JPS61241356A - Granular polycarbonate resin composition containing carbon fiber and production thereof - Google Patents

Abstract

PURPOSE:The titled composition, obtained by heating a solution of a polycarbonate containing carbon fibers in methylene chloride while keeping the suspended oil-in-water state and evaporating the methylene chloride, and having improved handleability and quality. CONSTITUTION:A granular polycarbonate resin composition obtained by incorporating a solution of a polycarbonate in methylene chloride in 0.5-30wt% concentration with water and carbon fibers, e.g. chopped fibers or milled fibers having <=10mm length, at <=95/5, preferably 5/95-90/10 weight ratio and heating the resultant mixture while keeping the suspended oil-in-water state below the melting point of the polycarbonate to evaporate the methylene chloride and having the particle size distribution of 3-8 n in the formula of Rosin-Rammler's distribution formula [R is oversize cumulative distribution (wt%); DP is particle diameter (mm); n is a constant], 0.5-6mm particle diameter (DP50) of the 50% oversize cumulative weight and 0.1-0.6g/ml bulk density.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a granular polycarbonate resin composition containing carbon fibers and a method for producing the same. Specifically, the present invention relates to a carbon fiber-containing granular polycarbonate resin composition that contains carbon fibers and has excellent handling properties and quality, and its production@.

[Conventional technology]

As a polycarbonate resin composition containing carbon fibers, polycarbonate powder or pellets and carbon fibers are mixed and fed to an extruder, the polycarbonate is melted, kneaded and extruded, and the resulting pellets are formed into pellets using a molding machine. There are known ways to do this. (Tokuko Akij/-
However, in this method, it is necessary to heat the polycarbonate to a melting temperature, and if carbon fibers are present at this time, the thermal decomposition of the polycarbonate will be promoted, and the molecular weight of the polycarbonate in the resulting composition will decrease. is lower than the initial molecular weight. Also, at this time, mix the carbon fibers thoroughly in order to disperse them uniformly in the resin! However, this kneading causes the carbon fibers to break, reducing their effectiveness as a reinforcing agent, and the molded pieces made from these pellets have poor mechanical strength. For this reason, molded products manufactured using this pellet cannot exhibit sufficient performance. Moreover, carp mixing using an extruder is not completely satisfactory as it consumes a large amount of electricity for melting and heating the polymer and kneading υ. Also, increase the blending amount of charcoal * M miscellaneous, for example, 30
If the amount exceeds % by weight, it becomes difficult to smoothly feed the mixture of polycarbonate and carbon fiber to the extruder.

Also, polycarbonate resin is different from thermoplastic resins such as polyethylene, polyvinyl chloride, polystyrene, etc.)
Since the viscosity in the molten state is extremely high, it is technically difficult to uniformly mix carbon fibers in a heated state using an extruder.

[Purpose of the invention]

As a result of extensive research into polycarbonate resin compositions containing carbon'X fibers, the present inventors have found that when adopting specific means, power and heat are not required, such as methods using an extruder or kneader. Don't be cheap, from low compounding amounts to extremely high compounding 1
1 carbon fiber, and carbon N1. It is possible to produce a granular polycarbonate resin composition with oriented webs and a uniform particle size, and this granular composition can be fed as is to an injection molding machine, so that the polycarbonate molecules in the molded piece and the charcoal are The present invention was completed based on the knowledge that the chance of reducing the mechanical strength due to the bending of 1 m fibers can be reduced. The purpose is to provide a granular polycarbonate resin composition with excellent quality, and its gist is that the particle size distribution is according to the distribution formula n is 3~r, cumulative weight on sieve!0 particle size (Dpso) is 0.j-4, bulk density is 0./~O0
This is a granular polycarbonate resin composition of Ov/Ht.

This granular polycarbonate resin composition can be produced by heating a methylene chloride solution of carbon fiber-functionalized polycarbonate while maintaining an oil-in-water suspension state to evaporate the methylene chloride.

[Structure of the invention]

The present invention will be explained in detail below.

The granular polycarbonate resin composition of the present invention is separated from a PCM solution (a solution of polycarbonate in methylene chloride) at a temperature lower than the melting point of the polycarbonate resin. Carbon fiber and polycarbonate resin compositions are not preferred because they cause a decrease in molecular weight when exposed to high temperatures.

The n term is 3 to 4, preferably 3 to 4. Although it is not inconvenient that this value is high, it is difficult to industrially produce a value that is too high. On the other hand, if it is too small, the effects of the present invention cannot be obtained.

The shape may be either a lump or a spindle as described later, within the range of pso from O0!~≦.Also, the bulk t?B degree may be O0/~0.69/d for the reasons described later. selected from among them.

The polycarbonate resin targeted by the present invention includes a covalent group represented by the general formula -80- or -802-, R is a hydrogen atom, a heptavalent hydrocarbon group, or a halogen group, and the same type of polycarbonate resin is used. It may also be of different types. R
' represents a covalent hydrocarbon group, and the aromatic nucleus may have a halogen atom or a heptavalent hydrocarbon group. A polycarbonate resin obtained by an interfacial method or a bath liquid polymerization method is coated with mate in the presence of an acid binder such as methylene chloride and caustic or pyridine.

Specific examples of the dihydroxydiaryl compound represented by the above general formula include bis(guhydroxyphenyl)methane, /,/-bis(4t-hydroxyphenyl)ethane, 2,2-bis(4t-hydroxyphenyl)cropane, co, --bis(terhydroxyphenyl)butane,
λ, λ-bi/((4t-hydroxyphenyl)octane, his(4t-hydroxyphenyl)phenylmethane,
2. 2-bis(4t-hydroxy-3-methylphenyl)propane, /, /-bis(4t-hydroxy-3-
tert-butylphenyl)propane, J, J-His(4t
-hydroxy-3-bromophenyl)propane, -2,
2-bis(guhydroxy-j,j-dibromophenyl)clopane, -1λ-bis(4t-hydroxy-3,j
-bis(hydroxyaryl)alkanes such as -dichlorophenyl)propane, /,/-bis(4t-hydroxyphenyl)cy/C+pentane, /,/-bis(4
Bis(hydroxyaryl)cycloalkanes such as t-hydroxyphenyl)cyclohexane,
Dihydroxydiphenyl ether, p,4t'-dihydroxy-3,i'--/dihydroxydiarylethers such as methyldiphenyl ether M, a,4t
〆-dihydroxydiphenyl sulfide, 4t, 4t'
- dihydroxydiaryl sulfides such as dihydroxy-3,3'-dimethyldiphenyl sulfide, g
, 4t'-dihydroxydiphenyl sulfoxide, gβ
I-Dihydroxy-3.3 Dihydroxydiaryl sulfoxides such as 3-dimethyldiphenyl sulfoxide, yβIβ zidroxydiphenyl sulfone, a, 4
Examples include dihydroxydiarylsulfones such as t'-dihydroxy-3,3/-dimethyldiphenylsulfone.

These are used alone or in a mixture of λ or more types,
In addition to these, dihydroxy compounds such as hydroquinone, resorcinol, Hiroshi, Nagi-dihydroxydiphenyl, dicarboxylic acid halides such as terephthal chloride and isophthaloyl chloride, and diamines such as piperazine and dipiperazyl are used in combination. It's okay.

As the organic solvent, methylene chloride is used, or other mortar such as chloroform, carbon tetrachloride, /1.2-dichloroethane, /, /
, -monotrichloroethane, tetrachloroethane, chlorobenzene, etc.

As the carbon fiber, various known carbon fibers manufactured using rayon, acrylonitrile, pitch, lignin, etc. as raw materials can be used.

Further, carbon fibers having a length of 208 mm or less can be used, but if the length is too long, there is a risk that stable operation will be disturbed, such as getting caught in the stirring blade.

Specifically, chopped fibers having a diameter of 10111 or less (fiber m-&=<關、3關), milled fibers (average fiber length about 0.2 times), and the like can be mentioned. There is no problem even if the sizing agent is attached, but since the cost of carbon fibers increases, it is not necessary to attach the sizing agent.

Next, a method for producing the granular polycarbonate resin composition of the present invention will be explained in detail.

Preparation method There is no particular restriction on the mixing order of the charcoal One method is to suspend carbon fibers in water and add an organic solvent solution of polycarbonate resin to transfer the carbon fibers to the organic solvent solution.One method is to prepare the champion at the same time. Methods include dispersing the polymer and adding a methylene chloride solution.

stirring Stirring is performed in a normal stirring tank.

It does not matter whether there is a baffle or not.

For stirring, you can also use Konwa-made items such as squid pallets, but
The peripheral speed of the tip of a turbine, fan turbine, 7 audler, etc. that stirs at a relatively high speed is /, Om/5
tsc or more is preferable, and if the tip peripheral speed of b00,000 is slow, the shape of the granules becomes large, so it is preferable6. Distillation It is easiest to distill off the solvent by heating it from the heating jacket of the stirring tank. . The heating temperature is preferably within the range from the boiling point of the organic solvent to the black point (J)/<7"C. There is no particular problem if the heating is carried out above 10°C, but the high density of the particles obtained It is better to keep it within the range of λor near b0. As for granulation, when operations are carried out under the conditions described above, carbon fibers will aggregate with the polymer as a contact medium, but they will not simply aggregate but will have a different shape. The shape of the granules varies depending on the length of the carbon fiber used, and usually the fiber length is / I1
When it is less than 1, it is accumulated on the sieve! Average IEl diameter of O1% (
DP! Jl) 2>' 0. The carbon fibers are arranged and aggregated in a lump related to ~, and the carbon fibers are coated with a polymer.

Also, when the carbon fiber length is /u or more, the dragon length is usually 0. J -411ρ carbon fibers are coated with a polymer and the carbon fibers are arranged in a certain direction in a spindle shape, DP
,. is 0. A granulated product of −41 m is obtained.

If the particle size of the granulated product is too small, the particles will scatter during handling noise, and if it is too large, it will be difficult to bite into the screw of the molding machine. Also, when using it as a masterbatch, the particles are so... 7 and the dilution ratio is large, the dispersion of carbon fibers becomes poor.

The bulk density is 0°7 to Ojf/d, preferably 0.2 to 0.
It is 6f/m. If the high density is too low, it will be eaten up quickly during molding, and it will be disadvantageous in terms of continuous packaging, hopper charging chamber, etc. On the other hand, it is difficult to industrially manufacture one with a large value (006 V/-).

Polycarbonate resin magnetism in organic solvent solution Organic solvent l
@The concentration of polycarbonate resin in the liquid is 0. ! ~30 emperors
%, preferably 2 to 20% by weight. In extremely high rocky conditions, it becomes difficult to disperse additives. On the other hand, if the degree of modification is too low, productivity will be poor. O Ratio of carbon fiber to polycarbonate resin #! ! maintenance/
Polycarbonate tota j/j * Below the child's height, preferably!
/The light is 0/10.

Carbon fiber! Technically there is no problem if it is less than J%, but when considering the first update as a master patch, there is little benefit if it is less than J%.

Carbon fiber/polycarbonate is 9! /! Above this level, the effect of the polycarbonate on the charcoal fg fibers is insufficient, making it impossible to granulate carbon fibers.

θl1l (t% or less, preferably 0.7 to
It is 30% by weight. If the amount is greater than 4 to t% by weight, granules with a good shape cannot be obtained. A low concentration is not particularly inconvenient in practice, but it is not a good idea because the amount of processing is small.

driving The invention can be carried out either batchwise or continuously.

Other fillers The granular polycarbonate resin composition of the present invention may contain the following fillers together with carbon fibers.

As fillers, any filler that is practically insoluble in water and organic solvents can be used. Specific examples of powdered fillers include silica, alumina, silica alumina, titania, magnesia, zinc white, and carbonate. Calcium, barium carbonate, aluminum sulfate, barium sulfate, gypsum, calcium silicate, Merck, kaolin, pennite, diatomaceous earth, silica, quartz powder, pumice powder, feldspar powder, graphite powder, glass powder, mica, metal powder, etc. can give. In addition, specific examples of fibrous materials include glass fiber, metal whiskers,
Examples include potassium titanate fiber and asbestos.

〔Example〕

Examples will be described below, but the present invention is not necessarily limited to slippage. In the examples, parts indicate weight.

In addition, the particle size is calculated by integrating the amount of charge on the sieve! It is indicated by Ochi (D2..), and the particle size distribution is Showa! October 2, 3rd year! Published by Maru Tatami, ``
Rosin- described on page 23 of "Revised Surrounding Board Chemical Engineering Handbook"
It is shown as the value of n in Rammler (o-Schiff, Rammler → distribution formula % formula %).

Example of producing granules: 4t, 4t'-dioxydiphenyl-λ, -propane (bisphenol A) 4C Reacted with methylene chloride and phosgene in the presence of an aqueous solution of caustic soda, resulting in purified polycarbonate (polycarbonate) 2.000 parts of methylene chloride f# of polycarbonate, 2.000 parts of water/♂, and 3200 parts of carbon fiber [manufactured by Toho Rayon ■, trade name HTA-7, cut to 0.1113+ and desized with a solvent, 3200 parts of carbon fiber [manufactured by Toho Rayon ■, product name] The mixture was placed in a stirring tank with a jacket and stirred with a multi-plate fan turbine blade lever at 4 torr and 0 m to disperse it well.Next, hot water of 4 to C or higher was poured through the jacket to heat it, and the evaporated methylene chloride was distilled into a gas distillate. It was extracted from the exit pipe to the outside of the υ system, condensed, and collected. Approximately 30
After a few minutes had elapsed, when almost no methylene chloride was distilled out, the contents were filtered through a wire mesh to obtain granules.

The resulting granules were uniformly shaped lumps of λ~zyxyiB consisting of 70% carbon fiber and 20% polycarbonate. The bulk density measured after drying is O,g3? /d
, the average particle diameter (Dp, .) is λ, 3, particle size distribution (n value)
It was 0.

This polycarbonate resin granule is referred to as granule A.

Granular body production example-λ Granular body production example-/Instead of carbon fiber, average grains 41E0.
/My polycarbonate resin powder-2oo.

and water/♂, o o o s are charged into a 2Jt jacketed agitator 41, and J 4t is charged with a single stage of Z fan turbine
The polycarbonate resin powder was well dispersed by stirring with Or, p, and m. Warm water was then poured into the jacket to maintain the same temperature at 4tj°C. In this warm water, dissolve 3,00 θ parts of the polycarbonate resin powder in methylene chloride, 2 g,
000 parts/l of polymer solution using a pump
/Hr, and granulation is performed while coating with resin powder. The evaporated methylene chloride was extracted from the thread through the gas distillation tube, condensed, and collected. When the supply of the polymer solution was completed and almost no methylene chloride with a diameter of about 30 minutes had been distilled out, the contents were passed through a wire mesh to obtain a granulated product.

The obtained granules are particles of 0 Ju-j.

Did you measure it after drying? lII density is 0. tO9/d, average particle size 5k (Dps6) was 2.7u, and particle size distribution (n value) was 2.

This polycarbonate sanitary resin granule is referred to as granule B.

Pour 1 rsh liquid into a jacketed Nigoo (capacity: 4 tot) with set type blades. /Hr -t" to produce polycarbonate resin granules while evaporating methylene chloride. The bulk density measured after drying this powder was 0.
．． 72t/d, average particle diameter (Dpea) is 0, J'
01m, the particle size distribution (n value) was /.

000 parts of this granular material and carbon fiber [manufactured by Toho Rayon, trade name HTA-0, (V8, fiber length 1 mm: 17
000 parts were tri-blended and processed using a 4tO extruder. The size, J, and length were made into short lengths. This pellet will be referred to as granular material C.

Granule production example - Stirring tank with jacket of 2jt (Material: 8[]8-j#)
K water/It and carbon [m [manufactured by Toho Rayon, product name E]
After cutting TA-7 into 01jIII, carbon fiber [J00t] desized with a solvent was charged, and stirred at 2 u Or, p, m with 2 μ fan turbines to disperse it.
Pour hot water over 4tj℃ into the jacket to reduce the internal temperature (tj
Keep at ℃.

Next, 3,200 parts of polycarbonate resin was dissolved in ♂, 000 parts of methylene chloride solution, and this liquid was pumped into 6
The mixture was charged into a granulation tank at 17 kir, and the methylene chloride was evaporated before granulation. The evaporated methylene chloride was extracted from the tank through a gas distillation tube and condensed. After about 30 minutes, when almost no methylene chloride was distilled out, the contents were filtered through a wire mesh to obtain granules.

The resulting granules were uniformly shaped lumps of 2 to 4 tons, 1 mg, consisting of 20 pieces of carbon fiber and 10% polycarbonate resin. The bulk density measured by dry fL measurement is 0,311
7d! The average particle size (Dpso) was -16 yen, and the particle size distribution (n value) was 3.6.

This polycarbonate resin granule is made into a granule.

Example of producing granular material - separable flask with jacket of 60/l water 6θOd,
Of polycarbonate? Methylene chloride solution 4ty, and carbon fiber [manufactured by Kureha Chemical @: M-104tT:
(all fiber length; 0.!, fiber diameter 2//μ)] Insert 309 and y fan turbine 11t28 ≦0θr, p0m
Stir to disperse well. Then Jakela) K&θ~1
Heating was carried out by flowing hot water at 0°C, and the evaporated methylene chloride was extracted from the system through a gas distillation tube, condensed, and collected. After approximately 3θ minutes had elapsed, when 11 methylene chloride had been distilled out, the contents were filtered through a wire mesh to obtain a granulated product.

The resulting granules were particles of 2 11111-j ml, containing ero% carbon fiber and 120 ml of polycarbonate. The high density measured after drying is 0. j/l/m.

What is the particle size distribution (n value)? , was 0.

Granule production example-6 Water 6θOd,
Add 4 tons of polycarbonate j% methylene chloride solution and carbon fiber [manufactured by Kureno 1 Chemical ■: c-10iT (fiber length 2jj1m, fiber good; //μ)]♂f into 7 pieces.
The mixture was well dispersed by stirring at 600r and plm in the λ stage of the turbine. Next, ao-to'c hot water was flowed through the jacket to heat it, and the evaporated methylene chloride was extracted from the jacket through the gas distillation tube, condensed, and collected. After about 30 minutes, when almost no methylene chloride was distilled out, the contents were filtered through a wire mesh to obtain granules.

The resulting granules were composed of 10 inches of carbon fiber and 0 inches of polycarbonate, and had a diameter of 2 ml 1 f3.
A spindle-shaped product was obtained. The bulk density measured after drying was 0°/19/aA, and the particle size distribution (n value) was 3.7.

The granules obtained by the method of granule production example-7 to granule production example-da are tri-blended, and this is used as a raw material in a vent injection molding machine (Japan Steel Works Hm-iooB).
We attempted to form a tensile, bending, and engineered God impact piece using mV).

Molding was performed at a resin temperature of 300°C, injection time of 10 seconds, and Iv-2.
It was conducted at JA13C. The obtained molded piece has tensile strength,
Elongation, bending strength, bending modulus, and engineering zod impact value were measured.

The results are shown in Table-7.

Example 7 When a granular material was molded using the injection molding machine described above, there was no scattering of the granular material during handling, and it was well penetrated into the extruder screw. The molecular weight of the obtained molded piece is shown in Table-
As shown in Figure 2, the decrease in molecular weight was smaller than that of a molded piece made from a pellet kneaded in an extruder (prior art). Also,
The mechanical properties of the molded piece are R'f in the molded piece: fiber length is 0.0 because the fiber length does not break due to kneading during extrusion welding. Jju (σ, -〇+u in the conventional technology), and the tensile strength and bending strength were increased by 30% compared to the conventional product.

Comparative Example-/When molded in the same manner as Example-7 using granular material C,
Although the handleability was good, the molecular weight decreased due to thermal deterioration during melt pelletization in an extruder. Furthermore, as shown in Table 1, since the carbon fibers in the molded piece were short, the tensile strength and bending strength were reduced, and the surface of the molded piece lacked gloss.

Example - One granule A/λ! In the tri-blend of part θ and 3710 parts of granular material B, there was no scattering of the granular materials during handling, and there was no disturbance in the extruder screw.

The molecular weight, mechanical properties, and surface of the molded piece are 5s Example-
It was as good as / and had no problems.

The results are shown in Table 19.

〔Effect of the invention〕

According to the manufacturing method of the present invention, there are no problems such as dust generation or scattering during handling, and the fluidity in a silo or hopper is good. When the granulated product obtained in the present invention is used as a masterbatch, the filler is contained at a high [1K] level, so a large dilution ratio can be adopted, and thus costs can be reduced.

In addition, when used for direct molding, products containing a high degree of filler, which could not be produced conventionally, can be easily obtained. Since the molded piece obtained at this time does not have a kneading operation using an extruder, the carbon fibers in the molded piece are long and the mechanical 51
Ii The storm becomes stronger.

Sender: Mien Kasei Kojo Co., Ltd. Representative Patent Attorney Hase - Others/names Procedural amendment (voluntary) Showa to July 73rd

Claims (2)

[Claims] (1) A carbon fiber-containing granular polycarbonate resin composition separated from an organic solvent solution of carbon fiber-containing polycarbonate at a temperature lower than the melting point of the polycarbonate, and having a particle size distribution according to the Rosin-Rummler distribution formula R = 100exp (- bD_p^n) (wherein, R is the integrated distribution on the sieve [wt%], D_p is the particle diameter [mm], and b is a constant), and n is 3 to 8, and 50% of the integrated weight on the sieve is A granular polycarbonate resin composition having a particle size (D_p_5_0) of 0.5 to 6 mm and a bulk density of 0.1 to 0.6 g/ml. (2) A method for producing a granular polycarbonate resin composition containing carbon fibers, which comprises heating a methylene chloride solution of polycarbonate containing carbon fibers while maintaining an oil-in-water suspension state to evaporate the methylene chloride.