JPS58215448A - Carbon fiber-reinforced thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a carbon fiber-reinforced thermoplastic resin compsn. having excellent mechanical properties and processability and greatly improved electrical conductivity, by adding a small amount of an inorg. phosphorus compd. and/or an organophosphorus compd. CONSTITUTION:A compsn. consisting of 40-97wt% arom. polycarbonate, 3- 60wt% carbon fiber and 0-50wt% glass fiber is prepd. 0.1-1.0pt.wt. at least one member selected from inorg. phosphorus compd. such as phosphoric acid and/or organophosphorus compd. such as trimethyl phosphite is blended with 100pts.wt. said compsn. to obtain the desired carbon fiber-reinforced thermoplastic resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a carbon-bound, fiber-reinforced thermoplastic resin composition, and more particularly to a carbon fiber-reinforced aromatic polycarbonate composition that has excellent electrical conductivity and mechanical strength.

Carbon fiber-reinforced thermoplastic resin compositions, which are made by uniformly dispersing carbon fibers in thermoplastic resin, have special properties such as high mechanical strength such as high rigidity, and low mold shrinkage. Due to its rigidity.

It is widely used in various fields as a material for mechanical parts that require dimensional accuracy. It is also known that increasing the amount of carbon fiber added increases conductivity, and it has come to be used in fields where this property is essential. however,
In order to obtain the desired electrical properties, it is usually necessary to add a large amount of carbon fiber. For this reason, when a carbon fiber-reinforced thermoplastic resin composition is produced, for example, by kneading a thermoplastic resin and carbon fibers, the separation of the resin and carbon fibers results in poor stability when producing 51q, and the resulting pellet Currently, there are problems such as poor fluidity when molding using. Furthermore, carbon fibers are extremely expensive, and together with the aforementioned poor productivity, carbon fiber-reinforced resin compositions have become increasingly expensive, and their uses have been greatly limited.

As a result of studies to solve the above-mentioned problems, the present inventor has discovered that a carbon AN fiber-reinforced Atagawa plastic resin composition contains a small amount of unsupported phosphorus compound and/or organic phosphorus compound. kt JS, 4 Qualitative is significantly improved, and -4<1+
/, - It is possible to impart mechanical properties and workability,
, >, ) is W, Ill L , and the present invention has been achieved.

Immediately 6, the present invention low! A-*m, Silica carbonate 40-971)j ta≠, Carbon twill 13-60 layers and Glass ##M11)-50 -, J゛Resin composition 1001i'lA31i PI, I
4tk h+ Zr Il:j, 2 or more types of inorganic phosphorus compounds and/or 1
dhlt 4・Combination 1. - (It is a carbon fiber reinforced marine VIJ + 1.4 #i fat composition with unique characteristics.

In the present invention, Iri 41 (-44N-Apricot 1^Polycarbonate is divalent] -Nova and /J-Bone,-) = +j precursor by a solution method! I24. It is what is produced in the market. Typical examples of divalent phenol σJ include 2,2-his(4-1=luyasifnyl)propane[bis71nor^]11°su(4-human μxypheninot)meta7. 2.2-bis(4-hydroxy-3
, 5-jime f) 1 no ni sword) propane, 2, 2-bis (
4-Hydroxy-3,5-digpmphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxyphenyl)sulfide, bis(4-human I: Preferred dihydric phenols include bis(4-
hydroxyphenyl) alkanes, especially hisphenol A
The main raw material is In addition, in carbonate precursor and 1-1, carbonyl halide, carbonyl ester 7
1+) or halopormate, etc. are added, and the monthly salary is phosgene, diphenyl capo 4-+.

It is a mixture of dihaloformate and straw of dihydric phenol. In producing aromatic polycarbonate, the above dihydric phenols can be used alone or in combination of two or more. It is also possible to use a mixture of two or more of the aromatic polycarbonates thus obtained2.
The molecular weight of the aromatic polycarbonate is generally 10,000 to 100,000, preferably 15,000 to 60,000. 4. Producing aromatic polycarbonate having these molecular weights. y (excluding (-1) trI) 1 - mackerel regulator, I to improve processability, -me Vr toge AIIQ, ■, or 4- to promote reaction, Mb addition ( :1j Haibaroku no.

The fibers in the 16th present invention Ill-4'-ZI charcoal are generally cellulose-injected 1,7 krill #&! I11, By firing lignin, petroleum or 41 return thread special 1''-f-Y as a raw material, Nj? There are different types of charcoal * the length of the shroud is usually 0,0
It is in the range of 5 to 10 yen, (Y1'J, s to 15μ. This carbon fiber is chopped 1゛, 1 land, r
+-ping, strand l', mizl l' --
. The surface of carbon fiber increases H-111#i with resin-4
There is no problem even if the surface treatment example ★- is epoxy treatment, methane treatment 311, etc.

On-site textiles ^Illll1. t' 1 to 60% by weight, preferably 115 to 5.
41, small sex, and 60 double phase chiwoko
The fluidity in V-shape becomes poor, and 5 − − addition=[! 1 is not preferable because it significantly inhibits 1.

The composition of the present invention may contain θ~50*i% of glass fibers. Any glass fiber that is used for aromatic polycarbonate can be used without any problem. Generally, E glass with a small alkali-containing lid is preferred.

The glass fiber diameter is preferably 5 to 20 μm, and the glass fiber cone length is preferably 0.01 to 10% in the pellet. The surface of the glass fiber may be treated to improve adhesion with the resin, for example, treated with a silane coupling agent, and is preferably used. The blending of glass fiber shows the effect of improving the impact resistance of the resin composition of the present invention,
In addition, there is no effect of improving the conductor or sexiness, which is preferable.

Preferred specific examples of the inorganic phosphorus compound and/or organic phosphorus compound used in the present invention are as follows. Examples of inorganic phosphorous compounds include metasonic acid, metaphosphoric acid, primary hypophosphorous acid, and phosphorous acid.

Phosphoric acid, piphosphoric acid, etc., preferably phosphorous acid.

Phosphoric acid and its alkaline earth metal salts or 6- are curved lead JIK@silk roux r・a4. Examples of phosphorus compounds include 71 examples of phosphoric acid, liptyl phosphate, 1-phosphorus, and phosphorus.・Dil phosphate, tripheni/l
-Posphae 1,1 liqueμ ethyl phosphate,;-
Riocouf-ruphos 7: r-t, triethylphosphinr, -), nf-! - Lucresinotophosphate.

Diphenyl senyl phosphate.

Tributylic T-1 phosphate, dimethyl gosfur phenylphosphonate, 3.5-ditardialp.f
-Lu 4-11F "l xybenzylphosphonic acid dimethyl ester, dibutyl phosphate.

Geocouple phosphate 11 silylable pyruphosphate
1.l (dodemisu, light phenylphosphonic acid,
Dimethyl nyspur (1) xybenzylphosphonate (1); also phosphorous acid ester example
11F1-1-nylphosphite, trimethyl-1Sulfy-1-, tricresyl phosphite, nympheninoC nonylphenyl phosphite.

Tris (Noni sword) - 1l Nitsuto) bosphite, triisooctylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite i, l-lysotecylphosphite, F-lilaurylphosphite, triocudecylphosphite, Trioleyl phosphite, trilauryl trithiophosphite, diindecyl phosphite, dilauryl phosphite, dioleyl phosphite, tris(2,4-ditardylphenyl) phosphite, distearylpentaerythritol diphosphite, etc. , and alkaline earth gold salts or lead group metal salts, with trimethyl phosphite and triphenyl phosphite being preferred.

Kowara's phosphorus compound is aromatic polycarbonate 40~
97*Quantity, carbon fiber 3~60 weight #chi and glass fiber θ
A very small amount, that is, 0.01 to 1.0 parts by weight, is blended per 100 parts by weight of a resin composition having a weight ratio of ~50. The mechanism of action is not clear (.) has the effect of significantly improving conductivity.

If the amount of phosphorus compound added is less than 0.01 part by weight,
Improving effectiveness of rice I! If it does not exceed 1.0 parts by weight, the stability during extrusion may be affected by foaming during thermoforming of the product. This is not desirable because M)i tjJ)^J'lt- is caused during the period when the condition becomes worse.

Any known method can be used to prepare the tree composition of the present invention. For example, mixing and extruding a mixture of aromatic polycarbonate, #1 elementary fiber, glass fiber, and phosphorus compound using a ←-It, b, or twin-screw extruder, or a Pan Bali mixer. For example, a method of molding the molded material using a heating roller or the like, or a method of directly molding the molded material by injection molding using a molding machine. Friend, Rui:t-! II 7 Kōten II Various methods are listed, such as a method in which one or more of millicarbonate, carbon wire fiber, glass cloth, and phosphorus compound are mixed in advance, and then the remaining material is kneaded. However, either method produces a moderate effect.

The effect will be expressed as needed in the case of the tree of light (111). , fillers, dyes and pigments, etc. are included beforehand. Also other conductive properties 9
- It is also effective to add fillers such as acetylene black and Ketjen blank.

The carbon fiber-reinforced resin composition of the present invention has significantly improved rigidity and conductivity, which is superior to the stable example of the 1-dimension test, making it a useful resin that can be widely used in many fields where these properties are required. It is a typeface.

The present invention will be explained below with reference to Examples, but it is not necessarily limited to stiffness.

Examples 1 to 11 and Comparative Examples 1 to 5 Aromatic polycarbonate (manufactured by Teijin Chemicals, Panlite L
-1250) and chopped strand carbon fiber (manufactured by Toho Rayon Co., Ltd.; HTA-C6-8) with a cut length of 6 were dried in a hot air circulation dryer at 120°C for 6 hours.
Preliminary mixing was performed in a tumbler at the blending ratio shown in Table 1.

Immediately thereafter, the mixture was extruded into pellets using a single-screw vent extruder (30 mm, L/D=28) with the cylinder temperature set at 300°C.

10- Next issue; see you again! After drying at 120°C for 6 hours, a test piece was molded using an open nozzle screw injection molding machine (5 ounces) with NlAl # cylinder temperature at 300°C and mold temperature at 100°C. , its volume resistivity and bending strength were determined to be 611. The urination is shown in Table 1.

As is clear from the first figure, the resin composition of the present invention has much higher conductivity than that of aromatic polycarbonate simply reinforced with carbon fibers. It is possible to reduce the amount of carbon fiber filled in order to obtain conductivity, and at the same time has excellent mechanical strength.

Examples 12 to 17 and Comparative Examples 6 to 10 Aromatic polycarbonate (manufactured by Yotaikasei Co., Ltd.; Panlite L
-1250), chopped strand carbon fiber with a cut length of 6u (manufactured by Toho Rayon Co., Ltd.; HTA-C6-8) and chopped strand glass fiber with a cut length of 3 Ill (Nitto Keisha 411; as3PE-401) 12
After drying in a hot air circulation dryer at 0°C for 6 hours, the resin composition obtained in Example 91 was mixed in the same manner as in Examples 1 to 11 or Comparative Examples 1 to 5 at the compounding ratio shown in Table 2. Volume resistivity and bending strength were measured in the same manner as in Examples 1 to 11 or Comparative Examples 1 to 5. The results are shown in Table 2.

It is clear from Table 2 that the composition of the present invention has much higher 4W properties than the one made by reinforcing carbonate with carbon fibers and only t-. (
A carbon fiber filled cocoon can be used to obtain a conductivity of 1-1.
In history, 411I (which also has IN strength at the same time)
<+rrt fat composition.

Procedures Amendment Written in July 1982 by the Commissioner of the Japan Patent Office 1 Indication of the case Japanese Patent Application No. 57-98443 2 Name of the invention Carbon fiber reinforced thermoplastic resin composition 3 Person making the amendment Relationship with the case % Pestle Applicant 1-6-21 Nishi-Shinbashi, Minato-ku, Tokyo Teijin Kasei Ltd. Representative Yoshiki Yamazaki 4th Representative 2-1-1-5 Uchisaiwai-cho, Chiyoda-ku, Tokyo Details of the invention in the specification to be amended Column 6 "Explanation" Contents of the amendment (1) In the second page, line 2 of the specification, the words "mechanical parts" have been replaced with "
"Mechanical parts" K Corrected.

(2) On page 3, line 10, the text "0,1~1.0" is corrected to "o, o +~1.O".

(3) On page 5, line 9 of the same page, ``Usually 0.05~+oJ'' is corrected to [Usually 0.01~10 in pellets].

(4) On page 7, line 2, the phrase ``for example, tributyl'' should be corrected to ``for example, trimethyl phosphate, triglythyl.''

(5) On page 7, line 13, the phrase 1, preferably phenyl, is corrected to ``preferably trimethyl phosphate, phenyl.''

(6) In Table 1 on page 12, in Example 1, in the column of “Phosphorus compound”, “Trimethylphosphine L 1.O
j Correct door 7 to ``trimethyl phosphate o, + J.

(7) In Example 2 in Table 1 on page 12, in the column for phosphorus compound 1, replace "tt l, QJ" with "
Corrected to O, lJ.

= 2- 1- (81rrrl No. +4 page #12 Example 12 in the table
In r IJ y, in the column of IC conversion & substance 1, "trimethyl phosphite o, +, 1" is corrected to [trimethyl phosphite-1-o, + J.

and -3-

Claims (1)

[Claims] Aromatic polycarbonate 40-97% by weight. Carbon fiber #3-60 weight percentage and glass fiber 0-50 weight%
One or more inorganic phosphorus compounds and/or 0.01 parts by weight of a composition consisting of
A carbon fiber-reinforced thermoplastic resin composition, characterized in that it contains a portion of 1,11.