JPH03212452A - Glass fiber-reinforced thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a glass fiber-reinforced thermoplastic resin composition suitable for various electric part materials, mechanical part materials, office machines and heating instruments having excellent mechanical strength containing a thermoplastic resin, glass fibers and alkali metal titanate powder. CONSTITUTION:(A) 40-95 pts.wt. thermoplastic resin is mixed with (B) 5-60 pts.wt. glass fiber having 0.5-6mm length, preferably a glass fiber of chopped strand type to obtain a glass fiber-reinforced resin. Next, a titanium raw material compound (e.g. water-containing titanium oxide) is mixed with an alkali metal raw material compound (e.g. sodium carbonate) in a molar ratio of TiO2 to A2O (5.5-6.0):1 (A is alkali metal) to obtain a mixed slurry and the resultant slurry is dried with spraying, then burned to obtain secondary particles, thus said particles are crushed to obtain (C) an alkali metal titanate powder (preferably sodium hexatitanate, etc.) having 0.05-1mum average diameter. Next, 100 pts.wt. above-mentioned glass fiber-reinforced resin is mixed with 0.1-10 pts.wt. above-mentioned alkali metal titanate powder to afford the objective glass fiber-reinforced thermoplastic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high strength glass fiber reinforced thermoplastic resin composition.

16-Example of Water Glass fiber reinforced thermoplastic resins have excellent mechanical strength and four-method stability, so they are used in various electrical parts, mechanical parts, automobile parts, office equipment, and heating appliances. It is used for. Usually, it is rarely used without coloring, and is generally used in chromatic colors such as black, white, blue, or red. Titanium oxide, which is an alternative white material, is used.

However, when titanium oxide is added to glass fiber-reinforced thermoplastic resins, there is a problem in that mechanical strength and dimensional stability decrease. That is, when glass fibers and titanium oxide are melted and kneaded into a thermoplastic resin, titanium oxide scratches the surface of the glass fibers, making the glass fibers more likely to break during melting and kneading. Since the length of the glass fibers is reduced and the reinforcing effect is reduced, properties such as high strength and good dimensional stability, which are characteristics of glass fiber reinforced resins, are impaired.

In order to reduce the lumping phenomenon, titanium oxide and thermoplastic resin, and glass fiber and thermoplastic resin are kneaded and extruded separately to form pellets 11, and then both pellets are mixed by injection molding. The master pan thousand method of coloring is used. However, in this system ζJ, the two-line extruder is
Furthermore, since the ready-to-use material is kneaded in an injection molding machine where the kneading effect is small, there are problems such as color unevenness is likely to occur.

As described above, conventional glass fiber-reinforced thermoplastic resin compositions colored white have problems with strength and dimensional stability, or have problems with manufacturing costs and manufacturing technology. had.

The present invention uses conventional white-colored glass fiber reinforcement [which does not have the disadvantages of thermoplastic resin compositions, has excellent mechanical strength and dimensional stability, and can be manufactured at low cost and easily. An object of the present invention is to provide a glass fiber-reinforced thermoplastic resin composition that is colored white.

Doyo 111 [The present invention includes a thermoplastic resin, glass fiber, and alkali metal titanate powder! I! The thermoplastic resin used in the present invention includes general-purpose resins such as polypropylene, vinyl chloride, and ABS resin, polybutylene terephthalate, polyamide, and polyethylene terephthalate. Lid tote, polycarbonate, polyphenylene oxide,
Examples include engineering plastics such as polyphenylene sulfide and polyacetal, but are not limited to these.

The glass fibers used in the present invention may be of any type, such as roving type or chopped strand type, but chopped strand type is preferably used from the viewpoint of productivity. Regarding the glass fiber length, the effect of the present invention is more pronounced when the fiber length is longer, but when considering the workability during kneading and the wear of the kneader,
．． It is preferable to have a length of about 5 to 60 mm. The amount of glass fiber filled is distributed in the range of 5 to 60 parts by weight based on 95 to 40 parts by weight of the thermoplastic resin. In other words, the distribution amount is 5
Below 60 parts by weight, the effect of the present invention cannot be expected, and below 60 parts by weight, the fluidity during kneading decreases.
-1 Mitsukawa is not right.

The alkali metal titanate powder used in the present invention includes sodium titanate powder, potassium titanate powder, rubidium titanate powder, etc. Rubidium titanate powder is preferably used. The size of the alkali metal titanate powder is 0.05 as an average diameter determined by the sedimentation method.
~1 μm is appropriate. That is, even if the average diameter is smaller than 0.05 μl or larger than 1 μl, the hiding power and coloring power will be low, which is not preferable. The alkali metal titanate powder that can be used in the present invention is typically produced by the following method.

That is, T i O, pair A 20 (A is Na, Rh
(indicating an alkali metal such as) is 5.5 to 6.0:
After spray-drying a mixed slurry of a titanium raw material compound and an alkali metal raw material compound, which are distributed in equal proportions, the mixture is fired at 600 to 900°C to form secondary particles of alkali metal titanate fine particles. It is possible to form granules and then grind the granules into primary particles by wet grinding or the like.

In the production of the alkali metal titanate powder, titanium raw materials include hydrous titanium oxide, titanium dioxide, and rutile ore. (A20)
Compounds that produce , such as their hydroxides, carbonates, and nitrates, can be mentioned.

The amount of the alkali metal titanate powder added is 0 to 100 parts by weight of a glass fiber reinforced resin consisting of soil, thermoplastic resin = 40 to 95 parts by weight, and glass fiber: 5 to 60 parts by weight.
．． It ranges from 1 to 10 parts by weight. Addition amount: If it is less than 0.1 part by weight, the coloring effect will be insufficient, and if it is added in more than 10 parts by weight, it will not solidify the coloring effect and will be meaningless.

The thermoplastic resin composition of the present invention may optionally contain stabilizers against heat or light, talc, clay wallastonite, mica, kaolin, etc.V) Fillers, dyes or other colored pigments other than titanium oxide, etc. It is also possible to add various additives.

Colored pigments to be mixed with the alkali metal titanate powder include, for example, yellow lead, hexagonal pigment, chrome vermilion, Bengara, color blue-cyanine blue, etc., but are not particularly limited. These preferred mixing ratios are usually 5 to 20% of the alkali metal titanate powder.
It is about parts by weight.

The resin composition of the present invention is prepared by putting composition components such as glass fibers and pigments into a kneading machine such as an extruder in the same way as ordinary resin compositions, melting and kneading the resulting pellets, and then processing the resin composition. It can be obtained by known molding methods such as pressure molding or injection molding.

The obtained molded product exhibits little decrease in the fiber length of the glass fibers, and has high strength and excellent attachment stability.

The present invention will be explained in more detail with reference to Examples below. The following examples are given for illustrative purposes only and are not intended to limit the scope of the invention. In addition, unless otherwise specified below, parts indicate parts by weight. , 2000 g of a hydrous titanium oxide slurry containing 31°5 SO is stirred and then 155 g of fp Natriuno powder is added. This slurry is heated at an inlet temperature of 250-260°C and an outlet temperature of 90-100°C.
Spray dry at 00°C. Next, this dry tri f
m in an alumina crucible and heated at a heating rate of 2 in an electric furnace.
After firing under the conditions of 00°C 7'', firing temperature 800°C, and holding time 3 hours, the temperature was lowered at a rate of 200°C/hour.

After putting the baked product into 81 hot water in a stainless steel container,
After stirring with a homomixer for 1 hour, it is washed with r. Next, the washed cake was redispersed in 81 water and ground for 2 hours using an alumina ball mill.

This product was identified by X-ray diffraction and was found to be a single phase of sodium hexatitanate. It was found that the product had an average diameter.

2 parts of the obtained sodium hexatitanate particles, 30 parts of chopped strand glass fiber with a length of 3 U, and nylon 664.
! ! Made by Ube Industries, product name: UBE Nylon 202
0B) 68 parts in a twin-screw extruder AS- manufactured by Nakatani Kikai Co., Ltd.
The pellets were melted and kneaded at a temperature of 280° C. using No. 30 to form pellets.

leμ100− 2 parts of rutile-type titanium oxide, 3zyg long) Tiyo Nov.

30 parts of stranded glass fiber and 68 parts of nylon 66 resin (manufactured by Ube Industries, trade name: UBE Nylon 2020B) were mixed into 28 parts by a twin-screw extruder AS-30 manufactured by Nakatani Kikai.
It was melted and kneaded at a temperature of 0''C to form a pellet.

After drying the pellets of Example 1 and Comparative Example 1 at 120°C for 10 hours using a vacuum dryer, injection molding (cylinder Temperature 260-280℃, mold temperature 80℃)
A test piece for measuring tensile strength was obtained. In addition, a part of the molded test piece was burned, and the average length of the glass fibers in the molded product was measured. The strength and average length measurement results are shown in Table 1. (Table 1) Tensile strength (K gf/cy2) Average fiber length (front shoulder)
Example 1. 1750 0.37
Bisame Example 1 1480 0.23 As is clear from the table, the strength of the molded article of the resin composition of the present invention using sodium titanate particles as the white pigment is higher than that of the resin composition using titanium oxide as the white pigment. greater than the strength of the molded product.

This is considered to be because the glass fiber length in the molded article of the resin composition of the present invention is maintained longer than the glass fiber length in the molded article of the resin composition using titanium oxide.

After dispersing 480 g of No. JI Nuea Anatase type titanium oxide in water 21, potassium carbonate powder 1402 is added. This slurry is heated to an inlet temperature of 250 to 260℃ and an outlet temperature of 90 to 100℃.
Spray dry at ℃. Next, this dried product was placed in an alumina crucible and fired in an electric furnace at a heating rate of 150°C/hour, a firing temperature of 770°C, and a holding time of 2 hours, and then at a rate of 200°C/hour. The temperature drops.

After putting the baked product into 21 hot water in a stainless steel container,
After stirring with a homomixer for 1 hour, wash with a sieve. Next, the washed algae was redispersed in 21 water and pulverized for 1 hour using an alumina ball mill.

The second product was identified by X-ray diffraction as a single phase of potassium hexatitanate. Further, when the particle size was examined using Horiba's automatic particle size distribution analyzer CAPA500, it was found to be a product with an average diameter of 0.6 μl.

2 parts of the potassium hexatitanate powder, 30 parts of chopped strand glass fiber with a length of 3 U, and 68 parts of polybutylene terephthalate resin (manufactured by Polyplastics, trade name: DURANEX 2000) were subjected to twin-screw extrusion manufactured by Nakatani Kikai. The mixture was melted and kneaded using an AS-30 machine at a temperature of 210°C to form a berelent.

ratio ``bite'' pull ≦L 2 parts of rutile titanium oxide, 3# shoulder chop.

30 parts of strand glass fiber and 68 parts of polybutylene terephthalate resin (manufactured by Polyplasti Nox, trade name: Jurao Sox 2000) were melted and kneaded at a temperature of 210°C using a twin-screw extruder AS-30 manufactured by Nakatani Kikai. It was made into pellets.

After drying the pellets of Example 2 and Comparative Example 2 at 120°C for 10 hours using a vacuum dryer, injection molding (cylinder The temperature is 200° (the mold temperature is 70°C),
A test piece for measuring tensile strength was obtained. In addition, a part of the molded test piece was burned and the average length of the glass fibers in the molded product was measured.9 The strength and average length measurement results are shown in Table 2.

(Table 2) Tensile strength (K gf/cm2) Average fiber length (+u+) Example 2 1450 0, 32
Comparative Example 2 1240 0.21 2 parts of the sodium hexatitanate particles used in Example 1, 40 parts of chopped strand glass fiber with a length of 3 U, polyphenylene sulfide resin (manufactured by Kureha Chemical Industry, trade name;
58 parts of Fortron K P S 214) were melted and kneaded at a temperature of 320'C using a twin-screw extruder AS-30 manufactured by Nakatani Kikai to form a pellet. , 40 parts of chopped strand glass fiber with a length of 3 x z, and 58 parts of polyphenylene sulfide resin (manufactured by Kureha Chemical Industries, trade name, Fortron KPS-214) were added to a twin-screw extruder AS~ manufactured by Nakatani Kikai.
The mixture was melted and kneaded at a temperature of 30°C to 320°C to obtain Pere Soto.

After drying the pellets of Example 3 and Comparative Example 3 at 120°C for 10 hours using a vacuum dryer, injection molding (cylinder temperature 320°C, mold temperature 150°C> to obtain a test piece for tensile strength measurement.A part of the molded test piece was also burned to measure the average length of the glass fibers in the molded product.

The strength and average length measurement results are shown in Table 3. Example 3 1730 0.30 Comparative Example 31510 0.19 2 parts of potassium hexatitanate particles used in Example 2, length 3I 25 parts of Pudostrand glass fiber, polycarbonate resin (manufactured by Idemitsu Petrochemical, trade name: Taflon l-2500)
Part 73, Nakatani If! Mechanical twin screw extruder AS-30
Melt and knead at a temperature of 290"C to form a paste.

Comparative Example 4 2 parts of rutile-type titanium oxide, 25 parts of chopped strand glass fiber with a length of 3 u, and 73 parts of polycarbonate resin (manufactured by Idemitsu Petrochemical, trade name: Taflon A-2500) were subjected to twin-screw extrusion manufactured by Nakatani Kikai. 290 by machine AS-30
It was melted and kneaded at a temperature of °C to form pellets.

After drying the pellets of Example 4 and Comparative Example 4 at 120°C for 12 hours using a vacuum dryer, the pellets were injection molded using a 5AV-30-30 injection molding machine manufactured by Yamagen Seiki. (290°C, mold temperature 90°C) to obtain a test piece for measuring tensile strength. In addition, a part of the molded test piece was burned, and the average length of the glass fibers in the molded product was measured. The strength and average length measurement results are shown in Table 3.

(Table 4) Tensile strength (Kgf/c shoulder 2) Average fiber length (shoulder j) Example 4 1130 0.35 comparative example, 4 980 0.25 large 1
(i) 2 parts of the potassium hexatitanate particles used in Example 2, 20 parts of chopped strand glass fiber with a length of 3 U, ABS
Resin (manufactured by Ube Cycon, product name: Cycorank UT-3
0) 78 parts using a twin-screw extruder AS-30 manufactured by Nakatani Kikai Co., Ltd.
The mixture was melted and kneaded at a temperature of 290°C to form pellets.

1 part 1 Rutile type titanium oxide 2 parts, length 3 cm chopped straw〉'20 parts ABS resin manufactured by Kube Saikon Product name: Cycora Tsukushi I T-30) 78 parts manufactured by Nakatani Kikai Co., Ltd. 290 by twin screw extruder AS-30
It was melted and kneaded at a temperature of °C to form pellets.

After drying the pellets of Example 5 and Comparative Example 5 at 120°C for 8 hours using a vacuum dryer,
Injection molding was performed using an AV-30-30 injection molding machine (cylinder temperature: 290" C1 mold temperature: 90°C) to obtain a test piece for measuring tensile strength. Also, a part of the molded test piece was burned, of glass fiber in molded products.

The average length was measured. The strength and average length measurement results are shown in Table 5.

(Table 5) Tensile strength (K gf/cm2) Average fiber length (zz) Example 5 1020 0.29 Comparative example 5 880 0.18 2 parts of potassium hexatitanate particles used in Example 2, length 311
20 parts of chopped strand glass fiber and 78 parts of polyacetal resin (manufactured by Polyplastics, trade name: Duracon M-90) were put into a twin-screw extruder AS manufactured by Nakatani Kikai Co., Ltd.
-30 at a temperature of 200°C and kneaded to form pellets.

2 parts of L1-corroded rutile type titanium oxide, 20 parts of chopped strand glass fiber with a length of 3H, and 78 parts of polyacetal resin (manufactured by Polyplastics, trade name: Duracon M-90) were subjected to twin-screw extrusion manufactured by Nakatani Kikai. 200 by machine AS-30
It was melted and kneaded at a temperature of °C to form pellets.

After drying the pellets of Example 6 and Comparative Example 6 at 120°C for 8 hours using a vacuum dryer, injection molding was performed using an S A V-30-30 injection molding machine manufactured by Yamaguchi Seiki f1. (Cylinder temperature: 190°C, mold temperature: 80°C) to obtain a test piece for measuring tensile strength. In addition, a part of the molded test piece was burned, and the average length of the glass fibers in the molded product was measured.

The strength and average length measurement results are shown in Table 6.5 (Table 6) Tensile strength (Kgf7'cy2) Average fiber length (Table II) Example 6 121.0 0.34
Comparative Example t-, 10300, 21 Example: 3 parts of potassium hexatitanate particles, 20 parts of Chiyo Tsubuto strand glass fiber with a length of 3 IN,
A polypropylene resin manufactured by Kube Industries, trade name: IBE Polypro, 17091-(K > 77 parts) was melted and kneaded at a temperature of 240°C in a twin-screw extruder manufactured by Nakatani Machinery at a temperature of 5-30 to form pellets. Soto.

Luxian-Honjiru-type acid (3 parts Hinataf, 20 parts chopped strand glass fiber with a length of 33111 mm, polypropylene resin (
Manufactured by Ube Industries, product name: UBE Polypro J709HK)
77 parts were melted and kneaded at a temperature of 240° C. using a twin-screw extruder AS30 manufactured by Nakatani Kikai to form pellets.

After drying the pellets of Example 7 and Comparative Example 7 at 120°C for 8 hours using a vacuum dryer,
Injection molding (
Cylinder temperature was 240°C, mold temperature was 70°C>, a nine-prong test piece was obtained for tensile strength measurement, and a part of the molded test piece was burned to measure the average length of the glass fibers in the molded product. The strength and average length measurement results are shown in Table 7.

(Table 7) Tensile strength (K gf/cm2) Average fiber length IN) Example 7 450 0.40 Comparative example 7 380 0.27 [Effect of the invention] L? J. As is clear from the above results, the glass fiber-reinforced thermoplastic resin composition according to the present invention has excellent mechanical strength, so it can be used in various electrical parts, mechanical parts, automobile parts, office equipment, and Suitable for use in heating appliances, etc.

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Claims (1)

[Claims] Glass fiber-reinforced thermoplastic resin composition comprising a thermoplastic resin, glass fiber, and alkali metal titanate powder