respect to the polyamide resin based on the copper in the copper compound.
pm, particularly preferably 50 to 800 ppm. When the addition amount is less than 10 ppm, it is difficult to sufficiently exert the effect of improving the weather resistance. When the addition amount exceeds 1000 ppm, the effect of improving the weather resistance is saturated, and the effect of increasing the addition amount is increased. On the contrary, corrosion on metals such as polymerization reactors, extruders, and molding machines, corrosion of metals inserted into molded articles, and the like are likely to occur.

Further, the copper compound in the present invention is more preferably used in combination with an iodine compound. Examples of the iodine compound include potassium iodide, magnesium iodide, ammonium iodide, and the like, and iodine alone may be used. More preferably, it is potassium iodide. The preferred compounding amount of the iodine compound is the gram atomic ratio of the iodine element and the copper element to the polyamide resin ([iodine] /
[Copper]) is 5 to 30, more preferably 10 to 25. If it is less than 5, a sufficient weather resistance improving effect cannot be obtained, and if it is more than 30, corrosion on metals such as polymerization reactors, extruders, molding machines, etc., corrosion of metals inserted into molded articles, etc. tend to occur. Become.

The method of blending, mixing, and kneading in the production of the reinforced polyamide resin in the present invention and the order thereof are not particularly limited, and they are mixed by a commonly used mixer such as a Henschel mixer, a tumbler, a ribbon blender or the like. do it. As the kneader, a single-screw or twin-screw extruder is usually used.

The molded article according to the present invention can be obtained by producing a composition pellet by the above-described extruder and molding the pellet into an arbitrary shape by compression molding, injection molding, extrusion molding or the like. In that case, for example, in injection molding, the condition is, for example, a molding temperature of 250 to 31.
A molding method in a range of 0 ° C. and a mold temperature of 40 to 120 ° C. can be exemplified.

The reinforced polyamide resins of the present invention may contain one or more conventional additives, such as stabilizers and inhibitors against oxidation, heat and UV degradation, as long as the objects of the invention are not impaired. Agents and release agents, coloring agents including dyes and pigments, nucleating agents, foaming agents, plasticizers, inorganic fillers, flame retardants, antistatic agents, and the like can be appropriately added.

The molded article according to the present invention is, for example, a molded article for automobile parts such as an outer door handle, a wheel cap, a roof rail, a door mirror base, a room mirror arm, a sunroof deflector, a door handle, a crescent, a French drop, and the like. It can be particularly preferably used for molded parts.

[0058]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the evaluation method is as follows. [Sulfuric acid relative viscosity] According to JIS K6810, 1 g of polymer was dissolved in 100 ml of 95.5% sulfuric acid,
Measure at 5 ° C.

[Terminal amino group concentration (unit: milliequivalent /
kg)] The sample was dissolved in 90% phenol and titrated with 1 / 50N hydrochloric acid at 25 ° C. to calculate. [Terminal carboxyl group concentration (unit: meq / kg)] A sample was dissolved in benzyl alcohol at 160 ° C.
It was calculated by titration with a solution of 0 N potassium hydroxide in ethylene glycol using phenolphthalein as an indicator.

[Quantitative determination of copper element and iodine element] As a method for determining the copper element and the iodine element in the polyamide resin molded body, the molded body was pulverized, and the copper element was determined by burning the sample combustion residue with an aqueous hydrochloric acid solution. The ICP method was used after the adjustment, and the determination of the iodine element was measured by an ion electrode method after extracting the sample with boiling water.

[Determination of Unit Concentration of Aromatic Ring-Containing Polymer in Polyamide] The unit concentration of the aromatic ring-containing polymer was set to 2% by weight, deuterated trifluoroacetic acid was used as a solvent, and FT-NMR DPX400 manufactured by Brucker was used.
Was used to measure 1H-NMR. The measurement conditions are described below.

Measurement temperature: 30 ° C. Pulse width: 2.5 μsec Pulse repetition time: 3.0 sec Integration number: 128 In determining the chemical shift value, tetramethylsilane was used as a reference substance.

[Mechanical properties] IS-50 manufactured by Toshiba Machine Co., Ltd.
Screw rotation speed 200rpm using EP injection molding machine
m, 3 mm thick A under molding conditions of resin temperature 290 ° C
An STM type 1 was molded, and the molded piece was used as a sample for measuring physical properties. Tensile breaking strength and flexural modulus were measured according to ASTM D638 and D790, respectively.

[Ultraviolet yellowing] SPECTRONICS
The evaluation was performed using an ENF-260C / J ultraviolet irradiation device manufactured by CORPORATION. Irradiation surface is 145 × 45
mm wavelength range, UV wavelength 254 μm, UV intensity 420
Exposure was performed at room temperature for 8 hours under the conditions of μW / cm 2 and a distance between the sample and the ultraviolet lamp of 15 cm. The color tone of the molded plate before and after exposure was measured, and the change in the b value was determined using a color difference meter ND-300A manufactured by Nippon Denshoku Co., Ltd. It can be determined that the smaller the color difference (Δb), the better the yellowing resistance.

[Gloss retention after UV exposure] Using an IS150E injection molding machine manufactured by Toshiba Machine Co., Ltd., the filling time was about 1.5 seconds at a cylinder temperature of 290 ° C. and a mold temperature of 120 ° C. The injection pressure and injection speed were appropriately adjusted to obtain an injection molded plate of 100 × 90 × 3 mm.

This injection-molded plate was subjected to a xenon arc-type accelerated weathering tester (XENOTEST 1200C manufactured by Atlas Co., Ltd.).
(PS) using a black panel at a temperature of 83 ° C. for 600 hours. As a method for evaluating the gloss retention, the gloss of a molded plate before and after exposure is measured, and the ratio of the value after exposure to the value before exposure is expressed as a percentage. The gloss value was measured using the Horiba handy gloss meter IG320 for the center of the obtained test piece.
Gs60 ° was measured according to IS-K7150.

[Polyamide and Inorganic Filler Used in Examples and Comparative Examples] [Polyamide] a1: Nylon 66 / 6I copolymer; produced according to Production Example 1.

A2: Nylon 66; Leona 1300 manufactured by Asahi Kasei Corporation a3: Nylon MXD6; Reny 6002 manufactured by Mitsubishi Engineering-Plastics Corporation

[Inorganic filler] b1: Glass fiber manufactured by Asahi Fiberglass Co., Ltd. CS03JA416 Average fiber diameter 10 μm b2: Wollastonite Hayashi Kasei Co., Ltd. trade name VM-8N

[Triazine derivative] c1: 2- (2-hydroxy-4-hexyloxy-phenyl) -4,6-diphenyl-1,3,5-triazine Trade name TINUBIN 1577FF c2: 1,3,5-tris (3,5-di-t-butyl-
4-hydroxybenzyl-S-triazine-2,4,6
-(1H, 3H, 5H) Trion Trade name ADK STAB A0-20

[Phosphite compound] d1: bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite trade name ADK STAB PEP-36 Weight loss rate at 310 ° C. 5% d2: bis (2,4-Di-t-butylphenyl) pentaerythritol diphosphite Trade name ADK STAB PEP-24G Weight loss rate at 310 ° C. 10%

D3: Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphite P-EPQ Weight loss at 310 ° C. 15% d4: Tris (2,4- Di-t-butylphenyl) phosphite Product name Irgafos 168 Weight loss at 310 ° C 36%

[0073]

[Production Example 1] (Production of nylon 66 / 6I copolymer) Equimolar salt of adipic acid and hexamethylenediamine 2.0k
g, 0.5 kg of equimolar salt of isophthalic acid and hexamethylenediamine and 2.5 kg of pure water were charged into a 5-liter autoclave and sufficiently purged with nitrogen while stirring.
The temperature was raised from room temperature to 220 ° C. in about 1 hour while stirring was continued.

Thereafter, the internal pressure of the autoclave was increased to 1.77.
The temperature was raised to 260 ° C. over about 2 hours while removing water from the reaction system so as to obtain MPa. Then stop heating,
The autoclave was sealed and cooled to room temperature over about 8 hours, yielding about 2 kg of polymer. The obtained polymer was pulverized and subjected to solid-phase polymerization at 200 ° C. for 8 hours under a nitrogen stream using a 10-liter evaporator to further increase the molecular weight.

Relative viscosity of sulfuric acid by solid phase polymerization (ηr: 1 g of polymer / 100 ml of 95.5% sulfuric acid, measured at 25 ° C.)
Increased from 1.38 to 2.30. The obtained polyamide had a terminal carboxyl group concentration of 102, a terminal amino group concentration of 54, and a terminal carboxyl group ratio of 65%.

[0076]

Production Example 2 2.00 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.50 kg of equimolar salt of isophthalic acid and hexamethylenediamine and 0.0 of adipic acid
15 kg and 2.5 kg of pure water were charged into a 5 L autoclave and stirred well. After sufficiently purging with N2, the temperature was raised from room temperature to 220 DEG C. over about 1 hour with stirring.

At this time, the internal pressure becomes 1.77 MPa due to the natural pressure of the steam in the autoclave, but the internal pressure becomes 1.77 MPa.
The heating was further continued while removing water outside the reaction system so as not to make the pressure more than a. After 2 hours, the internal temperature is 260 ℃
, The heating was stopped, the discharge valve of the autoclave was closed, and the mixture was cooled to room temperature over about 8 hours.

After cooling, the autoclave was opened, and about 2 kg of the polymer was taken out and pulverized. The obtained pulverized polymer was placed in a 10-L evaporator under a nitrogen stream for 200 hours.
Solid-state polymerization was performed at 8 ° C. for 8 hours. Relative viscosity of sulfuric acid by solid-state polymerization (ηr: 1 g of polymer / 100 ml of 95.5% sulfuric acid)
(Measured at 25 ° C.) changed from 1.33 to 2.04. The resulting polyamide had a terminal carboxyl group concentration of 15%.
5, the terminal amino group concentration was 31, and the terminal carboxyl group ratio was 83%.

[0079]

Examples 1 to 4 Polyamide resin 1 obtained in Production Example 1
The triazine derivative and the phosphite compound were mixed in an amount of 00 parts by weight as shown in Table 1 and melt-kneaded in an extruder to obtain polyamide resin pellets. The polyamide resin pellet was molded and subjected to ultraviolet exposure evaluation. Table 1 shows the results.

As can be seen from the results, the specific triazine derivative and the phosphite compound are blended with the aromatic ring-containing polyamide resin having a specific sulfuric acid relative viscosity range and a specific terminal carboxy group ratio range according to the present invention. It can be seen that a composition having excellent ultraviolet yellowing resistance and gloss retention can be obtained.

[0081]

Example 5 A mixture of 50 parts by weight of a1 as a polyamide, 0.1 part by weight of c1 as a triazine derivative, and 0.1 part by weight of d1 as a phosphite compound was mixed with a TEM35 φ biaxial extruder manufactured by Toshiba Machine Co., Ltd. Machine (set temperature 280
C., a screw rotation speed of 300 rpm) from a feed hopper, and 50 parts by weight of b1 as an inorganic filler from a side feed port, and the melt-kneaded product extruded from a spinneret is cooled in a strand form and pelletized. Thus, a reinforced polyamide resin composition was obtained. The obtained composition was molded, and the yellowing and the gloss retention after ultraviolet irradiation were evaluated. The results are shown in Table 2. It can be seen that a molded article obtained by using the composition of the present invention has little discoloration even after irradiation with ultraviolet rays and has a high gloss retention.

[0082]

Examples 6 and 7 Except that the types and amounts of polyamide, inorganic filler, triazine derivative and phosphite compound were changed as shown in Table 2 when producing the reinforced polyamide resin composition in Example 5. Is Example 5
Was carried out in the same manner as Table 2 shows the evaluation results.

[0083]

Comparative Examples 1 and 2 In producing a reinforced polyamide resin composition in Example 5, the polyamide resin obtained in Production Example 2 was used as the polyamide, and in Comparative Example 1, both the triazine derivative and the phosphite compound were used. Without
Comparative Example 2 was carried out in the same manner as in Example 5, except that only the triazine derivative was used. Table 2 shows the composition and evaluation results. Thus, it can be seen that even if the triazine derivative or the phosphite compound is lacking, excellent UV discoloration resistance and gloss retention as in the present invention cannot be obtained.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

Industrial Applicability The reinforced polyamide resin and polyamide resin composition of the present invention, when formed into a molded article, have excellent yellowing resistance and gloss retention as compared with conventional ones. Outer door handles, wheel caps, roof rails, door mirror stays, rearview mirror arms, wiper arms, sunroof deflectors, motor covers, door levers, window levers, automotive exterior parts such as chairs and desk legs, industrial equipment, etc. It can be suitably used in a wide range of fields.

Continued on the front page F-term (reference) 4J002 CL031 DD039 DD079 DD089 DE078 DE099 DE188 DF039 DG039 DG048 DH008 DH048 DJ008 DJ038 DJ048 DJ058 DK008 DL008 EE049 EG049 EG079 EU186 EW067 FA018 FA048 FA088 FB108 FD108 FD 080 FD FD 080 FD160 FD170 FD200 FD320 GL00 GN00

Claims (6)

[Claims] 1. A sulfuric acid relative viscosity (ηr) of 1.5 to 2.8.
And the terminal carboxyl group ratio is 55 to 85%.
And a triazine derivative in an amount of from 0.05 to 100 parts by weight of a polyamide resin containing at least 3 to 90 mol% of an aromatic ring-containing polymer unit in its structure.
0.5 parts by weight and a phosphite compound 0.05 to 0.5
A polyamide resin composition characterized by containing by weight. 2. The polyamide resin composition according to claim 2, wherein the phosphite compound is a pentaerythritol type phosphite. 3. The polyamide resin composition according to claim 2, wherein the triazine derivative is a hydroxyphenyltriazine. 4. The polyamide resin 30 to 7 according to claim 1.
0 part by weight and 70 to 30 parts by weight of an inorganic filler, and 0.05 to 0.5 part by weight of a triazine derivative and 0.1 to 100 parts by weight of the polyamide resin.
A polyamide resin composition containing from 0.5 to 0.5 part by weight. 5. The polyamide resin composition according to claim 4, wherein the phosphite compound is a pentaerythritol type phosphite. 6. The polyamide resin composition according to claim 4, wherein the triazine derivative is a hydroxyphenyltriazine.