JP2001302914A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which excels in sliding characteristics (PV value, friction, and wear characteristics) and, simultaneously, excels in heat resistance, flowability upon melting, strength, and toughness. SOLUTION: The resin composition comprises 100 pts.wt. resin component of the sum of (A) an aromatic polyamideimide resin to be obtained by conducting the imidation reaction after completion of >=70% amidation reaction in reacting an aromatic tricarboxylic anhydride or an aromatic tricarboxylic anhydride and an aromatic tetracarboxylic anhydride with a diisocyanate compound and (B) a polyarylene sulfide resin, and (C) 0.1-30 pts.wt. organic clay composite to be obtained by treating a swelling layered silicate with an organic cation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel resin composition having excellent slidability (friction and wear properties), low specific gravity, and excellent heat resistance, fluidity and strength upon melting, and toughness. Related to

[0002]

2. Description of the Related Art Aromatic polyamideimide resin is a plastic material having excellent heat resistance, mechanical strength, electrical properties, chemical resistance and self-lubricating properties. In many cases, injection molding is difficult because of poor quality. Therefore, by blending a polyarylene sulfide resin (hereinafter abbreviated as PAS resin) represented by a polyphenylene sulfide resin (hereinafter abbreviated as PPS) having excellent melt fluidity, heat resistance, slidability and melting property are improved. It is known that a molding material having excellent fluidity at the time can be obtained. (Patent No. 2860
No. 43)

However, in the above-mentioned molding materials, a resin composition having a sufficient mechanical strength typified by flexural modulus cannot be obtained unless a filler is compounded. Therefore, a considerable amount of reinforcing material such as glass fiber or carbon fiber is required. It is common to add.

However, when these fillers are added,
Although the mechanical strength is improved, the conventional sliding characteristics have been greatly reduced, which is a new problem.

[0005]

SUMMARY OF THE INVENTION The problem to be solved by the present invention is as follows, without impairing the slidability of a resin composition obtained by alloying an aromatic polyamideimide resin and a PAS resin using a conventional technique. It is to improve the mechanical strength.

[0006]

Means for Solving the Problems In order to solve these problems, the present inventors have made intensive studies, and as a result, by adding a specific organoclay composite, the conventional slidability was improved. It has been found that the mechanical strength can be improved while maintaining it. That is, in the present invention, when the (A) aromatic tricarboxylic anhydride, or the aromatic tricarboxylic anhydride and the aromatic tetracarboxylic anhydride are reacted with the diisocyanate compound, the amidation reaction is completed by 70% or more. And then with respect to 100 parts by weight of the total resin component comprising the aromatic polyamideimide resin obtained by performing the imidization reaction and (B) the polyarylene sulfide resin.
(C) An object of the present invention is to provide a resin composition containing 0.1 to 30 parts by weight of an organoclay composite obtained by treating a swellable layered silicate with an organic cation.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The production of the aromatic polyamide-imide resin as the component (A) used in the resin composition of the present invention is generally carried out by appropriately performing a polymerization temperature, a reaction time, and a method for adding a catalyst. It can be performed by controlling the amidation reaction and the imidation reaction, but basically, the amidation reaction is carried out under the condition that the imide group formation reaction does not occur until the amide group formation reaction is substantially completed, Then, the reaction can be carried out under conditions that cause an imidization reaction.

In order to obtain the aromatic polyamide-imide resin used in the present invention, as a method of performing an imidization reaction after the completion of the amidation reaction, a method of controlling the polymerization temperature is simple. That is, an aromatic tricarboxylic anhydride (including partially containing an aromatic tetracarboxylic anhydride) and a diisocyanate compound in a solvent at 50 to 100 ° C, preferably 60 to 100 ° C, more preferably 80 to 100 ° C. And the amidation reaction is 70% or more, preferably 80%, more preferably 90%, and most preferably
After completion of 95% or more, usually 100 to 200 ° C, preferably 105 to 200 ° C, and more preferably 110 to 1
This is a method in which an imidization reaction is performed in a temperature range of 80 ° C.

[0009] The reaction temperature of the aromatic tricarboxylic anhydride (including partially containing the aromatic tetracarboxylic anhydride) with the diisocyanate compound is an important condition, and by controlling this, the reaction temperature of the present invention can be improved. The aromatic polyamideimide resin constituting the resin composition used in the present invention can be produced. The temperature in each stage may be set as long as it is within the temperature range. For example,
The temperature may be raised, kept at a constant temperature, or a combination of these, but it is preferable to keep the temperature at a constant. When the temperature of each stage is lower than this range, the amide group and the formation reaction of the imide group are not completed, and as a result, the degree of polymerization of the obtained aromatic polyamideimide resin does not increase. Things become brittle. When the temperature of the amidation reaction is higher than the above range, the reaction of forming an amide group and the reaction of forming an imide group occur at the same time, so that the obtained aromatic polyamideimide resin is inferior in melt fluidity and retention stability. Become something.

The reaction time between the aromatic tricarboxylic anhydride and the diisocyanate compound is usually 3 times for the amidation reaction.
0 minute to 5 hours, preferably 30 minutes to 2 hours, and the imidization reaction is usually 30 minutes to 10 hours, preferably 1 minute to 1 hour.
8 hours to 8 hours. If the respective reaction times are too short, the degree of polymerization of the aromatic polyamideimide obtained will not be increased, and the resin composition of the present invention will be brittle. On the other hand, if the respective reaction times are too long, the resulting aromatic polyamide-imide resin will have poor melt fluidity. It is necessary to track the components of the amide group and the component of the imide group during the polymerization reaction, and this method can be performed by a known infrared spectroscopy or gas chromatogram method.

The aromatic tricarboxylic acid used for producing the aromatic polyamide-imide resin used in the resin composition constituting the present invention is a compound represented by the following general formula.

[0012]

Embedded image (In the formula, Ar represents a trivalent aromatic group containing at least one benzene ring.)

Specific examples of Ar include the following, but two or more compounds may be used in combination.

[0014]

Embedded image Among these, aromatic tricarboxylic anhydrides include:
Trimellitic anhydride is preferred.

The above aromatic tricarboxylic anhydrides of 0 to 5
It is also possible to replace 0 mol% with aromatic tetracarboxylic anhydride. However, if the amount of the aromatic tetracarboxylic anhydride is larger than the above range, the obtained aromatic polyamideimide resin tends to be brittle. The aromatic tetracarboxylic anhydride is a compound represented by the following general formula.

[0016]

Embedded image (In the formula, Ar ₁ represents a trivalent aromatic group containing at least one benzene ring.)

Specific examples of the aromatic tetracarboxylic anhydride are as follows.

[0018]

Embedded image

The diisocyanate compound used for producing the aromatic polyamideimide resin used in the resin composition constituting the present invention is a compound represented by the following general formula.

O ＝ C ＝ N−RN−C ＝ O (wherein R represents a divalent aromatic and / or aliphatic group)

Specific examples thereof include the following, but a mixture of two or more compounds can also be used.

[0022]

Embedded image

Particularly preferred are m-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-
Examples include tolylene diisocyanate and methylene di (4-phenyl isocyanate).

In order to produce an aromatic polyamideimide resin suitable for the resin composition used in the present invention, an aromatic tricarboxylic anhydride component (which can contain the above-mentioned dicarboxylic acid and tetracarboxylic anhydride) can be used. When the number of moles of the diisocyanate component is A and B, the molar ratio between the two is preferably maintained at 0.9 <A / B <1.1, and more preferably 0.99 <A / B. B <1.01
Is to be kept.

In the present invention, a solvent is used to smoothly produce an aromatic polyamideimide resin. The solvent used is not particularly limited as long as it is inert to the diisocyanate compound.
Examples of the solvent include a solvent having compatibility with an aromatic polyamideimide produced such as methylpyrrolidone and dimethylformamide, and a polar solvent having no compatibility with an aromatic polyamideimide produced such as nitrobenzene and nitrotoluene. These may be used alone or as a mixture. Preferred are solvents such as N-methylpyrrolidone and dimethylformamide which are compatible with polyamideimide. These solvents are used at a ratio of 0.1 to 4 mol / l based on the ratio of the monomer raw material to the solvent.

Various catalysts can be used for the production of the aromatic polyamide-imide resin constituting the resin composition used in the present invention. However, the amount of the catalyst should be minimized in order not to impair the moldability during melting. It should be stopped and preferably not used as long as the polymerization rate is at a sufficient level. Specific examples of the catalyst include tertiary amines such as pyridine, quinoline, isoquinoline, trimethylamine, N, N-diethylamine, and triethylamine; metal salts of weak acids such as cobalt acetate and cobalt naphthenate; heavy metal salts;
Examples thereof include alkali metal salts.

The water content of the polymerization system composed of a solvent, a monomer and the like is preferably kept at 500 ppm or less, more preferably 100 ppm or less, most preferably 50 ppm or less. The water content in the system is 50
If it exceeds 0 ppm, the degree of polymerization of the aromatic polyamideimide of the present invention is not increased, so that it is not preferable.

The aromatic polyamideimide resin constituting the resin composition of the present invention is precipitated and washed with alcohols such as methanol and isopropanol, ketones such as acetone and methyl ethyl ketone, and hydrocarbons such as heptane and toluene. Although it is recovered as a powder, it is not possible to directly concentrate the polymerization solvent. Furthermore, after concentrating to a certain extent, a method of removing the solvent under reduced pressure with an extruder or the like to form pellets can also be performed.

The degree of polymerization of the aromatic polyamideimide resin suitable for the resin composition used in the present invention is from 0.15 dl / g to 0.15 dl / g in terms of reduced viscosity measured in dimethylformamide at 30 ° C. at a concentration of 1 g / dl. 1.0 dl / g is suitably used, and more preferably 0.2 dl / g to 0.1 dl / g.
6 dl / g is most preferably 0.2 to 0.5 dl / g.
g.

The PAS resin as the component (B) used in the resin composition of the present invention is represented by the formula [-Ar-S-]
(However, -Ar- is an arylene group.) An aromatic polymer having a repeating unit of arylene sulfide as a main constituent element. [-Ar-S-] is 1
When defined as moles (basic moles), the PA used in the present invention is
S is a polymer containing this repeating unit usually at least 50 mol%, preferably at least 70 mol%, more preferably at least 90 mol%. Examples of the arylene group include a p-phenylene group, an m-phenylene group, a substituted phenylene group (the substituent is preferably an alkyl group having 1 to 6 carbon atoms, or a phenyl group), p, p′-di. Phenylene sulfone group, p, p'-biphenylene group, p, p '
-Diphenylenecarbonyl group, naphthylene group and the like. As the PAS resin, a polymer having mainly the same arylene group can be preferably used, but from the viewpoint of processability and heat resistance, a copolymer containing two or more types of arylene groups can also be used.

Among these PAS resins, PP having a repeating unit of p-phenylene sulfide as a main constituent element
S resin is particularly preferred because it has excellent processability and is industrially easily available. In addition, polyarylene ketone sulfide and the like can be used. Specific examples of the copolymer include a random or block copolymer having a repeating unit of p-phenylene sulfide and m-phenylene sulfide, a random or block copolymer having a repeating unit of phenylene sulfide and a repeating unit of arylene ketone sulfide, phenylene sulfide And a random or block copolymer having a repeating unit of the formula (1) and a repeating unit of an arylene sulfone sulfide. These PAS resins are preferably crystalline polymers. The PAS resin is preferably a linear polymer from the viewpoint of toughness and strength. Such a PAS resin can be obtained by a known method of polymerizing an alkali metal sulfide and a dihalogen-substituted aromatic compound in a polar solvent (for example, JP-B-63-33775).

Examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide. Sodium sulfide or the like generated by reacting NaSH and NaOH in the reaction system can also be used.
Examples of the dihalogen-substituted aromatic compound include, for example, p-dichlorobenzene, m-dichlorobenzene, 2,5-dichlorotoluene, p-dibromobenzene, 2,6-dichloronaphthalene, 1-methoxy-2,5-dichlorobenzene, , 4'-dichlorobiphenyl, 3,5-dichlorobenzoic acid, p, p'-dichlorodiphenyl ether,
4,4'-dichlorodiphenylsulfone, 4,4'-dichlorodiphenylsulfoxide, 4,4'-dichlorodiphenylketone and the like can be mentioned. They are,
Each of them can be used alone or in combination of two or more.

A small amount of a polyhalogen-substituted aromatic compound having three or more halogen substituents per molecule can be used in order to introduce a slight branched or cross-linked structure into the PAS resin. Preferred examples of the polyhalogen-substituted aromatic compound include 1,2,3-trichlorobenzene, 1,2,3-tribromobenzene, 1,2,4-trichlorobenzene, 1,2,4-tribromobenzene,
Examples thereof include trihalogen-substituted aromatic compounds such as 1,3,5-trichlorobenzene, 1,3,5-tribromobenzene, and 1,3-dichloro-5-bromobenzene, and alkyl-substituted products thereof. These can be used alone or in combination of two or more. Among these, 1,2,4-trichlorobenzene, 1,1,
3,5-Trichlorobenzene and 1,2,3-trichlorobenzene are more preferred.

Examples of the polar solvent include aprotic organic amides represented by N-alkylpyrrolidone such as N-methyl-2-pyrrolidone, 1,3-dialkyl-2-imidazolidinone, tetraalkylurea, hexaalkylphosphoric triamide and the like. Solvents are preferred because the stability of the reaction system is high and a high molecular weight polymer is easily obtained. The PAS resin used in the present invention has a temperature of 310 ° C. and a shear rate of 1200.
/ Melt viscosity measured per second is usually 10 to 600 Pa ·
s, preferably 50 to 550 Pa · s, more preferably 70 to 550 Pa · s. When two or more PAS resins having different melt viscosities are blended and used, the melt viscosity of the blend is preferably within the above range.
It is particularly desirable that the PAS resin has a melt viscosity of 100 Pa · s or more from the viewpoint of mechanical strength and toughness. If the melt viscosity of the PAS resin is too low, physical properties such as mechanical strength and toughness may be insufficient. If the melt viscosity of the PAS resin is too large, the melt fluidity may be insufficient, and the injection moldability and the extrusion moldability may be insufficient.

As the PAS resin used in the present invention, a resin washed after the polymerization can be used.
It is preferable to use an aqueous solution containing an acid such as hydrochloric acid or acetic acid, a solution treated with a mixed solution of water and an organic solvent, or a solution treated with a salt solution such as ammonium chloride. In particular, when a PAS resin washed in a mixed solvent adjusted to acetone: water = 1: 2 (volume ratio) until the pH becomes 8 or less is used, the melt flowability and mechanical properties of the resin composition are increased. Physical properties can be further improved.

The PAS resin used in the present invention is 100 μm.
It is desirable that the particles have an average particle diameter of at least m. If the average particle size of the PAS resin is too small, the amount of feed is limited during melt extrusion by an extruder,
The residence time of the resin composition in the extruder is prolonged, which may cause problems such as deterioration of the resin composition. Further, this is not desirable in terms of manufacturing efficiency.

The organoclay composite as the component (C) of the resin composition of the present invention is a complex obtained by treating a layered silicate with an organic cation. Examples of the layered silicate include those mainly composed of so-called clay minerals, and typical examples thereof include smectite, vermiculite, and mica. Examples of smectites include montmorillonite, beidellite, hectorite, saponite and the like. Vermiculite includes dioctahedral vermiculite and trioctahedral vermiculite, and examples of mica include teniolite, tetrasilicic mica, muscobite, illite, sericite, phlogovite, biotite, and the like. These silicates may be natural minerals, or may be those synthesized by hydrothermal synthesis, melting method, solid phase method and the like.

As the organic cation used in the present invention, 1
Secondary to secondary and tertiary amines and their salts, quaternary ammonium salts, diamines and amino acid derivatives and their salts are mentioned. Examples of the primary amine include coconutamine, stearylamine, oleylamine and the like. Examples of the secondary amine include distearylamine, dimethylcoconutamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, and dimethylstearylamine. As the tertiary amine,
Examples include dilauryl monomethylamine and trioctylamine. As the quaternary ammonium salt, octadecyltrimethylammonium salt, dodecyltrimethylammonium salt, stearyltrimethylammonium salt, alkyltrimethylammonium salt, behenyltrimethylammonium salt, stearyldimethylethylammonium salt, alkyldimethylethylammonium salt, behenyldimethylethylammonium salt, Stearyl diethyl methyl ammonium salt, alkyl diethyl methyl ammonium salt, behenyl diethyl methyl ammonium salt, benzyl dimethyl stearyl ammonium salt, benzyl dimethyl behenyl ammonium salt, benzyl methyl ethyl stearyl ammonium salt, dibehenyl dihydroxy ethyl ammonium salt, dodecyl monomethyl diethanol ammonium salt, Dioctadime Le ammonium salts. Examples of the diamine include stearyl propylene diamine and tallow propylene diamine. Examples of the amino acid derivatives include coconutamine acetate, stearylamine acetate and the like.
Among them, quaternary ammonium salts are preferable, and among them, octadecyltrimethylammonium salt and dioctadecyldimethylammonium salt are suitably used.
Further, the salt is not particularly limited, but chloride or bromide is preferred.

As a method of treating the layered silicate with the above-mentioned organic cation, the layered silicate powder is suspended in a solvent such as water or alcohol, the organic cation is added in the form of a salt, and the mixture is stirred. It is obtained by washing and drying. By this treatment, the metal cations existing between the layers of the layered silicate are replaced with the organic cations and coordinated between the layers to form an organic clay complex. The ion exchange capacity of the layered silicate can be measured by a method such as a methylene blue adsorption method (Japan Bentonite Industry Association test method, JBAS-107-91). The organic cation substitution amount is calculated from a weight loss due to thermal decomposition of an organic substance using a thermogravimetric device such as a suggestive heat / thermobalance measurement (TG-DTA) device.

The amount of the organic cation substituted in the organoclay composite according to the present invention is expressed in milliequivalents per 100 g of the layered silicate, and is generally from 25 to 260 meq / 100 g, preferably from 50 to 200 meq / 100 g. In particular, 75 to 150 meq / 100 g is suitable.

The resin components (A) and (B) of the resin composition of the present invention are based on (A)
The aromatic polyamide-imide resin of the component is usually 5 to 95% by weight, preferably 20 to 70% by weight, more preferably 2 to 70% by weight.
The amount is 0 to 65% by weight, and the amount of the PAS resin as the component (B) is usually 5 to 95% by weight, preferably 30 to 80% by weight, and more preferably 35 to 80% by weight. When the component (A) exceeds 95% by weight, the fluidity at the time of melting decreases,
If it is less than 5% by weight, the heat resistance will decrease.

The organoclay composite of the component (C) is usually added in an amount of 0.1 to 100 parts by weight of the total of the components (A) and (B).
-30 parts by weight, preferably 1-20 parts by weight, are added.
When the amount of the component (C) is larger than this amount, the dispersibility becomes insufficient,
If the amount is small, the effect of improving mechanical strength cannot be expected.

The resin composition used in the present invention may be prepared by melt-kneading an aromatic polyamide-imide resin, a PAS resin, or an organic clay composite, or may be prepared by polymerizing the aromatic polyamide-imide resin in advance. Add the complex,
Thereafter, either of the methods of melt kneading with the PAS resin may be used. . The melt-kneading temperature is from 250 to 400C, preferably from 280 to 360C. The kneading method can be performed using an extruder, a kneader, a Banbury mixer, a mixing roll, or the like, but a preferred method is a method using a twin-screw extruder.

The resin composition used in the present invention may contain, if desired, pigments, compatibilizers, lubricants, plasticizers, stabilizers, ultraviolet rays, flame retardants, additives of flame retardant auxiliaries, and other additives. Other components, such as resins and elastomers, can be appropriately compounded. Also,
Fillers can also be added as long as the sliding characteristics are not impaired.

Examples of the pigment include titanium oxide, zinc sulfide and zinc oxide.

The compatibilizing agent is used for improving the compatibility between the aromatic polyamideimide resin and the PAS resin. Typical examples thereof include γ-aminopropyl trialkoxysilane compounds and γ-glycol. Functional group-substituted alkyl / alkoxysilane compounds such as sildoxypropyl / trialkoxysilane, γ-mercaptopropyl / trialkoxysilane, γ-isocyanatopropyl / trialkoxysilane, and γ-ureidopropyl / trialkoxysilane; Tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-biphenyl diisocyanate, 4,4 '
-Aromatic polyisocyanates such as diphenyl ether diisocyanate and triphenylmethane triisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and meta-xylylene diisocyanate; thioisocyanates; and polyhydric alcohol addition of the aromatic or aliphatic polyisocyanates. Body, water adduct,
Amine adducts, exemplified by isocyanurate-modified counterparts, polyisocyanate compounds, bisphenol A, diglycidyl ether of bisphenols such as resorcinol, hydroquinone, catechol, and epoxy resins,
Epoxy group-containing compounds such as novolak type epoxy resin, epoxidized polyolefin, and epoxidized soybean oil can be exemplified.

Typical examples of the lubricant include mineral oil, silicone oil, ethylene wax, polypropylene wax, metal salts such as sodium stearate, metal salts such as sodium montanate, and montanamide.

Examples of the flame retardant include phosphoric esters such as triphenyl phosphate, brominated compounds such as decabromobiphenyl, pentabromotoluene, and brominated epoxy resins; and nitrogen-containing phosphorus compounds such as melamine derivatives. Can be A flame retardant aid may be used, and examples thereof include compounds such as antimony, boron, and zinc.

As other additives, sliding aids such as tetrafluoroethylene, sterically hindered phenols, stabilizers such as phosphite compounds, oxalic acid diamide compounds, and ultraviolet rays exemplified by sterically hindered amine compounds There are absorbents and the like.

Examples of other resins include epoxy resin,
Examples thereof include phenoxy resins, polyesters such as polyethylene terephthalate and polybutylene terephthalate, and aromatic resins such as polyphenylene ether, polysulfone, polycarbonate, polyether ketone, polyether imide, and polyether ether ketone.

Examples of the elastomer include polysulfide rubber, polyester elastomer, polyamide elastomer, polyesteramide elastomer, polyolefin elastomer, silicone rubber, fluoro rubber and the like.

Examples of the filler include mainly fibrous fillers such as glass fiber, milled fiber, carbon fiber, potassium titanate fiber, boron fiber, and silicon carbide fiber. Those treated with a silane coupling agent can be suitably used.

In the present invention, (C) a swellable layered silicate is treated with an organic cation with respect to 100 parts by weight of the aromatic polyamideimide resin (A) and the PAS resin (B). A resin composition containing 0.1 to 30 parts by weight of the organoclay composite is obtained. The molding is performed by a usual injection molding method, and the cylinder temperature is 29.
The temperature is set in the range of 0 to 360 ° C, and the mold is desirably set to 120 to 160 ° C in order to obtain sufficient heat resistance. Also,
It is desirable to perform heat treatment after molding for the purpose of improving heat resistance and removing residual stress. In particular, when the mold temperature is 120
If the molding is performed at a temperature lower than ℃, it is preferable to perform a heat treatment. The method of heat treatment is not particularly limited,
For example, a usual hot-air oven, microwave oven or microwave oven is used. Heat treatment temperature is usually 150-3
00 ° C, preferably 180 to 280 ° C, most preferably 200 to 260 ° C, and the heat treatment time varies depending on the treatment temperature, but usually 30 seconds to 48 hours, preferably 1 hour to 1 hour.
Perform at normal pressure or reduced pressure for 36 hours.

[0054]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The substances used in the following examples and comparative examples are those manufactured by the following and synthetic examples.

Synthesis Example 1 (Production of aromatic polyamide-imide resin) Water content 15 pp
m-N-methylpyrrolidone was charged into a reactor equipped with a 5-liter stirrer, a thermometer, and a reflux condenser fitted with a drying tube filled with calcium chloride at the tip. Here, 555 g (50 mol%) of trimellitic anhydride, followed by
503.3 g (50 mol%) of 2,4-tolylene diisocyanate were added. The water content in the system when trimellitic anhydride was added was 30 ppm. Initially, the temperature of the contents was set to 90 ° C. over 20 minutes from room temperature, and polymerization was carried out at this temperature for 50 minutes. While the polymerization was being performed, the amount of the isocyanate group reduced and the amount of the imide group formed in 2,4-tolylene diisocyanate were measured. The measurement was performed by sampling a small amount of the reaction solution with a syringe and quantifying the absorption at 2276 cm ^-1 of the isocyanate group by infrared spectroscopy. When polymerization was carried out for 50 minutes, the amount of isocyanate groups was reduced to 50 mol%, but no absorption of imide groups was observed. This confirmed that the amidation reaction was completed before the imidation reaction occurred. After that, it takes 115 minutes to reach 115 ° C.
The polymerization was continued for 8 hours while maintaining the temperature. After the polymerization was completed, the polymer solution was dropped into 6 liters of methanol with vigorous stirring. The precipitated polymer was separated by suction filtration, further redispersed in methanol, washed well, filtered and dried at 135 ° C. for 6 hours to obtain a polyamideimide powder. Dimethylformamide solution (concentration 1.0
g / dl) and the reduced viscosity at 30 ° C. was measured to be 0.25 dl / g.

Synthesis Example 2 (Production of an organoclay composite) Montmorillonite (Kunipia F, manufactured by Kunimine Industries: ion exchange capacity: 115 meq /
100 g) of a 2% by weight aqueous dispersion was prepared and allowed to swell by standing overnight. Next, the aqueous solution is heated to 60 ° C., and a 5% by weight aqueous solution of octadecyltrimethylammonium chloride is gradually added with stirring (corresponding to the ion exchange capacity of montmorillonite), and the cation exchange reaction proceeds. After stirring at 60 ° C. for 1 hour, the mixture is filtered and washed three times with hot water at 60 ° C. The solid obtained is 60
The resulting mixture was dried with a hot-air dryer at 12 ° C. for 12 hours. When the interlayer distance of the obtained organoclay composite was analyzed with an X-ray diffractometer, it was 20.3 °. The organic cation substitution amount was 20% by weight as a result of measurement using a thermogravimeter.

Example 1 50 parts by weight of the aromatic polyamideimide resin produced in Synthesis Example 1 and a PPS resin (W-205 manufactured by Kureha Chemical Industry Co., Ltd.)
A, melt viscosity measured at a shear rate of 1200 / sec is 100
Pa · s) was blended with 5 parts by weight of the organoclay mineral produced in Synthesis Example 2 with respect to 50 parts by weight,
The resin composition was produced by melt-kneading at 20 ° C. and pelletizing. The pellet was injection molded to obtain a 1/8 inch thick bending test piece. Using this test piece, bending strength and bending strain (Shimadzu Corporation Autograph: AG5000)
B) was measured. The heat distortion temperature (18.6 kg / cm ² load) was also measured using this test piece under a nitrogen atmosphere (Yasda Seiki Co., Ltd. HD-500-PC). The sliding characteristics were measured by molding a sliding ring and using a thrust friction and wear tester (manufactured by Orientec). Steel (S45C) was used as a mating material. The results are shown in Table 1.

Example 2 Example 1 was repeated except that the PPS resin shown in Table 1 was used.
A resin composition was manufactured and evaluated in the same manner as described above.

Example 3 A resin composition was prepared in the same manner as in Example 1, except that an organic clay composite (B) was produced using dioctadecyldimethylammonium chloride as the organic cation. evaluated.

Comparative Example 1 50 parts by weight of the aromatic polyamideimide resin produced in Synthesis Example 1 and a PPS resin (W-205 manufactured by Kureha Chemical Industry Co., Ltd.)
A, melt viscosity measured at a shear rate of 1200 / sec is 100
5 parts by weight of montmorillonite (Kunimine Industries: Kunipia F: ion exchange capacity: 115 meq / 100 g) not treated with an organic cation was blended with 50 parts by weight of Pa · s) at 320 ° C. using a twin screw extruder. And melt-kneaded in a pellet to produce a resin composition. Injection molding and measurement of physical properties were performed in the same manner as in Example 1.

Comparative Example 2 50 parts by weight of the aromatic polyamideimide resin produced in Synthesis Example 1 and a PPS resin (W-205 manufactured by Kureha Chemical Industry Co., Ltd.)
A, melt viscosity measured at a shear rate of 1200 / sec is 100
20 parts by weight of glass fiber (manufactured by Asahi Fiberglass Co., Ltd .: CS03JAFT523) is blended with 50 parts by weight of Pa · s), melt-kneaded at 320 ° C. using a twin-screw extruder to pelletize the resin composition. Manufactured. Injection molding and measurement of physical properties were performed in the same manner as in Example 1.

Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 PAI resin 50 50 50 50 50 PPS resin (A) 50 50 50 50 PPS resin (B) 50 Organized montmorillonite (B) 5 Organized montmorillonite (B) 5 Untreated montmorillonite 5 Glass fiber 20曲 げ Flexural strength (MPa) 100 90 100 80 100 Flexural modulus (GPa) 8 9 8 5 8 Bending strain (%) 2.0 1.8 1.9 1.8 1.8 DTUL (° C) 230 240 235 190 240 240 Limit PV (kg / cm ² · cm / s) A * 1 1800 2000 1700 1700 600 B * 2 1500 1500 1500 1400 100 550 C * 3 1000 1300 1000 800 400 Dynamic friction coefficient 0.14 0.14 0.15 0.14 0.32 ratio abrasion loss ^{2.0 1.8 2.5 5.2 10.2 (10 -2} mm 3 / kg ・ km) ─────────────────────────────────── PPS resin (A): Kureha Chemical Industry W-205A PPS resin (B): Dainippon Ink and Chemicals, Inc. C-106 Organized montmorillonite (A): Octatedecyltrimethylammonium chlorite treated product Organized montmorillonite (B): Dioctatesilyl methylammonium chloride treated product * 1 Test speed; V = 10cm / s, * 2 Test speed; V = 50cm / s, * 3 Test speed; V = 150cm / s

[0063]

According to the present invention, (C) a swellable layered silicate is treated with an organic cation with respect to 100 parts by weight of a resin component comprising (A) an aromatic polyamideimide resin and (B) a polyarylene sulfide resin. A resin composition containing 0.1 to 30 parts by weight of an organoclay composite obtained by the above method, which has excellent slidability (friction and wear properties), low specific gravity, heat resistance, and melting Excellent in fluidity, strength and toughness, especially satisfying both slidability and mechanical strength which could not be achieved by the conventional technology of improving mechanical strength by compounding filler. It is intended to provide a resin composition which can be used. This can be obtained for the first time by blending the aromatic polyamide-imide resin specified in the present invention and the polyarylene sulfide resin composition with an organic clay composite obtained by treating a swellable layered silicate with an organic cation. It is considered to be based on the effect.

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[Procedure amendment]

[Submission date] June 20, 2000 (2006.2.
0)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0057

[Correction method] Change

[Correction contents]

Example 1 50 parts by weight of the aromatic polyamideimide resin produced in Synthesis Example 1 and a PPS resin (W-205 manufactured by Kureha Chemical Industry Co., Ltd.)
A, 5 parts by weight of the organoclay mineral produced in Synthesis Example 2 was blended with 50 parts by weight of a melt viscosity measured at a shear rate of 1200 / sec at 310 ° C. of 1200 Pa / s) and blended with a twin-screw extruder. The mixture was melt-kneaded at ℃ and pelletized to produce a resin composition. This pellet is injection molded and
A / 8 inch thick bending test piece was obtained. Using this test piece, bending strength and bending strain (Shimadzu Corporation Autograph: AG5000B) were measured. Heat deformation temperature (18.
(6 kg / cm ² load) was also measured using this test piece in a nitrogen atmosphere (Yasda Seiki Co., Ltd. HD-500-PC).
The sliding characteristics were measured by molding a sliding ring and using a thrust friction and wear tester (manufactured by Orientec). Steel (S45C) was used as a mating material. The results are shown in Table 1.
It was shown to.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction contents]

Comparative Example 1 50 parts by weight of the aromatic polyamideimide resin produced in Synthesis Example 1 and a PPS resin (W-205 manufactured by Kureha Chemical Industry Co., Ltd.)
A, montmorillonite not treated with organic cations (Kunimine F. Kunipia F: ion exchange capacity 115 meq / 1) with respect to 50 parts by weight of a melt viscosity measured at a shear rate of 1200 / sec at 310 ° C. and a shear rate of 1200 / sec.
00g) 5 parts by weight were blended and 3 parts were extruded using a twin screw extruder.
The mixture was melt-kneaded at 20 ° C. and pelletized to produce a resin composition. Injection molding and measurement of physical properties were performed in the same manner as in Example 1.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction contents]

Comparative Example 2 50 parts by weight of the aromatic polyamideimide resin produced in Synthesis Example 1 and a PPS resin (W-205 manufactured by Kureha Chemical Industry Co., Ltd.)
A, 50 parts by weight of melt viscosity measured at a shear rate of 1200 / sec at 310 ° C. of 100 Pa · s) was mixed with 50 parts by weight of glass fiber (CS03JAFT52 manufactured by Asahi Fiberglass Co., Ltd.).
3) blend 20 parts by weight and use a twin screw extruder to
The mixture was melt-kneaded at 0 ° C. and pelletized to produce a resin composition. Injection molding and measurement of physical properties were performed in the same manner as in Example 1.

 ──────────────────────────────────────────────────続 き Continued on front page F-term (reference) 4J002 CM04W CN01X DJ006 FB086 FD016 4J043 PA01 PC015 QB21 QB26 QB58 RA05 RA34 SA11 SB01 TA11 TA21 TA22 TB03 UA041 UA121 UA122 UA131 UA132 UA261 VAUB UB 012 UB 012 XA11 XA13 XA16 XA19 YA06 ZA05 ZA12 ZA31 ZA41 ZA60 ZB51

Claims (4)

[Claims] (A) When reacting an aromatic tricarboxylic anhydride with a diisocyanate compound, an aromatic polyamide-imide resin obtained by performing an imidation reaction after the amidation reaction is completed at 70% or more. (B) Total resin component 10 consisting of polyarylene sulfide resin
A resin composition comprising (C) 0.1 to 30 parts by weight of an organic clay complex obtained by treating a swellable layered silicate with an organic cation with respect to 0 parts by weight. 2. The resin composition according to claim 1, wherein a part of the aromatic tricarboxylic anhydride is changed to an aromatic tetracarboxylic anhydride. 3. An aromatic polyamide-imide resin obtained by carrying out an amidation reaction at 50 to 100 ° C. and an imidization reaction at 100 to 200 ° C. in producing the aromatic polyamide-imide resin. The resin composition as described in the above. 4. An aromatic polyamide-imide resin obtained by carrying out an amidation reaction at 50 to 100 ° C. and an imidation reaction at 105 to 200 ° C. in producing the aromatic polyamide-imide resin. The resin composition as described in the above.