JPH07150035A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition, comprising an aromatic polysulfone resin, a polyamide resin and an amino group-containing aromatic polysulfone resin and excellent in balance among physical properties such as heat and chemical resistances and moldability. CONSTITUTION:This thermoplastic resin composition comprises (A) 5-95wt.% aromatic polysulfone resin, (B) 95-5wt.% polyamide resin (e.g. nylon 6) and (C) an aromatic polysulfone resin having amino groups in an amount of >=20X10<-6> equiv. based on 1g resin in an amount of 1-95wt.% based on the total amount of the resin composition. Furthermore, the component (A) is preferably a resin at (10-60):(40-90) mol% ratio of a unit, produced by condensing hydroquinone with a dihalogenosulfone compound and expressed by formula I to a unit, produced by condensing 4,4'-biphenol with the dihalogenosulfone compound and expressed by formula II. The component (C) is prepared by using, e.g. a dihydric phenol compound and a bivalent aminophenol compound in combination. p-Aminophenol is preferred as the bivalent aminophenol compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition comprising an aromatic polysulfone resin and a polyamide resin.

[0002]

2. Description of the Related Art Aromatic polysulfone resins are known as engineering plastics having excellent heat resistance. However, there is a problem that the chemical resistance, moldability and impact resistance are not always good. As an improvement method thereof, for example, Japanese Patent Publication No. 57-2744 and Japanese Patent Laid-Open No. 56-13
3356, JP 62-280256, JP 46-6234
Japanese Patent Laid-Open Nos. 53-129248 and 3-273056 disclose a composition in which a polyamide resin is blended. However, the composition obtained by the above method is not always satisfactory in balance of physical properties such as heat resistance, moldability, mechanical properties and chemical resistance.

[0003]

It is an object of the present invention to provide a thermoplastic resin composition having an excellent balance of physical properties such as heat resistance, moldability, mechanical properties and chemical resistance.

[0004]

The present invention provides a thermoplastic resin composition comprising an aromatic polysulfone resin (A) 5 to 95% by weight and a polyamide resin (B) 95 to 5% by weight. The aromatic polysulfone resin is characterized by containing 1 to 95% by weight of the aromatic polysulfone resin (C) having an amino group of 20 × 10 ⁻⁶ equivalent or more per 1 g of the resin composition as a whole, as the aromatic polysulfone resin. It relates to a plastic resin composition.

The aromatic polysulfone resin as the component (A) of the composition of the present invention has the general formula-(Ph-X ₁ -Ph-X ₂ ----- Ph-X _i )-(where X ₁ to X _i is a bonding group or a direct bond connecting aromatic rings, at least one of which is a SO ₂ group, and Ph represents an aromatic ring) is an aromatic polysulfone resin having a repeating unit represented by As a connection, SO
Other than _two groups, aliphatic groups, O, S, CO, COO, CO
There is a bonding group such as NH or a direct bond of an aromatic ring. In particular, those used in the aromatic polysulfone resin of the present invention are preferably SO ₂ , O, or a direct bond of an aromatic ring.

Specific examples of the aromatic polysulfone resin of the present invention include those having the following repeating units, but the invention is not limited thereto.

-(Ph-SO ₂ -Ph-O-Ph-C
_{(CH 3) 2 -Ph-O} ) -, - (Ph-SO 2 -Ph-O) -, - (Ph-SO 2 -Ph-O-Ph-O) -, - (Ph-SO 2 -Ph -O-Ph-Ph-O) -, - (Ph-SO 2 -Ph-Ph-SO 2 -Ph-O-P
and repeating units such as h-O)-.

The above-mentioned aromatic polysulfone resin is generally a polycondensation reaction of a dihalogenosulfone compound and a dihydric phenol compound in an organic polar solvent in the presence of an alkali metal compound, or an alkali of a dihydric phenol previously synthesized. It can be produced by a polycondensation reaction between a metal disalt and a dihalogenosulfone compound.

Specific examples of the dihydric phenol compound include:
For example, hydroquinone, catechol, resorcin,
4,4'-biphenol, bis (hydroxyphenyl) alkanes such as 2,2-bis (4-hydroxyphenyl) propane, dihydroxydiphenylsulfones, dihydroxydiphenylethers, or at least one of the hydrogens of their benzene rings, Suitable substituents (eg, lower alkyl groups such as methyl group, ethyl group, propyl group,
Alternatively, there may be mentioned those substituted with a substituent such as a lower alkoxy group such as a methoxy group and an ethoxy group. Alternatively, divalent thiophenols may be used instead of the above dihydric phenol compounds. It is also possible to use a mixture of two or more of the above dihydric phenol compounds.

In the present invention, an aromatic polysulfone resin produced by charging hydroquinone and 4,4'-biphenol as a dihydric phenol compound in a specific ratio is excellent in heat resistance and mechanical properties and is preferably used. .

That is, a repeating unit of the following formula formed by condensation of hydroquinone and a dihalogenosulfone compound
(I),

[Chemical 1]

And a repeating unit of the following formula (I) produced by condensation of 4,4'-biphenol with a dihalogenosulfone compound:
I),

[Chemical 2] The ratio of 0 to 70:30 to 100 (mol%), especially 10 to 6
An aromatic polysulfone-based resin having a ratio of 0:40 to 90 (mol%) is preferable.

The dihydric phenol compound is preferably used in a substantially equimolar amount with the dihalogenosulfone compound. In order to control the molecular weight of the aromatic polysulfone-based resin produced, the dihydric phenol compound may be used in an equimolar amount to a slight excess amount or an excessive amount amount. For this purpose, small amounts of monohalogenodiphenyl compounds or monohydric phenol compounds can be added to the polymerization solution.

Specific examples of the dihalogenosulfone compound include, for example, 4,4'-dichlorodiphenylsulfone and 4,4 '.
-Dihalogenodiphenyl sulfones such as difluorodiphenyl sulfone, 4,4'-bis (4-chlorophenylsulfonyl) biphenyl, bis (halogenophenylsulfonyl) biphenyl such as 4,4'-bis (4-fluorophenylsulfonyl) biphenyl Kind of things can be mentioned.

The molecular weight of the above aromatic polysulfone-based resin is not particularly limited, but the reduced viscosity (ηsp / c) measured at 30 ° C. for a solution of N-methyl-2-pyrrolidone at a concentration of 0.5 g / 100 ml as a solvent is , 0.2 to 2.0 are preferable, and 0.
Those of 25 to 1.5 are particularly preferably used. When the molecular weight is smaller than the above range, the mechanical properties of the aromatic polysulfone resin are deteriorated, and when it is larger than the above range, moldability is deteriorated, which is not preferable.

Component (B) of the composition of the present invention is a polyamide resin. The polyamide resin is one having an acid amide bond (-CONH-) in the molecule, and specifically,
Polymers or copolymers obtained from ε-caprolactam, 6-aminocaproic acid, ω-enanthlactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, α-piperidone, for example, ,
Examples thereof include polycaprolactam, lactam polylaurate, and polyaminoundecanoic acid. Hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, polymers obtained by polycondensing diamines such as metaxylenediamine and dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, For example, polyhexamethylene adipamide (nylon 66), polyhexamethylene azelaic acid amide (nylon 69), polyhexamethylene sebacic acid amide (nylon 610), polyhexamethylene dodecanedioic acid amide (nylon 612), polytetramethylene Examples thereof include a condensate of a diamine such as adipic amide (nylon 46) and a dicarboxylic acid, a copolymer, or a mixture thereof. Further, as the above-mentioned polyamide resin, it is possible to use a resin in which the raw material ratio of diamine and dicarboxylic acid is changed to change the ratio of the carboxylic acid group and the amino group of the terminal functional group.

The molecular weight of the polyamide resin used in the present invention is not particularly limited, but the average molecular weight is 8,000 to 50,00.
0, particularly 10,000 to 30,000 is preferable.

Component (C) of the composition of the present invention is an aromatic polysulfone resin having 20 × 10 ⁻⁶ equivalents or more of amino groups per 1 g of resin. The aromatic polysulfone resin has the formula
The aromatic aminophenol compound represented by (III)

[Chemical 3] (In the formula, X is a chemical bond or -SO _2- , -O-, -S-, -C
A bridged group selected from the group consisting of O- and -CR ¹ R ^2- ,
R ¹ and R ² represent hydrogen, an alkyl group or an alkoxy group,
p is 0 or 1. ) For example, it can be produced by using it together with a dihydric phenol compound when producing the aromatic polysulfone resin (A). As the aromatic aminophenol compound, p-aminophenol can be preferably used. Usually, the aromatic aminophenol compound represented by the formula (III) is added to 0.001 mol per mol of the divalent phenol compound.
It is preferable to use 1 mol or more.

The component (C) of the present invention is an aromatic polysulfone resin having 20 × 10 ^-6 equivalents or more, more preferably 30 × 10 ^-6 equivalents or more of amino groups per 1 g of the resin. resin
By using an aromatic polysulfone resin having an amino group content of 20 × 10 ⁻⁶ equivalents or more per 1 g, the thermoplastic resin composition has improved dispersibility between the aromatic polysulfone resin and the polyamide resin and has an excellent balance of physical properties. Is obtained.

The molecular weight of the aromatic polysulfone-based resin of the above component (C) is not particularly limited, but the reduced viscosity measured at 30 ° C. for a solution of N-methyl-2-pyrrolidone at a concentration of 0.5 g / 100 ml ( η sp / c) is preferably 0.2 to 2.0, and 0.25 to 1.5 is particularly preferably used.

In the present invention, the mixing ratio of each component of the composition is 5 to 95% by weight of the component (A) aromatic polysulfone resin, 95 to 5% by weight of the component (B) polyamide resin, and As an aromatic polysulfone resin, an aromatic polysulfone resin having 20 × 10 ⁻⁶ equivalents or more of amino groups per 1 g of the resin.
(C) is 1 to 95% by weight of the total amount of the resin composition.

The mixing ratios are heat resistance, chemical resistance, moldability,
And the balance of physical properties such as mechanical properties,
When the amount is out of the above range, the balance of these physical properties is lost. That is, when the proportion of the aromatic polysulfone resin exceeds 95% by weight, the effect of improving the moldability is small.

20 g of amino groups are added per 1 g of the resin of component (C).
1 wt% of aromatic polysulfone resin with 10 ^-6 equivalents or more
By mixing the above, the dispersibility of the aromatic polysulfone resin and the polyamide resin is improved, and a thermoplastic resin composition having an excellent balance of physical properties can be obtained.

The composition of the present invention may contain a rubber-like polymer in addition to the above components. Examples of the rubber-like polymer include polybutadiene rubber, ethylene-propylene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-
Examples thereof include butadiene copolymer rubber, acid-modified rubber such as maleic anhydride and itaconic anhydride, and glycidyl group-modified rubber such as glycidyl methacrylate and glycidyl acrylate. In addition, acrylonitrile-butadiene copolymer rubber, chlorinated polyethylene, acrylic rubber, styrene-butadiene block copolymer rubber (S
B, SBS), styrene isoprene-based block copolymer rubber (SI, SIS) and their hydrogenated products (SEB, SEB,
SEBS, SEP, SEPS) and modified functional groups thereof, or a graft copolymer obtained by grafting styrene and / or acrylonitrile or methyl methacrylate onto these rubber-like polymers, styrene-butadiene copolymer rubber and styrene-acrylonitrile. ABS resin, AAS resin, ACS resin, AES resin, MBS resin, MAS resin, etc. which consist of a blend with resin etc. or these combinations can be mentioned. Examples of the production method include known production methods such as emulsion polymerization method, suspension polymerization method, solution polymerization method, and bulk polymerization method. By adding the above rubber-like resin, physical properties such as impact resistance (notched Izod strength) of the composition are further improved.

Polyethylene, polypropylene, ethylene / vinyl acetate copolymers, ethylene / propylene copolymers, styrene / butadiene copolymers, hydrogenated styrene / butadiene copolymers are further added to the extent that the characteristics of the composition of the present invention are not impaired. Thermoplastic resins such as polymers, polyvinyl chloride resins and polycarbonates, thermosetting resins such as phenol resins, melamine resins, silicone resins and epoxy resins, glass fibers, carbon fibers, boron fibers, silicon carbide fibers, asbestos fibers. , Reinforcing agents such as metal fibers, clay, mica, silica, graphite, glass beads,
One or more fillers such as calcium carbonate and talc, or an antioxidant, a heat stabilizer, an anti-UV agent, a flame retardant, a pigment, an antistatic agent, and a colorant may be added.

There are no particular restrictions on the method of blending the components of the present invention, but they can be blended by kneading using a conventional kneader. For example, it can be obtained as pellets by melt-kneading using a single-screw extruder, a twin-screw extruder, a mixing roll, a Banbury mixer or the like. The pellets are molded into an arbitrary shape such as a film, a pipe or a tube by injection molding, blow molding, extrusion molding or the like.

[0027]

The composition of the present invention has chemical resistance, moldability,
It is a thermoplastic resin that has a good balance of physical properties such as heat resistance and impact resistance.
It can be used as a material for machine parts, medical and tableware fields.

[0028]

【Example】

(Preparation method of test piece) After the composition was pelletized, the test piece was manufactured by Sumitomo Heavy Industries, Ltd. injection molding machine Nestal SG100 (mold clamping force 10
0 ton) was used to prepare a test piece. (1) Tensile strength It was measured according to ASTM D638. (2) Tensile elongation It was performed according to ASTM D638. (3) Deflection temperature under load Measured according to ASTM D648. (4) Izod impact strength (with notch) It was performed according to ASTM D256. (5) Chemical resistance A test piece (1/8 inch in thickness) was immersed in acetone, and after 24 hours, a visual inspection was performed. (Amino group equivalent) The amino group equivalent of the aromatic polysulfone resin (C) was calculated by potentiometric titration.

Synthesis Example 1 (Production of Aromatic Polysulfone Resin) 133.5 g of 4,4'-dichlorodiphenyl sulfone and 96.4 g of 2,2-bis (4-hydroxyphenyl) propane were mixed with 500 ml of N-methyl-2-pyrrolidone. And dissolve in 70% nitrogen.
65 g of potassium carbonate heat-treated at 30 ° C. for 30 minutes was reacted with stirring at a temperature of 180 ° C. for 8 hours in a nitrogen atmosphere. After the reaction,
Nitrogen pressure of 1.5 kg / cm ² to separate inorganics from polymerization solution
The resulting solution was filtered to obtain a polymerization solution. Polymerization solution 300g ethanol
The polymer was poured into 2000 ml and stirred at 5000 rpm to precipitate a polymer, which was filtered and separated to obtain a polymer. 50g of this polymer
Was washed with 500 ml of ethanol and then dried at 90 ° C. to obtain an aromatic polysulfone resin powder.

The reduced viscosity (ηsp / c) of the obtained aromatic polysulfone resin was 0.50.

Synthesis Example 2 (Production of Amino Group-Containing Aromatic Polysulfone Resin (2)) 4,4'-Dichlorodiphenylsulfone 122.5 g, 2,2-bis (4-hydroxyphenyl) propane 97.7 g, p-amino After 2.0 g of phenol was added to 500 ml of N-methyl-2-pyrrolidone and dissolved, 63.1 g of potassium carbonate which had been heat-treated in nitrogen at 70 ° C. for 30 minutes was heated and stirred under a nitrogen atmosphere at a temperature of 180 ° C. for 10 hours. After completion of the reaction, in order to separate the inorganic substance from the polymerization solution, the mixture was filtered at a nitrogen pressure of 1.5 Kg / cm ² to obtain a polymerization solution. Polymer (400 g) was poured into ethanol (2400 ml), the polymer was allowed to stand out while stirring at 5000 rpm, filtered and separated to obtain a polymer. 80 g of this polymer was washed with 500 ml of ethanol and then dried at 90 ° C. to obtain an aromatic polysulfone resin.

The reduced viscosity (ηsp / c) of the obtained aromatic polysulfone resin was 0.49, and the amount of amino groups was 83 × 10 ^-6 equivalents per 1 g of the aromatic polysulfone resin.

Synthesis Example 3 (Production of Aromatic Polysulfone Resin (3)) 4,4'-dichlorodiphenylsulfone 133.5 g, hydroquinone 23.4 g and 4,4'-biphenol 39.6 g were mixed with N-methyl-2-pyrrolidone. Add to 500 ml and dissolve, then in nitrogen 70
65 g of potassium carbonate heat-treated at 30 ° C. for 30 minutes was reacted under stirring in a nitrogen atmosphere at a temperature of 180 ° C. for 6 hours. After the reaction,
Nitrogen pressure of 1.5 kg / cm ² to separate inorganics from polymerization solution
The resulting solution was filtered to obtain a polymerization solution. Polymerization solution 300g ethanol
The polymer was poured into 2000 ml and stirred at 5000 rpm to precipitate a polymer, which was filtered and separated to obtain a polymer. 50g of this polymer
Was washed with 500 ml of ethanol and then dried at 90 ° C. to obtain an aromatic polysulfone resin powder.

The reduced viscosity (ηsp / c) of the obtained aromatic polysulfone resin was 0.55, and the repeating unit (I) and the repeating unit were
The ratio with (II) was 50:50 (mol%).

Synthesis Example 4 (Production of Amino Group-Containing Aromatic Polysulfone Resin (4)) 4,4'-Dichlorodiphenylsulfone 123.1 g, hydroquinone 22.8 g and 4,4'-biphenol 38.6 g were added to p-aminophenol. After 2.0 g and 500 ml of N-methyl-2-pyrrolidone were added and dissolved, 63.1 g of potassium carbonate which had been heat-treated in nitrogen at 70 ° C. for 30 minutes was stirred and reacted in a nitrogen atmosphere at a temperature of 180 ° C. for 8 hours. After completion of the reaction, in order to separate the inorganic substance from the polymerization solution, the polymerization solution was obtained by filtering at a nitrogen pressure of 1.5 kg / cm ² . 300g of polymerization solution is poured into 2000ml of ethanol, 5000rpm
After precipitating the polymer while stirring with, filtering and separating,
A polymer was obtained. 50 g of this polymer was washed with 500 ml of ethanol and then dried at 90 ° C. to obtain an aromatic polysulfone resin powder.

The reduced viscosity (ηsp / c) of the obtained aromatic polysulfone resin was 0.52, the ratio of repeating unit (I) to repeating unit (II) was 50:50 (mol%), and the amount of amino group was aromatic. The amount was 89 × 10 ⁻⁶ equivalent per 1 g of the group polysulfone resin.

Example 1 As a polyamide resin, UBE nylon 6 1030 was used.
B (manufactured by Ube Industries, Ltd.) was used. The aromatic polysulfone resin (1) produced in Synthesis Example 1 as component (A) is 65% by weight, the polyamide resin is 25% by weight as component (B), and the aromatic polysulfone produced in Synthesis Example 2 as component (C). Resin (2) was mixed in an amount of 10% by weight, and the mixture was melt-kneaded at 280 ° C. using a 30 mmφ twin screw extruder manufactured by Nakatani Machinery Co., Ltd. to obtain a resin composition of the present invention. Each evaluation experiment was conducted using this composition. The results are shown in Table 1.

Examples 2 and 3 Resin compositions were obtained in the same manner as in Example 1 except that the mixing ratios of the respective components were as shown in Table 1. Each evaluation experiment was conducted in the same manner as in Example 1 using this composition. The results are shown in Table 1.

Example 4 The aromatic polysulfone resin (3) produced in Synthesis Example 3 was used as the component (A), and the aromatic polysulfone resin (4) produced in Synthesis Example 4 was used as the component (C). A resin composition was obtained in the same manner as in Example 1 except that the mixing ratio of was set as shown in Table 2. Each evaluation experiment was conducted in the same manner as in Example 1 using this composition. The results are shown in Table 2.

Example 5 The same as Example 4 except that the aromatic polysulfone resin (4) produced in Synthesis Example 4 was used as the component (C) and the mixing ratio of each component was as shown in Table 2. To obtain a resin composition.
Each evaluation experiment was conducted in the same manner as in Example 1 using this composition. The results are shown in Table 2.

Example 6 In Example 4, MBS was further used as a rubber-like resin.
A resin composition was obtained in the same manner as in Example 1 except that a resin (trade name: Paraloid EXL-2602, manufactured by Kureha Chemical Co., Ltd.) was added and the mixing ratios of the respective components were as shown in Table 2. Each evaluation experiment was conducted in the same manner as in Example 1 using this composition. The results are shown in Table 2.

Example 7 In Example 4, an acid-modified MBS resin (trade name: Paraloid KCA-501 manufactured by Kureha Chemical Co., Ltd.) was further added as a rubber-like resin, and the mixing ratio of each component is shown in Table 2. A resin composition was obtained in the same manner as in Example 4, except that the procedure described above was used. Each evaluation experiment was conducted in the same manner as in Example 1 using this composition. The results are shown in Table 2.

Example 8 In Example 4, maleic anhydride-modified ethylene propylene rubber (melt flow rate 9, propylene content 22%, Nippon Synthetic Rubber Co., Ltd.) was further used as the rubber-like resin.
A resin composition was obtained in the same manner as in Example 4 except that the mixing ratio of each component was changed as shown in Table 2. Each evaluation experiment was conducted in the same manner as in Example 1 using this composition. The results are shown in Table 2.

Comparative Examples 1 and 2 In Example 1, the component (C) was not used, and the components (A) and
A resin composition was obtained in the same manner as in Example 1 except that the mixing ratio with (B) was changed as shown in Table 3. Each evaluation experiment was conducted in the same manner as in Example 1 using this composition. The results are shown in Table 3.

Comparative Example 3 In Example 4, the component (C) was not used, but the component (A) and the component
A resin composition was obtained in the same manner as in Example 4, except that the mixing ratio with (B) was changed as shown in Table 3. Each evaluation experiment was conducted in the same manner as in Example 1 using this composition. The results are shown in Table 3.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Seiji Ishikawa 8-1 Goi Minamikaigan, Ichihara-shi, Chiba Ube Industries Ltd. Chiba Research Institute (72) Inventor Masayuki Nakatani 8th Goiminamikaigan, Ichihara-shi, Chiba 1 Ube Industries, Ltd. Chiba Laboratory

Claims (1)

[Claims] 1. A thermoplastic resin composition comprising 5 to 95% by weight of an aromatic polysulfone resin (A) and 95 to 5% by weight of a polyamide resin (B), wherein the aromatic polysulfone resin is per 1 g of the resin. Aromatic polysulfone resin (C) having 20 × 10 ^-6 equivalents or more of amino groups is used in an amount of 1 to 95% of the total amount of the resin composition.
A thermoplastic resin composition, characterized in that the thermoplastic resin composition contains it in a weight percentage.