JPH043780B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention has excellent mechanical properties, thermal properties, and dimensional stability, and has improved thermal stability during processing.
The present invention relates to an aromatic polysulfone resin composition having good moldability and excellent plating properties. <Prior art> Aromatic polysulfones are used as engineering plastics with excellent heat resistance, strength, rigidity, flame retardance, and creep resistance in electrical and electronic parts, automobile parts, OA equipment parts, etc. However, when plating the surface of a molded article to give a metallic appearance or to form a conductive layer, the adhesion strength of the plating layer is insufficient, which limits its application. In order to improve such plating properties, a resin composition comprising aromatic polysulfone, potassium titanate fiber, and alkaline earth metal carbonate has been proposed (see JP-A-61-281151). <Problems to be Solved by the Invention> However, the proposed composition has the disadvantage that under the molding conditions of melt molding methods such as injection molding, it gels due to retention at high temperatures in the molding machine and loses fluidity, making it impossible to mold. There was a need for improvement. Also,
Even when molding is possible, there are drawbacks such as gelation on the surface of the molded product, which makes it not smooth, the appearance of the plating layer poor, and adhesion strength values being low and varying. Ta. The purpose of the present invention is to improve the thermal stability during processing without deteriorating the properties of aromatic polysulfone.
The object of the present invention is to provide an aromatic polysulfone resin composition which has good moldability and has improved adhesion strength, appearance and physical properties of a plating layer. <Means for solving the problems> The inventors continued their intensive research to achieve the above objectives. As a result, in a resin composition consisting of aromatic polysulfon, potassium titanate fiber, and alkaline earth metal carbonate, by blending potassium titanate fiber with a free potassium content of 0.25% by weight or less, the characteristics of aromatic polysulfon can be improved. The present inventors have discovered that it is possible to obtain a resin composition with improved thermal stability during processing, good moldability, and excellent plating properties without reducing the properties of the resin, and have completed the present invention. That is, the present invention contains 60 to 90% by weight of aromatic polysulfone, 3 to 30% by weight of potassium titanate fiber, and 3 to 3% by weight of alkaline earth metal carbonate.
This aromatic polysulfone resin composition is characterized in that the free potassium content in the potassium titanate fibers is 0.25% by weight or less in the resin composition consisting of ~30% by weight. However, the free potassium content in potassium titanate fibers can be determined by boiling the potassium titanate fibers in a predetermined amount of water for 20 hours, measuring potassium in the eluted water using an atomic absorption spectrometer (measuring wavelength
7665Å). Aromatic polysulfones used as components of the compositions of the present invention are defined as polyarylene compounds in which the arylene units are located randomly or ordered with ether and sulfonal linkages. For example, those with the following structural formulas (1) to (16) can be mentioned, but those with the structures (1), (2), and (6) have an excellent balance of physical properties and processability. This is preferable. Furthermore, aromatic polysulfone with a reduced viscosity of 0.3 to 0.6 measured at 25°C in a dimethyl formamide solution containing 1 g of polymer in 100 ml of solution has excellent physical properties such as heat resistance, strength, rigidity, and toughness, and moldability. It is more preferable as it has an excellent balance. The amount of aromatic polysulfon to be blended is suitably 60 to 90% by weight based on the total amount of aromatic polysulfon, potassium titanate fiber, and alkaline earth metal carbonate. If it is less than 60% by weight, the strength of the composition and the appearance of the molded product will be insufficient, and if it exceeds 90% by weight, the density strength and heat resistance of the plating layer will be insufficient. The potassium titanate fiber used in the present invention is a type of high-strength single crystal fiber (whisker), and its chemical composition is K ₂ O 6TiO ₂ , K ₂ O 6TiO ₂ 1/2
It is a needle-shaped crystal based on H ₂ O, and its typical melting point is 1300-1350°C. Average fiber length 5-150μm,
Those with an average fiber diameter of 0.05 to 2.0 μm are applicable,
Preferably, the average fiber length is 10 to 30 μm and the average fiber diameter is 0.1 to 0.5 μm. The amount of potassium titanate fibers to be blended is suitably 3 to 30% by weight based on the total amount of aromatic polysulfone, potassium titanate fibers, and alkaline earth metal carbonate. If the amount of potassium titanate fiber is less than 3% by weight, the effect of improving the physical properties of the composition will be insufficient, and if it exceeds 30% by weight, the appearance of the molded product and the plating layer will be poor. The potassium titanate fiber used in the present invention is
It is essential that the free potassium content in the fibers is 0.25% by weight or less. free potassium content
If it exceeds 0.25% by weight, the thermal stability of the aromatic polysulfone resin composition during melting will decrease, and the increase in viscosity due to retention during melting will become extremely large. Particularly, in the case of higher temperature and longer residence time or in the case of higher blending amount of potassium titanate fibers, the increase in viscosity becomes even greater, gelation occurs, fluidity is lost, and moldability becomes impossible. In addition, even if molding is possible, gelation is observed on the surface of the molded product and it is not smooth, the appearance of the plating layer becomes poor, the adhesion strength decreases, and there are variations in the value. . When the free potassium content in the potassium titanate fibers is 0.25% by weight or less, the increase in melt viscosity is extremely slight, but when it is 0.05% by weight or less, it is particularly preferable because no further increase in viscosity occurs even under severe conditions. The firing method, melting method, hydrothermal method, and flux method are known as methods for producing potassium titanate fibers, and the mixing ratio of the starting materials K ₂ O and TiO ₂ ,
The chemical composition K ₂ O of the fiber obtained, the value of n in nTiO ₂ and the fiber length are determined by the reaction temperature, basicity of the reaction system, etc. The method for producing potassium titanate fibers with a free potassium content of 0.25% by weight or less is not particularly limited, and by carrying out the above production method under selected appropriate conditions, it is possible to produce potassium titanate fibers with a low free K ₂ O content. , i.e. in terms of free potassium content.
Free potassium obtained by methods to obtain fibers of 0.25% by weight or less, or by conventional industrial manufacturing methods.
Fibers containing 0.15 to 0.40% by weight are fired at a high temperature of 500°C or higher, or released with water or acid.
Free potassium content by leaching _K2O
Examples include methods for obtaining fibers of 0.25% by weight or less. Alkaline earth metal carbonates, which are other important constituents of the present invention, include carbonates of magnesium, calcium, strontium, and barium. Preferably, calcium carbonate, magnesium carbonate, and a eutectic of calcium carbonate and magnesium carbonate are used. The eutectic of calcium carbonate and magnesium carbonate is so-called dolomite. The amount of alkaline earth metal carbonate is 3 to 30% by weight based on the total amount of aromatic polysulfone, potassium titanate fiber, and alkaline earth metal carbonate.
is appropriate. If the alkaline earth metal carbonate content is less than 3% by weight, the adhesion strength of the plating layer will be insufficient, and if it exceeds 30% by weight, the strength, which is a characteristic of aromatic polysulfone, will decrease. In order to more effectively improve the adhesion strength of the plating layer and maintain the strength of the composition, the content is preferably 5 to 20% by weight. There are no particular limitations on the means for blending the raw ingredients to obtain the composition of the present invention. aromatic polysulfone,
Potassium titanate fibers and alkaline earth metal carbonates can be fed separately to a melt mixer, or these raw materials can be premixed using a mortar, Henschel mixer, ball mill, ribbon blender, etc. It can also be fed to a melt mixer. The composition of the present invention may include antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, colorants such as dyes and pigments, flame retardants, flame retardant additives, etc., to the extent that the purpose of the present invention is not impaired. One or more conventional additives such as antistatic agents, antistatic agents, etc. can be added. Furthermore, a small amount of one or more of thermoplastic resins (eg, polyethylene, polypropylene, polyamide, polycarbonate, modified polyphenylene oxide, etc.) and thermosetting resins (eg, phenolic resin, epoxy resin, etc.) can also be added. Plating of a molded article made of the composition of the present invention can be carried out, for example, as follows. (Electroless plating operation) Preparation of substrate The injection molded product is annealed in a hot air circulation oven at 180-200°C for 3-5 hours. Degreasing OPC-260 Cleaner L (manufactured by Okuno Pharmaceutical Co., Ltd.) 100
ml/solution for 5 minutes at 65°C. Washing with water Etching Immerse in a mixed solution of 400 g of chromic anhydride and 220 ml of concentrated sulfuric acid at 78-82°C for 30 minutes. Water washing Neutralization Concentrated hydrochloric acid 50ml/Toppukyatsu CR-200
(manufactured by Okuno Pharmaceutical Co., Ltd.) for 5 minutes at room temperature. Washing Conditioner OPC-350 Conditioner M (Okuno Pharmaceutical Co., Ltd.)
Immerse in 30ml/solution (manufactured by Manufacturer, Inc.) for 3 minutes at 30℃. Water washing Pre-dip Immerse in concentrated hydrochloric acid 150ml/solution for 2 minutes at room temperature. Catalyzing Concentrated hydrochloric acid 150ml/and OPC-80 Catalyst M
(manufactured by Okuno Pharmaceutical Co., Ltd.) for 5 minutes at room temperature. Washing with water Accelerating OPC-555 Accelerator M (manufactured by Okuno Pharmaceutical Co., Ltd.)
Immerse in 100ml/solution for 7 minutes at 28°C. Water washing Electroless plating TMP chemical copper plating New 100 (manufactured by Okuno Pharmaceutical Co., Ltd.)
It is immersed in the solution for 7 minutes at room temperature to form a copper film of 0.3 to 0.5 μm. (Operation of electrolytic plating) In 200 g of copper sulfate/solution, the electrolessly plated specimen was used as the cathode and the phosphorous copper was used as the anode, and the electrolytic plate was applied at 3A/d.
Electricity was applied for 110 minutes at a current density of m ³ to form a plating film with a thickness of 50 μm. <Effects of the Invention> According to the present invention, aromatic polysulfone 60 to 90
% by weight, a resin composition consisting of 3-30% by weight of potassium titanate fibers and 3-30% by weight of alkaline earth metal carbonate, with a free potassium content of 0.25%.
By using potassium titanate fibers that are less than % by weight, the thermal stability during processing is improved without deteriorating the properties of aromatic polysulfone.
It is possible to obtain an aromatic polysulfone resin composition which has good moldability and has improved adhesion strength, appearance and physical properties of the plating layer. As shown in the comparative example below, resin compositions using potassium titanate fibers with a free potassium content of more than 0.25% by weight are inferior in moldability and surface smoothness of molded products, and have poor appearance after plating. Adhesion strength is also poor. In contrast, as shown in the examples below, the composition of the present invention has high tensile strength, flexural modulus, impact strength, and heat distortion temperature, and exhibits excellent thermal stability during melting. It shows the plating characteristic. <Example> Examples 1 to 4 Repeating structural unit of the following formula Aromatic polysulfone (Polyethersulfon 3600P manufactured by ICI) with free potassium 0.03%
Potassium titanate fiber containing (Titan Kogyo Co., Ltd.)
Manufactured by HT-200, fiber diameter 0.3~1.0μm, fiber length 20~
120μm) and alkaline earth metal carbonate as the first
Mix the composition shown in the table and use a twin screw extruder (Ikegai Iron Works).
After melt-kneading at a temperature of 330° C. using PCH-30 (manufactured by Co., Ltd.), the strands were cooled with water and then cut to obtain pellets. The obtained pellets were injection molded (using a Nestal 47/28 injection molding machine manufactured by Sumitomo Heavy Industries, Ltd.).
Cylinder temperature was set at 340 to 860°C and mold temperature was set at 150°C), a tensile test piece, a bending test piece, an Izot test piece, a test piece for measuring heat distortion temperature, and a plating test piece were obtained. Tensile strength, flexural modulus, isot impact strength, and heat distortion temperature are ASTM D-638, respectively.
Measured in accordance with D-790, D-256, and D-648.
In addition, after plating the plating test piece using the method described above, the adhesion strength was measured according to JIS C6481 (90° peeling,
Measurement was performed based on a peeling speed of 50 mm/min). The results are shown in Table 1. On the other hand, as a method for evaluating thermal stability during melting, a Koka type flow tester (manufactured by Shimadzu Corporation) was used.
400℃, load 50Kg/cm ² , nozzle diameter mmφ, land length
At 10 mm, the melt viscosity was compared between 5 minutes and 30 minutes of residence.
The results are shown in Table 1. All of them have high tensile strength, flexural modulus, impact strength, and heat distortion temperature, and exhibit excellent plating properties while exhibiting excellent thermal stability during melting. The above free potassium amount is determined by boiling a predetermined amount of the potassium titanate fiber in water for 20 hours, and then measuring the eluted water using a flame-light atomic absorption spectrometer (double beam type, Shimadzu Model 650, measurement wavelength 7665 Å). This is the value. Comparative Examples 1 to 3 Aromatic polysulfone and alkaline earth metal carbonate as in Example 1 except that potassium titanate fibers with a free potassium content of 0.28% by weight (Teismo D manufactured by Otsuka Chemical Co., Ltd.) were used. A test piece was prepared using The results are shown in Table 1. Regarding the melt viscosity, when the residence time with any composition was prolonged, gelation occurred and the melt viscosity increased significantly, but extrusion became impossible. In addition, in injection molding under relatively short residence time conditions, molding was possible and the physical properties did not deteriorate significantly, but gelled substances were observed on the surface, resulting in poor smoothness, poor appearance after plating, and poor adhesion. A decrease in strength was observed. Examples 5-6 and Comparative Examples 4-5 Repeating structural unit of the following formula aromatic polysulfone (manufactured by UCC)
Example except that potassium titanate fiber and alkaline earth metal carbonate were mixed in the proportions shown in Table 2, pelletizing temperature was 300℃, and injection molding cylinder temperature was 330-350℃. 1~
The same operation as 4 was performed. Note that for Examples 5 and 6, the same potassium titanate fibers as in Examples 1 to 4 containing 0.03% by weight of free potassium were used. For Comparative Examples 4-5, the same potassium titanate fibers as Comparative Examples 1-3 with free potassium of 0.28% by weight were used. The results are shown in Table 2. In both cases, similar results were obtained when polyether sulfone was used.

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Claims (1)

[Scope of Claims] 1. In a resin composition comprising 60 to 90% by weight of aromatic polysulfone, 3 to 30% by weight of potassium titanate fibers, and 3 to 30% by weight of alkaline earth metal carbonate, An aromatic polysulfone resin composition characterized in that the free potassium content is 0.25% by weight or less. (However, the free potassium content in potassium titanate fibers is determined by boiling a predetermined amount of potassium titanate fibers in water for 20 hours, and then measuring the potassium in the elution water using an atomic absorption spectrometer (measurement wavelength: 7665 Å). ) 2 The alkaline earth metal carbonate is calcium carbonate,
The aromatic polysulfone resin composition according to claim 1, which is one or two selected from the group consisting of magnesium carbonate and a eutectic of calcium carbonate and magnesium carbonate.