JPH06234914A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin compsn. which is excellent in the balance among properties such as heat resistance, moldability mechanical characteristics, and chemical resistance. CONSTITUTION:The compsn. comprises 5-95wt.% arom. polysulfone resin and 95-5wt.% polyamide resin provided the polysulfone resin contains 1-95wt.% (based on the compsn.) arom. polysulfone resin having phenolic hydroxyl groups in an amt. of 40X10<-6> equivalent or higher per g of the latter polysulfone resin.

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 a method for improving it, for example, Japanese Examined Patent Publication No. 57-2744 and Japanese Unexamined Patent Publication 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 total amount of the resin composition of the aromatic polysulfone resin (C) having 40 × 10 ⁻⁶ equivalents or more of phenolic hydroxyl groups per 1 g of the resin. It relates to a thermoplastic 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 -P
h-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
-Ph-O)-and the like repeating units.

The above-mentioned aromatic polysulfone resin is generally a polycondensation reaction of a dihalogenodiphenylsulfone compound and a dihydric phenol compound in an organic polar solvent in the presence of an alkali metal compound, or a divalent phenol synthesized in advance. It can be produced by a polycondensation reaction between an alkali metal disalt and a dihalogenodiphenyl sulfone 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. 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-based resin produced by using hydroquinone and 4,4'-biphenol as a dihydric phenol compound at a specific charge ratio is excellent in heat resistance and mechanical properties and is preferably used. .

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

[Chemical 1]

And a repeating unit (II) of the following formula formed by the condensation of 4,4'-biphenol and a dihalogenodiphenyl sulfone compound,

[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 dihalogenodiphenyl sulfone 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.

Examples of the dihalogenodiphenyl sulfone compound include 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone.

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,
Those of 0.3 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.

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 40 × 10 ⁻⁶ equivalents or more of phenolic hydroxyl groups per 1 g of resin. The aromatic polysulfone resin has the same reaction as the above-mentioned aromatic polysulfone resin as the component (A), that is, in a polycondensation reaction of a dihalogenodiphenylsulfone compound and a dihydric phenol compound,
It can be produced by carrying out a polycondensation reaction by using an excess amount of a dihydric phenol compound with respect to a dihalogenodiphenyl sulfone compound.

The aromatic polysulfone resin as the component (C) of the present invention has 40 × 10 ^-6 equivalents or more of phenolic hydroxyl groups per 1 g of the resin. With an aromatic polysulfone resin having a phenolic hydroxyl group content of less than 40 × 10 ^-6 equivalents per 1 g of resin, the dispersibility of the aromatic polysulfone resin of component (A) and the polyamide resin of component (B) does not improve, and The balance of physical properties of the plastic resin composition is insufficient. The content of the phenolic hydroxyl group can be adjusted by the ratio of the dihydric phenol compound and the dihalogenodiphenyl sulfone compound.

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 particularly preferably 0.3 to 1.5.

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 the aromatic polysulfone resin, the aromatic polysulfone resin (C) having 40 × 10 ⁻⁶ equivalents or more of phenolic hydroxyl groups per 1 g of the resin 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.

When the mixing ratio of the aromatic polysulfone resin having 40 × 10 ⁻⁶ equivalents or more of phenolic hydroxyl groups per 1 g of the component (C) resin is less than 1% by weight, the aromatic polysulfone resin of the component (A) and the component (B) are mixed. (3) does not improve the dispersibility with the polyamide resin, and the balance of the physical properties of the thermoplastic resin composition is insufficient.

There is no particular limitation on the method of blending the respective components of the present invention, but they can be blended by kneading using an ordinary 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.

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.

[0026]

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.

[0027]

【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.

(Test Method for Specimen) (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.

Synthesis Example 1 (Production of Aromatic Polysulfone Resin (1)) 4,4′-Dichlorodiphenylsulfone 133.5 g and 2,2-bis (4-hydroxyphenyl) propane 96.4 g were mixed with N-methyl-2. -Pyrrolidone was added to 500 ml and dissolved, then 70% in 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, and the repeating unit (I) and the repeating unit were
The ratio with (II) was 50:50 (mol%). The amount of phenolic hydroxyl group is 19 × per 1g of aromatic polysulfone resin.
It was 10 ^-6 equivalent.

Synthesis Example 2 (Production of Aromatic Polysulfone Resin (2)) 4,4′-Dichlorodiphenylsulfone 119.2 g and 2,2-bis (4-hydroxyphenyl) propane 96.4 g were mixed with N-methyl-2. -Pyrrolidone was added to 500 ml and dissolved, then 70% in 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 0.49, and the repeating unit (I) and the repeating unit were
The ratio with (II) was 50:50 (mol%). The amount of phenolic hydroxyl group is 83 × per 1g of aromatic polysulfone resin.
It was 10 ^-6 equivalent.

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%). The amount of phenolic hydroxyl group is 22 × per 1g of aromatic polysulfone resin.
It was 10 ^-6 equivalent.

Synthesis Example 4 (Production of Aromatic Polysulfone Resin (4)) 4,4′-dichlorodiphenylsulfone 119.2 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 0.52, and the repeating unit (I) and the repeating unit were
The ratio with (II) was 50:50 (mol%). The amount of phenolic hydroxyl group is 89 x per 1g of aromatic polysulfone resin.
It was 10 ^-6 equivalent.

Example 1 As a polyamide resin, UBE nylon 6 1030 was used.
B (trade name: manufactured by Ube Industries, Ltd.) was used as the component (A).
% By weight, 30% by weight of polyamide resin as the component (B), and 20% by weight of the aromatic polysulfone resin (2) produced in Synthesis Example 2 as the component (C) are mixed, and the mixture is manufactured by Nakatani Machinery Co., Ltd. The resin composition of the present invention was obtained by melt-kneading at 280 ° C. using a shaft extruder. 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 70% by weight of polyamide resin as the component (B) and 30% by weight of the aromatic polysulfone resin (4) prepared in Synthesis Example 4 as the component (C) were mixed, and the same procedure as in Example 1 was conducted. A resin composition was obtained. 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 30% by weight of a polyamide resin as the component (B) and 70% by weight of the aromatic polysulfone resin (4) prepared in Synthesis Example 4 as the component (C) were mixed, and the same procedure as in Example 1 was carried out. A resin composition was obtained. 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 and 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.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Daimon 8-1 Goi Minamikaigan, Ichihara-shi, Chiba Ube Industries, Ltd. Chiba Research Institute (72) Masayuki Nakatani 8th Goi Minamikaigan, 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. A thermoplastic resin composition comprising an aromatic polysulfone resin (C) having 40 × 10 ⁻⁶ equivalents or more of a phenolic hydroxyl group in an amount of 1 to 95% by weight based on the total amount of the resin composition.