JPH10306212A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyamide resin composition, having excellent rigidity and toughness together and especially excellent in high-speed planar impact fracture characteristics and having balanced and excellent characteristics of molded product surface appearance and dimensional stability. SOLUTION: This polyamide resin composition is obtained by melt kneading 100 pts.wt. of a polyamide resin with 5-150 pts.wt. of a nonfibrous inorganic filler having 0.05-10 μm average particle diameter and/or a fibrous inorganic filler having 0.05-10 μm average fiber diameter except glass fibers. The resultant composition has >=4 g/m<2> of the polyamide component sticking to the inorganic filler based on a unit surface area measured by a BET method when dissolving the composition in hexafluoroisopropanol and recovering the inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyamide resin composition having excellent rigidity and toughness, particularly excellent in high-speed surface impact fracture characteristics, and excellent in the surface appearance and dimensional stability of a molded product in balance. It relates to a manufacturing method.

[0002]

2. Description of the Related Art In recent years, demands for higher performance of engineering plastics have been increasing more and more. Attempts have been made to improve the characteristics of thermoplastic resin materials in response thereto. For example, Polymer, 26, 1855 (1985) discloses that high impact strength is exhibited by blending an elastomer component with nylon 66 and finely dispersing it.
In addition, it is generally known that by adding an inorganic filler to a resin material, the heat resistance or the rigidity of the material is improved. However, these properties often impair other properties. For example, when an elastomer component is blended for the purpose of increasing the impact strength of the material, heat resistance and rigidity are impaired, and various inorganic fillers and reinforcing agents are blended to increase the heat resistance and rigidity of the material. In such a case, since the Izod impact strength and the surface impact strength are impaired, it is difficult to simultaneously improve the impact strength and the rigidity.

[0003] In addition, by incorporating a fibrous reinforcing agent such as glass fiber, rigidity is improved and notches are formed.
Although it is known that the Izod impact strength is improved, this method reduces the surface impact strength and the notch-free Izod impact strength as compared to the non-reinforced system, and also reduces the elongation of the material and the fiber shape. Due to the effect of the orientation of the toughening agent, it has unfavorable effects on engineering materials, such as anisotropy of mechanical properties and warping.

[0004] On the other hand, various studies have been made for the purpose of suppressing a decrease in impact strength caused when an inorganic filler other than a fiber shape is added to a resin material. For example, JP-A-61-3
No. 6340 discloses a method of coating glass beads with a coating agent such as a silane compound or a fluorocarbon compound of 1% by weight or less. However,
Although such a method is effective in suppressing a decrease in impact strength as compared with a material to which uncoated glass beads are added,
Only those having a lower impact strength than the non-filler system are obtained. It was also found that the method described does not provide sufficient tensile elongation at break and surface impact strength.

Further, as disclosed in JP-A-62-253652, a polyamide having a high glass transition temperature such as a polyphenylene ether resin, a rubbery polymer, and an unsaturated carboxylic acid are melt-kneaded with polyamide to obtain impact resistance. Attempts to achieve both heat resistance have been disclosed, but heat resistance and dimensional stability are insufficient, and even if an inorganic filler is simply added to improve this, impact resistance and high-speed surface impact fracture will occur. A material having a large decrease in characteristics and having sufficient characteristics could not be obtained.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention solves the above-mentioned problems, that is, it has both excellent rigidity and toughness, and particularly has excellent high-speed surface impact characteristics and a molded article surface appearance.
It is an object to obtain a polyamide resin composition having excellent characteristics with balanced dimensional stability.

[0007]

Means for Solving the Problems The present inventors have studied 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 non-fibrous inorganic filler having an average particle diameter of 0.05 to 10 μm and / or a fiber diameter of 0 excluding glass fibers. 0.05 to 10 μm fibrous inorganic filler 5-150
A polyamide resin composition characterized by being melt-kneaded in parts by weight, wherein the polyamide resin component adhered to the inorganic filler when the composition was dissolved in hexafluoroisopropanol and the inorganic filler was recovered was BET. Resin composition characterized by being at least 4 g / m ² per unit surface area of the inorganic filler as measured by the method, (2) (C) an olefin compound having a carboxylic anhydride group in a molecule or the olefin compound The polyamide resin composition according to (1), wherein the polymer of (A) is melt-kneaded in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the polyamide resin (A). (4) the polyamide resin composition according to the above (1) or (2), which is at least one member selected from aliphatic polyamide resins having a melting point of 200 ° C. or higher. The polyamide resin composition according to any one of the above (1) to (3), wherein the amide resin is at least one selected from nylon 66 and nylon 6, and (5) the olefin compound is maleic anhydride or itaconic anhydride. A polyamide resin composition according to any one of the above (1) to (4), which is at least one selected from glutaconic anhydride, citraconic anhydride, and aconitic anhydride; and (6) a polymer of an olefin compound. The polyamide resin composition according to any one of the above (1) to (4), which is polymaleic anhydride; (7) the inorganic filler is at least one selected from kaolin, wollastenite, and talc. To (6) the polyamide resin composition according to any one of (8) and (40) by weight of the polyphenylene oxide resin in an amount of 40 parts by weight or more based on 100 parts by weight of the polyamide resin (A). The polyamide resin composition according to any one of the above (1) to (7), wherein the polyamide resin composition is not added.

(9) A molded article having a plate-like portion comprising the polyamide resin composition according to any one of the above (1) to (8), (10) (A) 100 parts by weight of the polyamide resin, (B) A) a fiber diameter of 0.0 excluding non-fibrous inorganic filler and / or glass fiber having an average particle diameter of 0.05 to 10 μm;
A polyamide resin adhered to the inorganic filler when the composition is dissolved in hexafluoroisopropanol and the inorganic filler is recovered by melting and kneading 5 to 150 parts by weight of a fibrous inorganic filler of 5 to 10 μm. This is a method for producing a polyamide resin composition in which the component is 4 g / m ² or more per unit surface area of the inorganic filler measured by the BET method.

Further, the present invention relates to (11) an olefin compound having (C) a carboxylic anhydride group in a molecule or a polymer of the olefin compound, wherein (A) a polyamide resin 1
11. The method for producing a polyamide resin composition according to the above item 10, wherein the mixture is melt-kneaded in an amount of 0.05 to 10 parts by weight with respect to 00 parts by weight.

[0010]

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

The polyamide resin used in the present invention is:
Nylon containing amino acids, lactams or diamines and dicarboxylic acids as main components. Representative examples of the monomer forming the main component include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid;
Lactams such as -aminocaprolactam and ω-laurolactam, tetramethylenediamine, hexamerenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-
/ 2,4,4-trimethylhexamethylenediamine, 5
-Methylnonamethylenediamine, metaxylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl)
Cyclohexane, 1-amino-3-aminomethyl-3,
5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, amino Aliphatic, alicyclic, and aromatic diamines such as ethylpiperazine, and adipic acid, spearic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, and 2-chloroterephthalic acid
Aliphatic, alicyclic, such as methyl terephthalic acid, 5-methyl isophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid;
An aromatic dicarboxylic acid is mentioned, and 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, particularly useful polyamide resins are polyamide resins having a melting point of 200 ° C. or more and excellent in heat resistance and strength. Specific examples thereof include polycaproamide (nylon 6) and polyhexamethylene. Adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyhexamethylene adipamide / polyhexamethylene Terephthalamide copolymer (nylon 6
6 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66
/ 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I),
Examples include polyxylylene adipamide (nylon XD6) and mixtures or copolymers thereof.

Particularly preferred are nylon 6, nylon 66, nylon 610, nylon 6/66.
Examples include copolymers and nylon 6/12 copolymers. It is also practically preferable to use these polyamide resins as a mixture depending on required properties such as moldability, heat resistance, toughness, and surface properties.

The degree of polymerization of these polyamide resins 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 to 4.0. 0
Are preferred.

In the present invention, the non-fibrous inorganic filler having an average particle size of 0.05 to 10 μm used as the component (B) includes wollastenite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, and the like. Silicates such as bentonite, asbestos, talc and alumina silicate, alumina, metal compounds such as silicon oxide, magnesium oxide, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, calcium sulfate, sulfuric acid Non-fibrous fillers such as sulfates such as barium, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide and silica, which are hollow. And furthermore, It may be used in combination agent of two or more. Of these, particularly preferred fillers are talc, wollastenite, clay, and kaolin. Kaolin is most preferred for imparting a good balance of ductility and rigidity.

These non-fibrous inorganic fillers need to have an average particle size of 0.05 to 10 μm. If the average particle size is less than 0.05 μm, the agglomeration of the non-fibrous inorganic filler undesirably lowers the ductility and the molded product surface. When the particle diameter exceeds 10 μm, ductility and deterioration of the surface of the molded product are remarkable. The average particle size is preferably 0.1 to 5 μm, more preferably 0.1 to 5 μm.
３3 μm. In addition, these average particle diameters are measured by a sedimentation method.

Specific examples of the fibrous inorganic filler having a fiber diameter of 0.05 to 10 μm excluding glass fibers used as the component (B) include potassium whisker, zinc oxide whisker, aluminum borate whisker, alumina fiber, and carbon fiber. Silicon fiber, ceramic fiber, asbestos fiber, stone fiber,
It is a fibrous filler such as a metal fiber, a fibrous calcium carbonate, and a fibrous wollastenite, and two or more of these fillers can be used in combination. Among these, particularly preferred fillers are fibrous wollastenite and fibrous calcium carbonate. When glass fiber is used, the reason is not clear, but the effect of improving ductility is small, which is not preferable.

The fiber diameter of these fibrous inorganic fillers is 0.3.
It is necessary that the fiber diameter is 0.5 to 10 μm.
If the thickness is less than 05 μm, the fibrous inorganic filler is apt to aggregate, which is unfavorable because it lowers the ductility and the surface of the molded product. When the fiber diameter exceeds 10 μm, ductility and deterioration of the surface of the molded product are remarkable. The fiber diameter is preferably from 0.1 to 8 μm, more preferably from 1 to 6 μm. In addition, these fiber diameters are number average fiber diameters measured by using a microscope such as an electron microscope.

It is more advantageous to use these inorganic fillers after pre-treating them with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound or an epoxy compound. It is preferable from the viewpoint of obtaining the target strength. Particularly preferred are organic silane compounds, specific examples of which are γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, β-
Epoxy group-containing alkoxysilane compounds such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Mercapto group-containing alkoxysilane compounds such as mercaptopropyltriethoxysilane, and ureido group-containing alkoxy such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, and γ- (2-ureidoethyl) aminopropyltrimethoxysilane Silane compounds, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ An isocyanato group-containing alkoxysilane compound such as -isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2
Amino-containing alkoxysilane compounds such as -aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxypropyltrimethoxysilane, γ- Hydroxy group-containing alkoxysilane compounds such as hydroxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride And other alkoxysilane compounds containing a carbon-carbon unsaturated group. In particular, γ-methacryloxypropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane,
γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ-aminopropyltrimethoxysilane are preferably used. These silane coupling agents are preferably subjected to a surface treatment of the filler in advance and then melt-kneaded with the polyamide resin according to a conventional method.However, without performing the surface treatment of the filler in advance, the filler and the polyamide resin are used. When melt-kneading is used, a so-called integral blending method in which these coupling agents are added may be used.

In the present invention, the amount of the inorganic filler compounded with respect to 100 parts by weight of the polyamide resin is from 5 to 150 parts by weight in total of the non-fibrous inorganic filler and the fibrous inorganic filler. A range of parts by weight is more desirable. Especially from the balance between toughness and rigidity, and high-speed surface impact fracture characteristics,
45 parts by weight are preferred.

In the present invention, when the polyamide resin composition is dissolved in hexafluoroisopropanol and the inorganic filler is recovered, the polyamide resin component attached to the inorganic filler has a unit surface area of the inorganic filler measured by the BET method. 4 g / m ² or more.

The adhesion amount of the polyamide resin component can be determined as follows. The polyamide composition is dissolved in hexafluoroisopropanol to a concentration of 10% by weight. The obtained suspension is centrifuged to settle the inorganic filler and separated. The inorganic filler thus separated is suspended again in hexafluoroisopropanol so as to have a concentration of 10% by weight, separated by a centrifugal separator and collected, and dried by a vacuum dryer until no residual solvent is left. The obtained filler is measured with an infrared spectrophotometer, and the polyamide resin component adhering to the filler is quantified from the calibration curve of the characteristic absorption of the polyamide and the characteristic absorption of the filler (hereinafter referred to as (1) method). ). Also, among the components adhering to the filler, when the nitrogen-containing compound is considered to be substantially only polyamide, the recovered filler is subjected to elemental analysis to determine the nitrogen content and determine the amount of adhered nylon. (Method (2)). Further, when the component adhering to the filler is considered to be substantially a polyamide resin component, for example, the polyamide resin / filler /
In the case of a composition such as (a compound of 1% by weight or less based on 100% by weight of a polyamide resin), the obtained filler is subjected to a thermogravimetric analyzer, and is held in air at 120 ° C. for 5 minutes.
The temperature was raised to 500 ° C at a rate of 20 ° C / min.
By holding for 5 minutes and measuring the heating loss, the substantial amount of the polyamide resin component adhering to the filler can be determined (method (3)). In addition, when components such as a polymer substantially unnecessary for hexafluoroisopropanol were added as other components to the composition of the present invention, a method of removing them with an appropriate solvent or the like in advance was used. Thereafter, it is necessary to determine the amount of the adhered polyamide resin component by an infrared spectrophotometer or elemental analysis as described above.

In order to exhibit the effects of the present invention, it is essential that the polyamide resin component adhere to the filler in a predetermined amount or more. The amount adhering to the filler is 4 g / m ²
If it is less than 3, the effect of improving surface properties, tensile elongation, and imparting ductile destruction at high-speed surface impact are not sufficient, which is not preferable. The adhesion amount needs to be 4 g / m ² or more,
It is preferably at least 5 g / m ² .

In the present invention, glass fibers may be used in combination with the above-mentioned inorganic filler within a range not to impair the effects of the present invention. At this time, it is desirable that the adhesion amount is 4 g / m ² or more including glass fiber as an inorganic filler.

A preferred method for increasing the amount of nylon adhering to the filler is an olefin compound having a carboxylic acid anhydride group in the molecule which can be used as the component (C) in the present invention, or a polymer of such an olefin compound. The addition of coalescence. Specific examples of olefin compounds having a carboxylic acid anhydride group in the molecule or polymers of these olefin compounds include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, or these olefin compounds. Polymers. The polymer of the olefin compound contains a small amount of olefin other than the olefin compound having a carboxylic anhydride group in the molecule, such as styrene, isobutylene, methacrylic acid ester, and acrylic acid ester, which does not impair the effects of the present invention. Although it may be polymerized, it is preferable that the polymer be substantially composed of a polymer of an olefin compound having a carboxylic anhydride group in the molecule.
The polymerization degree of the olefin compound polymer is preferably 2 to 100, more preferably 2 to 50, and most preferably 2 to 20. Among these, maleic anhydride and polymaleic anhydride are most preferably used because of their high ductility and rigidity-imparting effects. As polymaleic anhydride, for example,
J. Macromol. Sci.-Revs. Macromol. Chem., C13 (2), 23
5 (1975) and the like can be used.

The addition amount of these olefin compounds or polymers of these olefin compounds is 100
0.05 to 10 parts by weight, based on the weight of the composition, is preferably 0.05 to 10 parts by weight in view of the effect of improving ductility and the fluidity of the obtained composition, and more preferably 0.1 to 5 parts by weight, more preferably 0 to 5 parts by weight. 0.1 to 1 part by weight, more preferably 0.1 to 1 part by weight.

The olefin compound having a carboxylic anhydride group in the molecule or a polymer of these olefin compounds used herein may have an anhydride structure when substantially melt-kneaded with a polyamide resin. The compound or the polymer of the olefin compound is hydrolyzed and subjected to melt-kneading in the form of a carboxylic acid or an aqueous solution thereof. It may be kneaded.

Conventionally, when a material having poor compatibility with polyamide, such as polyolefin or polyphenylene oxide, is alloyed with polyamide, maleic anhydride is melt-kneaded in advance with polyolefin or polyphenylene oxide in the presence of peroxide. In this way, maleic anhydride is graft-polymerized to polyolefin or polyphenylene oxide, and this is further kneaded with polyamide to cause the grafted maleic anhydride to react with the amino group of the polyamide to compatibilize both polymers. I have been. A filler is further added to such a composition (for example, Japanese Patent Application Laid-Open No. 1-3111).
46, JP-A-3-163164). However, in these methods, since maleic anhydride is mainly consumed for improving compatibility with nylon, it is not enough to increase the amount of the polyamide resin component adhered to the filler of the present invention. Cannot be given sufficient ductility.

Further, the polyamide resin composition of the present invention may contain a crystal nucleating agent such as an organic phosphorus compound and polyether ether ketone, a coloring inhibitor such as hypophosphite, and an antioxidant such as hindered phenol and hindered amine. Additives such as heat stabilizers, lubricants, UV inhibitors, and colorants.

The method for preparing the polyamide resin composition of the present invention is not limited to a particular method as long as it satisfies the requirements specified in the present invention. Specific and efficient examples include a raw material polyamide resin and an inorganic filler. The mixture of the agent and a specific olefin compound or a polymer of the olefin is supplied to a known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll, and the melting point of the nylon resin is adjusted to 220. ~ 330 ° C
And the like.

However, in order to obtain the composition of the present invention, it is necessary that a predetermined amount or more of the polyamide resin component adhere to the filler, and in order to achieve this, it is necessary to sufficiently control the kneading conditions. There is. For example, when a melt kneader is used, it is necessary to control the L / D (screw length / screw diameter) of the kneader, the presence or absence of a vent, the kneading temperature, the residence time, the addition position and the amount of each component. In general, it is preferable to increase the L / D and the residence time of the melt kneader in order to increase the amount of the deposit on the filler. In this case, it is preferable that the polyamide and the filler and the specific olefin compound or the polymer of the olefin compound are sufficiently brought into contact during melt-kneading, and it is not preferable to simultaneously present a large amount of other polymer components that inhibit this. For example, the polyphenylene ether may be added to the polyamide resin composition of the present invention within a range that does not impair the effects of the present invention, but the amount is preferably less than 40 parts by weight based on 100 parts by weight of the polyamide.

The nylon resin composition of the present invention thus obtained is excellent in terms of the surface appearance, dimensional stability, high-speed surface impact ductility, rigidity and ductility of the molded product, and is excellent in injection molding. And extrusion molding, it is particularly useful in the case of forming and using a molded product by blow molding, and by taking advantage of this advantage, it is suitably used as a molded product having a plate-like structure that requires ductile fracture at high-speed surface impact. Can be used. Here, the molded article having a plate-like structure has at least partially a molded part having a length of 10 times or more in the vertical direction with respect to the thickness of a predetermined portion of the molded article. These molded products include various forms such as lids, caps, containers, boxes, and plate-like materials.

[0033]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the blending ratios shown in Examples and Comparative Examples are all parts by weight.

In the following examples, the following methods were used to evaluate the material strength, the surface smoothness of the molded product, the adhesion amount of the polyamide resin, the surface area measurement, and the high-speed surface impact.

[Material strength] Measured according to the following standard method.

Tensile strength: ASTM D638 Flexural modulus: ASTM D790 Izod Impact strength: ASTM D256 [Surface smoothness] A square plate of 80 × 80 × 3 mm was injection molded, and the sharpness of the reflected image of the fluorescent lamp was measured on the surface of the obtained molded product. It was visually observed and used as an index of smoothness. ：: The outline of the fluorescent lamp is clearly observed, △: The outline of the fluorescent lamp is blurred, and X: The fluorescent lamp is not visible.

[Measurement of Surface Area by BET Method] A chip of the obtained resin composition was melt-kneaded, and the resulting resin composition was placed in air for 500 minutes.
The filler obtained as ash was heated for 5 hours at
The measurement was performed using LSORP36 (manufactured by Nippon Bell Co., Ltd.) while adsorbing nitrogen gas.

[Measurement of Amount of Polyamide Resin Component Adhered to Inorganic Filler] The filler obtained as the ash and the polyamide resin were mixed in a powder state, and infrared absorption was measured using an infrared spectrophotometer. A calibration curve is prepared in advance. Using hexafluoroisopropanol from the polyamide resin composition, the inorganic filler was separated by the method described above, its infrared absorption was measured, and the amount of attached nylon was quantified using a previously measured calibration curve. (Method (1)).

In the case of a composition comprising an olefin compound having a carboxylic anhydride group in a molecule of not more than 1 part by weight per 100 parts by weight of the polyamide resin, the inorganic filler and the polyamide resin, or a composition comprising a polymer of the olefin compound. Is
The heating loss value (method (3)) of the inorganic filler recovered with hexafluoroisopropanol was in good agreement with the value obtained by infrared absorption (method (1)) in the error range. Also,
When the nitrogen content of the other additives is 1 part by weight or less with respect to 100 parts by weight of the nitrogen content derived from the polyamide resin in the composition, the polyamide resin component quantitative value by elemental analysis (method (2)) is also red. Value obtained by external absorption ((1) method)
Well matched.

[High-speed surface impact test] Using a servo pulser EHF-U2H-20L type high-speed surface impact tester manufactured by Shimadzu Corporation, a square plate having a thickness of 2 mm was used as a sample, the tip diameter of the punch was 5/8 inch at 23 ° C, and the collision speed was high. The test was performed at 2.5 m / s.

Example 1 The melt kneading of a polyamide resin, an inorganic filler and an olefin compound having a carboxylic acid group in the molecule or a polymer of the olefin compound was carried out using a TEX30 twin screw extruder manufactured by Nippon Steel Works (L / D = 45). .5). 100 parts by weight of nylon 6 resin having a relative viscosity of 2.70 and a particle size of 0.8
Dry blending of 0.4 parts by weight of maleic anhydride with 16 parts by weight of kaolin and 100 parts by weight of a nylon resin surface-treated with a μm aminosilane was carried out at a cylinder temperature of 260 ° C. and a screw rotation speed of 150 rpm. The whole amount was supplied to a feeder of an extruder and melt-kneaded. The extruded gut was cooled and pelletized with a pelletizer.

This was injection-molded into various test pieces, and the surface smoothness, material strength, high-speed surface impact and the like were measured. The results are shown in Table 1. The adhesion amount of the polyamide resin component was determined by the method (1), the method (2), and the method (3), and agreed within the error range.

[0043]

[Table 1]

Comparative Example 1 Kneading, pelletizing, injection molding, and measurement of physical properties were carried out in exactly the same manner as described in Example 1 except that maleic anhydride was not added. The results are as shown in Table 2,
The composition obtained here has a small amount of the polyamide resin component attached to the inorganic filler, tensile elongation at break, impact value,
The high-speed surface impact properties were insufficient compared with the composition of the present invention shown in Example 1.

[0045]

[Table 2]

Examples 2 to 5, Comparative Examples 2 to 7 As shown in Tables 1 and 2, the types and amounts of polyamide resins, inorganic fillers, olefin compounds having carboxylic anhydride groups in their molecules, and the like, Except that the extrusion method was changed, melt kneading was performed in the same manner as described in Example 1,
Pelletization, injection molding, and measurement of physical properties were performed, and the results shown in Tables 1 and 2 were obtained. The polyamide resin component adhering to the filler is described in Examples 2 to 5 and Comparative Examples 2 to 5 in (1) method, (2)
Method and (3) method, and both agreed within the error range. Comparative Examples 6 and 7 were determined by the method (2).

As shown in Comparative Examples 2 and 3, even if the composition was exactly the same as that of Example 1, if the extrusion conditions were not appropriate, the amount of the polyamide resin component attached to the filler was insufficient. Tensile elongation, impact strength, high-speed surface impact properties,
It turns out that surface smoothness is inferior.

Further, even when the types of the nylon resin and the inorganic filler are different, the tensile elongation, the impact strength, the high-speed surface impact property, and the tensile elongation are clearly higher than in the case where (c) the olefin compound or the polymer of the olefin compound is not added. It can be seen that the surface smoothness is improved. When glass fibers were used, no remarkable improvement effect was observed (Comparative Examples 6 and 7).

Example 6, Comparative Examples 8 to 10 As shown in Table 3, a polyamide resin, an inorganic filler, a polyphenylene oxide resin and maleic anhydride were blended, and the mixture was melt-kneaded in the same manner as described in Example 1. Pelletization, injection molding, and measurement of physical properties were performed, and the results shown in Table 3 were obtained. The polyphenylene oxide was removed using chloroform, and the amount of nylon adhering to the filler was determined by infrared spectroscopy (method (1)) and elemental analysis (method (2)). When a large amount of polyphenylene oxide was added, the amount of adhered nylon decreased, and good characteristics could not be obtained.

[0050]

[Table 3]

[0051]

As described above, the nylon resin composition of the present invention has both excellent stiffness and toughness, especially excellent high-speed impact fracture characteristics, and balances the surface appearance and dimensional stability of a molded product. It is molded by injection molding, extrusion molding, blow molding, or the like, and can be suitably used, for example, as a molding material having a plate-like portion, in which high-speed surface impact characteristics are required.

Claims (11)

[Claims] 1. A non-fibrous inorganic filler having an average particle diameter of 0.05 to 10 μm and / or a fiber diameter excluding glass fibers of 100 parts by weight of (A) a polyamide resin.
A polyamide resin composition obtained by melting and kneading 5 to 150 parts by weight of a fibrous inorganic filler having a particle size of from 0.05 to 10 μm, wherein the composition is dissolved in hexafluoroisopropanol to recover the inorganic filler. A polyamide resin composition, wherein the amount of the polyamide resin component attached to the inorganic filler is 4 g / m ² or more per unit surface area of the inorganic filler measured by a BET method. 2. An amount of (C) an olefin compound having a carboxylic acid anhydride group in a molecule or a polymer of the olefin compound in an amount of 0.05 to 100 parts by weight of the polyamide resin (A).
The polyamide resin composition according to claim 1, wherein 10 to 10 parts by weight is melt-kneaded. 3. The polyamide resin composition according to claim 1, wherein the polyamide resin is at least one selected from aliphatic polyamide resins having a melting point of 200 ° C. or higher. 4. The polyamide resin according to claim 1, wherein the polyamide resin is at least one selected from nylon 66 and nylon 6.
The polyamide resin composition according to any one of the above. 5. The polyamide resin according to claim 1, wherein the olefin compound is at least one selected from maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, and aconitic anhydride. Composition. 6. The polyamide resin composition according to claim 1, wherein the polymer of the olefin compound is polymaleic anhydride. 7. An inorganic filler comprising kaolin, wollastenite,
The polyamide resin composition according to any one of claims 1 to 6, which is at least one selected from talc. 8. The polyamide resin composition according to claim 1, wherein no more than 40 parts by weight of the polyphenylene oxide resin is added to 100 parts by weight of the polyamide resin (A). 9. A molded article having a plate-like portion comprising the polyamide resin composition according to claim 1. A fiber diameter of (B) excluding non-fibrous inorganic filler and / or glass fiber having an average particle diameter of 0.05 to 10 μm per 100 parts by weight of (A) polyamide resin.
A polyamide resin adhered to the inorganic filler when the composition is dissolved in hexafluoroisopropanol and the inorganic filler is recovered by melting and kneading 5 to 150 parts by weight of a fibrous inorganic filler of 05 to 10 μm. A method for producing a polyamide resin composition wherein the component is 4 g / m ² or more per unit surface area of the inorganic filler measured by the BET method. 11. An amount of (C) an olefin compound having a carboxylic acid anhydride group in a molecule or a polymer of the olefin compound in an amount of 0.0
The polyamide resin composition according to claim 10, wherein 5 to 10 parts by weight are melt-kneaded.