JPH07173394A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition which is useful for car parts, excellent in chemical resistance, moldability, heat resistance and impact resistance by mixing a specific aromatic polysulfone resin with a polyalkylene terephthalate resin in a specific ratio. CONSTITUTION:The thermoplastic resin composition comprises (A) 5 to 95wt.% of an aromatic polysulfone resin, for example, having the recurring units of the formula and (B) 95 to 5wt.% of a polyalkylene terephthalate such as polybutylene terephthalate, and an aromatic polysulfone resin having more than 20X10<-6> equivalent of epoxy groups per gram of the resin is included in an amount of 1 to 95wt.% based on the total amount of the resin composition.

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 polyalkylene terephthalate 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, it is known to blend a polyalkylene terephthalate. For example, Japanese Examined Patent Publication No. 48-8257,
Japanese Patent Publication No. 57-2744 discloses a resin composition of polysulfone and polybutylene terephthalate. However, although the chemical resistance and moldability of the resin composition are improved by blending the polyalkylene terephthalate, the impact resistance is not improved and the balance of physical properties is not always satisfactory, and improvement is required. ing.

[0003]

OBJECTS OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin composition having an excellent balance of heat resistance, chemical resistance, moldability and impact resistance.

[0004]

The present invention provides a thermoplastic resin composition comprising an aromatic polysulfone resin (A) 5 to 95% by weight and a polyalkylene terephthalate resin (B) 95 to 5% by weight. Then, as the aromatic polysulfone resin, an aromatic polysulfone resin (C) having an epoxy group of 20 × 10 ⁻⁶ equivalents or more per 1 g of the resin is 1 to 1% of the total amount of the resin composition
It relates to a thermoplastic resin composition containing 95% by weight.

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 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. 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-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, 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.

The component (B) of the composition of the present invention is polyalkylene terephthalate. As the polyalkylene terephthalate, there is a polymer obtained by reacting terephthalic acid or its ester-forming derivative with alkylene glycol or its ester-forming derivative as a main raw material,
Further, 30 mol% or less of terephthalic acid may be replaced with other aromatic dicarboxylic acids or aliphatic dicarboxylic acids, and 30 mol% or less of alkylene glycol may be replaced with other aliphatic diols or alicyclic diols. May be. Aromatic or aliphatic dicarboxylic acids other than terephthalic acid used in such copolymers include isophthalic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, adipic acid,
Azelaic acid, sebacic acid, etc. can be mentioned.

Examples of alkylene glycols include polymethylene-α, ω-diols such as tetramethylene glycol, ethylene glycol and trimethylene glycol, neopentyl glycol, diethylene glycol,
Examples thereof include polypropylene glycol and polytetraglycol.

Component (C) of the composition of the present invention is an aromatic polysulfone resin having 20 × 10 ⁻⁶ equivalents or more of epoxy groups per 1 g of resin. The aromatic polysulfone resin is
It can be produced by modifying the aromatic polysulfone resin as the component (A). For example, a method of reacting a phenol sulfone having a phenolic hydroxy terminal or an amino terminal with an epoxy resin such as Bis-A
After adding a functional group such as a hydroxy group to tersulphone, a method of producing by reacting with epichlorohydrin, or a polyethersulfone polymerization liquid obtained by polycondensing a dihalogenodiphenyl compound and a divalent phenol,
It is possible to use a method in which epichlorohydrin is directly added and reacted to produce the compound.

The aromatic polysulfone resin of the component (C) of the present invention has an epoxy group of 20 × 10 ^-6 equivalent or more per 1 g of the resin,
More preferably, it has 30 × 10 ⁻⁶ equivalents or more. Resin 1
By using an aromatic polysulfone resin having an epoxy group content of 20 × 10 ^-6 equivalents or more per gram, the dispersibility of the aromatic polysulfone resin and the polyalkylene terephthalate resin is improved, and the thermoplastic resin has an excellent balance of physical properties. A composition 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 such that the aromatic polysulfone resin of the component (A) is 5 to 95% by weight, and the polyalkylene terephthalate resin of the component (B) is.
95 to 5% by weight, and as the aromatic polysulfone resin,
Aromatic polysulfone resin (C) having 40 × 10 ^-6 equivalents or more of amino groups per 1 g of resin is 1 to 95% by weight of the total amount of the resin composition.
Is.

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 epoxy groups per 1 g of resin of component (C)
A thermoplastic resin composition having an excellent balance of physical properties by improving the dispersibility of the aromatic polysulfone resin and the polyalkylene terephthalate resin by mixing 1% by weight or more of the aromatic polysulfone resin having × 10 ^-6 equivalents or more Is 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.

(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. Determination of epoxy groups (Determination of epoxy groups), 400 MHz ¹ H
-Performed by NMR.

Synthesis Example 1 (Production of Aromatic Polysulfone Resin (1)) 300 ml of N-methyl-2-pyrrolidone as an organic solvent, 69.4 g of 4,4'-dichlorodiphenylsulfone as dichlorodiphenylsulfone, and divalent pheno- Bisphenol-A [2,2-bis (4-hydroxyphenyl) propane] 5
A polysulfone polymer solution was obtained in the same manner as in Example 1 except that 6.8 g of the solution was stirred under a nitrogen atmosphere at a temperature of about 180 ° C. for 10 hours. The polysulfone resin obtained by the polymerization had a phenol group amount of 159 μeq / g and ηsp / c of 0.37.

Synthesis Example 2 (Production of Epoxy Group-Containing Aromatic Polysulfone Resin (2)) After cooling the polymerization solution of Synthesis Example 1 to 100 ° C., 31.4 g of epichlorohydrin was directly added to the polymerization solution (about 10 times the amount of phenol). mo
l) was added and stirred for 3 hours. After the completion of the reaction, in order to separate inorganic substances from the polymerization solution, the mixture was filtered under a nitrogen pressure of 1.5 Kg / cm ² to obtain a polymerization filtrate (polymer concentration: about 23% by weight). Polymerization filtrate 30
0 g was poured into 2000 ml of ethanol, the polymer was precipitated while stirring at 5000 rpm, and the polymer was obtained by separating by filtration. 50 g of this polymer was washed twice with 500 ml of ethanol and then dried at 90 ° C. to obtain a polysulfone resin powder having an epoxy group. The epoxy group content of the obtained polysulfone resin was 370.
μ equivalent / g, and reduced viscosity was 0.26.

Synthesis Example 3 (Production of Aromatic Polysulfone Resin (3)) In a 500 mL flask equipped with a stirrer, a thermometer and a reflux condenser, 300 ml of N, N-dimethylacetamide as an organic solvent,
Azeotropic dehydration toluene 30 ml, 4,4'-dichlorodiphenyl sulfone 67.9 g, hydroquinone 13.7 g, 4,4'-biphenol 23.2 g, and potassium carbonate 38 g were used under a nitrogen atmosphere at a temperature of about 160 ° C, 8 After stirring for a time, a polysulfone polymerization solution was obtained.

A part of this polymerization liquid was taken out and the phenol group was methoxylated using methyl chloride. After filtration, polysulfone was deposited using ethanol. Ethanol - After washing twice with Le, and dried under reduced pressure at 100 ° C., 400 MHz ¹ H
-The amount of methoxy groups in polysulfone was measured by NMR. The polysulfone resin obtained by the polymerization had a phenol group content of 373 μeq / g and ηsp / c of 0.26.

Synthesis Example 4 (Production of Epoxy Group-Containing Aromatic Polysulfone Resin (4)) After the temperature of the polymerization liquid of Synthesis Example 3 was lowered to 100 ° C., 31.4 g of epichlorohydrin was directly added to the polymerization liquid (about 10 times the amount of phenol). mo
l) was added and stirred for 3 hours. After the completion of the reaction, in order to separate inorganic substances from the polymerization solution, the mixture was filtered under a nitrogen pressure of 1.5 Kg / cm ² to obtain a polymerization filtrate (polymer concentration: about 23% by weight). Polymerization filtrate 30
0 g was poured into 2000 ml of ethanol, the polymer was precipitated while stirring at 5000 rpm, and the polymer was obtained by separating by filtration. 50 g of this polymer was washed twice with 500 ml of ethanol and then dried at 90 ° C. to obtain a polysulfone resin powder having an epoxy group. The epoxy group content of the obtained polysulfone resin was 370.
μ equivalent / g, and reduced viscosity was 0.26.

Example 1 As the polyalkylene terephthalate, polybutylene terephthalate (trade name: UBE-PBT-1000) was used.
Ube Industries, Ltd. was used. Synthesis Example 1 as component (A)
70% by weight of the aromatic polysulfone resin (1) produced in 1., 25% by weight of the polyalkylene terephthalate resin as the component (B), and 5% by weight of the aromatic polysulfone resin (2) produced in Synthesis Example 2 as the component (C). % Were mixed, and this 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 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 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]

Front page continued (72) Inventor Seiji Ishikawa 8-1 Goi Minami Kaigan, Ichihara, Chiba Ube Industries Ltd. Chiba Research Institute (72) Inventor Masayuki Nakatani 1-8 Goi Minami Kaigan, Ichihara, Chiba Ube Ko Sanba Co., Ltd. Chiba Research Center

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 polyalkylene terephthalate resin (B), wherein the aromatic polysulfone resin is a resin. 20 epoxy groups per gram
A thermoplastic resin composition comprising the aromatic polysulfone resin (C) having a concentration of × 10 ^-6 equivalents or more in an amount of 1 to 95% by weight based on the total amount of the resin composition.