JP2000226508A - Fiber-reinforced resin composition and molding product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having excellent impact resistance, warpage transformation electromagnetic wave shielding properties and combusti bility of thin wall part by adding a specific carbon fiber to a resin composition consisting of a polycarbonate resin and a liquid crystalline resin. SOLUTION: This composition comprises (A) 100 pts.wt. of a resin composition (i) 99.5-70 wt.% of a polycarbonate resin (e.g. an aromatic homo- or copolycarbonate having 0.2-3.0 dl/g logarithmic viscosity measured in 1.0 g/dl concentration in methylene chloride at 20 deg.C) and (ii) 0.5-30 pts.wt. of a crystalline resin [e.g. a liquid crystalline polyester composed of structural units of formulas I, II, and III (R1 is a group of formula IV or the like; R2 is a group of formula V or the like), a liquid crystalline polyester amide or a and liquid crystalline polycarbonate] and (B) 5-300 pts.wt. of a carbon fiber (e.g. PAN-based or a pitch-based carbon fiber) composed of >=60 wt.% of carbon fiber having 0.15-6 mm fiber length.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber reinforced resin composition excellent in fluidity, impact resistance, warp deformation, electromagnetic shielding properties and thin-walled flame retardancy, and a molded product thereof.

[0002]

2. Description of the Related Art Thermoplastic resins such as polycarbonates are being used as injection molding materials in a wide range of fields such as mechanical mechanism parts, electric and electronic parts, and automobile parts by utilizing their excellent characteristics. On the other hand, the demand for molded articles has increased with the progress of technology, and more complicated shapes have been demanded. Therefore, it has been desired to improve fluidity.

Therefore, an optically anisotropic liquid crystalline polymer characterized by a parallel arrangement of molecular chains is attracting attention because of its excellent fluidity and mechanical properties, and improves the fluidity and mechanical properties of a thermoplastic resin. Numerous alloying technologies are being studied for this purpose. JP-A-6-200129 is an example of a polycarbonate having a specified terminal group concentration. Numerous alloys with thermoplastic resins have been studied, such as PO
LYMER ENGINEERING AND SCIENCE, 1991, Vol.31, No.6 and Jo
urnal of applied Polymer Science, Vol. 62, (1996).

[0004]

However, when a filler is used, the flowability of which is slightly improved even though a material in which the terminal groups of polycarbonate are controlled as in JP-A-6-200129 is used. The impact strength is not improved, and simply blending does not improve the warp deformability. In addition, when a study was made using the liquid crystal polyester described in the above-mentioned literature, when simply blended, the same results as those in the above publication were obtained, and the impact resistance, warpage, and the like were not improved. Also, when a compatibilizer or the like is used to improve properties such as impact strength, it is presumed that a reaction occurs with the thermoplastic resin,
It was found that, although a decrease in impact properties was suppressed, the mixture was too mixed with the thermoplastic resin and did not exhibit a fluidity improving effect or a high electromagnetic wave shielding property. In addition, in the case of a simply blended alloy material, warpage and burrs are generated during molding, so molding must be performed under narrow molding conditions, and secondary processing such as deburring of the obtained molded product is required. In thin and large molded article applications such as a body (housing), use is limited.

Accordingly, the present invention solves the above-mentioned problems, and can be processed at the processing temperature of a conventional polycarbonate resin, and without impairing the conventional characteristics of the polycarbonate resin, and has an impact resistance, a warp deformation, and an electromagnetic shield. An object of the present invention is to obtain a fiber-reinforced resin composition excellent in heat resistance and thin flame retardancy and a molded product thereof.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention relates to (1) polycarbonate resin (A) 9
100 parts by weight of a resin composition comprising 9.5 to 70% by weight and 0.5 to 30% by weight of a liquid crystalline resin (B), and carbon fiber 5
A fiber reinforced resin composition comprising from 0.1 to 300 parts by weight, wherein at least 60% of carbon fibers in the composition have a fiber length of 0.15 to 6
(2) The fiber according to the above (1), wherein the liquid crystalline resin (B) is a liquid crystalline polyester comprising the following structural units (I), (II) and (III). Reinforced resin composition,

[0007]

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(Where R ₁ in the formula is

[0009]

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And R ₂ represents one or more groups selected from

[0011]

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And one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. (3) Red phosphorus having a conductivity of 0.1 to 1000 μS / cm with respect to 100 parts by weight of the total of the components (A) and (B) (provided that the conductivity is 5 g of red phosphorus and 100 mL of pure water is used). In addition, an extraction treatment is performed at 121 ° C. for 100 hours, and the filtrate after filtering red phosphorus is set to have a conductivity of extracted water diluted to 250 mL.) And / or a phosphate ester 0.1 represented by the following general formula (1): A fiber-reinforced resin composition according to the above (1) or (2), wherein

[0013]

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(Wherein R ^{3 to} R ¹⁰ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are the same or different. Represents an aromatic group or an aromatic group substituted with an organic residue containing no halogen, and Y represents a direct bond, O,
Represents S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh;
h represents a phenyl group. N is an integer of 0 or more.
K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. ). (4) Part or all of the polycarbonate resin (A), part or all of the liquid crystal resin (B), or a part of (A) and (B) to be finally contained and red phosphorus and / or Alternatively, the phosphoric acid ester is once melt-kneaded to prepare a resin composition having a concentration higher than the amount of red phosphorus and / or the phosphoric acid ester to be actually blended into the thermoplastic resin composition, and then described in (3) above. A method for producing a fiber-reinforced resin composition, characterized by producing a fiber-reinforced resin composition,
(5) A molded article obtained by molding the fiber-reinforced resin composition according to any one of the above (1) to (3), wherein the molded article has a plate shape or a box shape and a thickness of 1.2 mm or less. A molded article characterized in that the portion has 10% or more of the total surface area of the molded article.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The polycarbonate resin (A) used in the present invention has a carbonate bond and is obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. The aromatic homo or copolycarbonate resin has a logarithmic viscosity of 0.2 to 3.0 dl / g, particularly 0.3, measured at 20 ° C. at a concentration of 1.0 g / dl in methylene chloride. ~ 1.5dl / g
Are preferably used. Here, as the dihydric phenol compound, 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy-
3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis ( 4-hydroxy-3,
5-diphenyl) butane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis ( 4-Hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane and the like can be used, and these can be used alone or as a mixture.

Although the amount of the terminal group of the polycarbonate is not particularly limited, in order to further exert the effects of the present invention, the equivalent ratio (EP) / EP of the phenolic terminal group (EP) to the non-phenolic terminal group (EN) / It is preferable to use a polycarbonate resin having an (EN) of 1/20 or less, more preferably 1/40 or less, and still more preferably 1/70 or less.

The terminal group of the polycarbonate resin is measured by
For example, a polycarbonate resin is dissolved in acetic acid methylene chloride, and titanium tetrachloride is added thereto.
It can be measured by photometry at 46 nm.

The polycarbonate (A) is partially (typically 70% by weight or less, preferably 60% by weight or less, particularly preferably 50% by weight or less of the component (A)) in order to impart other properties. It can be replaced with a crystalline thermoplastic resin, and specific examples include polyester resins such as polybutylene terephthalate and polyethylene terephthalate.

The liquid crystalline resin (B) of the present invention includes, for example,
It is a resin capable of forming an anisotropic molten phase, and examples thereof include liquid crystalline polyester, liquid crystalline polyesteramide, liquid crystalline polycarbonate, and liquid crystalline polyester elastomer, and particularly, liquid crystalline polyester and liquid crystalline polyesteramide are preferably used.

The above-mentioned liquid crystalline polyester and liquid crystalline polyester amide are polyesters and polyester amides capable of forming an anisotropic molten phase, such as aromatic oxycarbonyl units, aromatic dioxy units, aliphatic dioxy units, and aromatic dioxy units. A liquid crystalline polyester comprising a structural unit selected from dicarbonyl units and the like and forming an anisotropic molten phase, or selected from the above structural units and aromatic iminocarbonyl units, aromatic diimino units, aromatic iminooxy units, etc. And liquid crystalline polyesteramides which are composed of different structural units and form an anisotropic molten phase.

Examples of the aromatic oxycarbonyl unit include, for example, p-hydroxybenzoic acid and 6-hydroxy-2-
Examples of the structural unit and aromatic dioxy unit generated from naphthoic acid and the like include 4,4′-dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, t Structural units formed from -butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenylether, and the like; Structural units formed from ethylene glycol and propylene glycol as dioxy units, and aromatic dicarbonyl units include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid,
Produced from 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid and the like. Examples of the structural unit and aromatic iminooxy unit include a structural unit generated from 4-aminophenol and the like.

Preferred examples of the liquid crystalline polyester forming the anisotropic molten phase include structural units (I), (II) and (III)
And liquid crystalline polyester amide.

[0023]

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(Where R ₁ in the formula is

[0025]

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R ₂ represents one or more groups selected from

[0027]

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And one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. The structural unit (I) is a structural unit generated from p-hydroxybenzoic acid, and the structural unit (II) is 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-
4,4′-dihydroxybiphenyl, hydroquinone,
t-butylhydroquinone, phenylhydroquinone,
Methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4′-
Structural units generated from one or more aromatic dihydroxy compounds selected from dihydroxydiphenyl ether or ethylene glycol, one or more aliphatic dihydroxy compounds selected from propylene glycol, etc., structural unit (III) terephthalic acid, isophthalic acid, 4,4 '
-Diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4 '
-Dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,4'-
The structural units generated from one or more aromatic dicarboxylic acids selected from diphenyl ether dicarboxylic acids are shown below. Of these, R ₁ is

[0029]

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And R ₂ is

[0031]

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Particularly preferred are

The liquid crystalline polyester of the present invention is a copolymer comprising the above structural units (I), (II) and (III), and the copolymerization amount is arbitrary. However, in order to exhibit the characteristics of the present invention, the following copolymerization amount is preferable.

That is, the structural units (I), (II) and (III)
In the case of a copolymer consisting of the above structural units (I) and (I
The total of I) is preferably from 30 to 95 mol%, more preferably from 40 to 90 mol%, based on the total of the structural units (I), (II) and (III). The structural unit (III) is the structural unit (I), (II)
70 to 5 mol% is preferable, and 60 to 10 mol% is more preferable, based on the total of (III) and (III). Also, structural units
The molar ratio of (I) to (II) [(I) / (II)] is preferably 7
5/25 to 95/5, more preferably 78/22.
９３93/7. The structural unit (III) is the same as the structural unit (I
It is preferably substantially equimolar to I).

The term "substantially equimolar" means that the units constituting the polymer main chain excluding the terminal are equimolar, but the units constituting the terminal are not necessarily equimolar.

As the liquid crystalline polyesteramide,
Polyester forming an anisotropic molten phase containing p-iminophenoxy units generated from p-aminophenol and p-aminocarboxy units generated from p-aminobenzoic acid in addition to the above structural units (I) to (III) Amides are preferred.

The liquid crystalline polyesters and liquid crystalline polyester amides which can be preferably used include, in addition to the components constituting the structural units (I) to (III), 3,3'-diphenyldicarboxylic acid and 2,2'-diphenyl Aromatic dicarboxylic acids such as dicarboxylic acid, adipic acid, azelaic acid,
Aliphatic dicarboxylic acids such as sebacic acid and dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylsulfone, 4,4'- Dihydroxydiphenyl sulfide,
Aromatic diols such as 4,4'-dihydroxybenzophenone and 3,4'-dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, Further copolymerization of aliphatic and alicyclic diols such as 1,4-cyclohexanedimethanol and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid in a range that does not impair the liquid crystallinity. I can do it.

The logarithmic viscosity of the liquid crystalline resin (B) used in the present invention can be measured in pentafluorophenol. At this time, 0.5 to 15.0 dl / g is preferable as a value measured at 60 ° C. at a concentration of 0.1 g / dl,
1.0 to 10.0 dl / g is particularly preferred.

The melt viscosity of the liquid crystalline resin (B) in the present invention is preferably 0.5 to 200 Pa · s, and particularly preferably 1 to 1 Pa · s.
50 Pa · s is more preferred. When a composition having better fluidity is to be obtained, the melt viscosity is preferably 100 Pa · s or less.

The melt viscosity is calculated as melting point (Tm) +10
It is a value measured by a Koka type flow tester under the condition of ° C and a shear rate of 1,000 (1 / second).

Here, the melting point (Tm) refers to the endothermic peak temperature (Tm1) observed when the polymer having undergone polymerization is measured from room temperature under a heating condition of 20 ° C./min in the differential calorimetry. , Tm1 + 20 ° C. for 5 minutes, then once cooled to room temperature under a temperature-lowering condition of 20 ° C./min, and then again measured at a temperature rising condition of 20 ° C./min (Tm2 ).

The melting point of the liquid crystalline resin is not particularly limited, but is preferably 340 ° C. or less, more preferably 330 ° C. or less from the viewpoint of dispersibility in the polycarbonate resin.
The lower limit is preferably 250 ° C. or higher. More preferably, it is 285-330 ° C.

The basic method for producing the liquid crystalline resin used in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method.

For example, in the production of the above liquid crystalline polyester, the following production method is preferably mentioned. (1) A polyester obtained from only a component excluding an oxycarbonyl unit-forming monomer such as p-hydroxybenzoic acid and p-acetoxybenzoic acid are heated and melted under a dry nitrogen stream, and the copolymerized polyester fragment is subjected to an acidolysis reaction. And then producing a liquid crystalline polyester by reducing the pressure and increasing the viscosity. (2) p-acetoxybenzoic acid and diacylated aromatic dihydroxy compounds such as 4,4'-diacetoxybiphenyl and diacetoxybenzene and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by a deacetic acid condensation polymerization reaction from a polymer. (3) Reaction of aromatic dihydroxy compounds such as p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl and hydroquinone with aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, and acetic anhydride. The phenolic hydroxyl group is acylated, and then a liquid crystalline polyester is produced by a deacetic acid polycondensation reaction. (4) Phenyl esters of p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4'-dihydroxybiphenyl and hydroquinone and diphenyl esters of aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid For producing liquid crystalline polyesters from polyphenols by a dephenol removal polycondensation reaction. (5) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and an aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, or isophthalic acid to form diphenyl esters, respectively.
A method in which an aromatic dihydroxy compound such as 4,4'-dihydroxybiphenyl or hydroquinone is added, and a liquid crystalline polyester is produced by a phenol-elimination polycondensation reaction. (6) In the presence of bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as a polymer or oligomer of a polyester such as polyethylene terephthalate or an aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate, the liquid crystal is prepared by the method of (2) or (3). A method for producing a conductive polyester.

Although the polycondensation reaction of the liquid crystalline polyester proceeds without a catalyst, metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and metallic magnesium can also be used.

The compounding ratio of the polycarbonate resin (A) and the liquid crystalline resin (B) used in the present invention is 99.5 to 30% by weight of (A) and 0 (B) with respect to the total of (A) and (B). .
5 to 70% by weight, preferably (A) 97 to 75% by weight,
(B) 3 to 25% by weight, more preferably (A) 95 to 8
0% by weight and (B) 5 to 20% by weight.

When the amount of the liquid crystalline resin (B) is too small, the effect of the present invention, particularly, the fluidity is not exhibited, and when the amount of the liquid crystalline resin is too large, particularly, the anisotropy of mechanical properties and the weldability of the resin during molding. The strength of the part decreases, which is not preferable.

The carbon fiber used in the present invention is a PAN-based or pitch-based carbon fiber, and is not particularly limited as long as it is generally used for reinforcing a resin. For example, a long fiber type or short fiber type chop is used. It can be selected from dostrand, milled fiber, and the like, but it is desirable to use a high-strength, high-elongation type to suppress fiber breakage during molding. Those with low strength are brittle,
The fiber length becomes extremely short due to fiber breakage during compounding and molding. As a result, the reinforcing effect, conductivity, etc., and the flame retardant effect due to the drop (drip) of the droplet when a flame retardant prescription is applied. It becomes difficult to obtain characteristics.

The carbon fibers in the fiber-reinforced resin composition of the present invention must have a fiber length distribution such that at least 60% of the carbon fibers are controlled in the range of 0.15 to 6 mm, and are preferred. As the fiber length distribution, the range of the fiber length to be controlled is 0.15 to 3 mm, more preferably 0.15 to 2 mm, and the content is preferably 70% by weight or more, more preferably 80% or more. weight%
That is all. By controlling the fiber length distribution in the above specific range, a balance of fluidity and impact resistance is obtained,
Also, the molded product has excellent electromagnetic wave shielding properties. If the fiber length distribution is too short than the above range, not only the strength of the resin, but also the impact properties, electromagnetic wave shielding properties, etc. decrease, while if it is too long, the fluidity decreases, and the surface appearance of the obtained molded article, In addition, because of high fluidity, a high pressure is applied to flow the resin to the end of the molded article, so that molding defects such as burrs may occur. The fiber length distribution is at least in the range of the fiber-reinforced resin composition (for example, in a pellet state) before being subjected to molding, and is desirably in such a range also in a molded article formed by molding such a fiber-reinforced resin composition.

In particular, PA which can obtain these characteristics
N-based carbon fibers are more desirable.

In the present invention, the amount of the carbon fiber added is determined based on the flowability of the composition and the impact resistance, from the viewpoints of the resin composition (A) and the resin composition (B) comprising the polycarbonate (A) and the liquid crystal resin (B). 5) to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the components)
More preferably, it is 25 to 100 parts by weight.

The method for measuring the fiber length distribution of carbon fibers in the composition is, for example, as follows: about 5 g of the composition is placed in a crucible at 550 ° C. × 7.
After time treatment and incineration, 10 of the remaining fillers
Collect 0 mg and disperse in 100 cc of soapy water.
Then, one to two drops of the dispersion are placed on a slide glass using a dropper, observed under a microscope, and photographed. The fiber length of the filler photographed is measured. Measurement is 50
Perform 0 runs to determine the fiber length distribution. When determining the fiber length of the carbon fiber, care must be taken because if the ashing conditions are incorrect, the fiber itself may be oxidized and burned, and it is desirable to incinerate in a nitrogen atmosphere. When the resin component of the fiber-reinforced resin composition to be used is soluble, the composition can be dissolved using a solvent, the fibers can be taken out, and the fiber length can be measured.

In addition, a filler other than carbon fiber can be used as necessary to impart mechanical strength and other properties to the fiber-reinforced resin composition. Non-fibrous fillers such as particles, plates, powders, and granules can be used. Specifically, for example, glass fiber, stainless fiber, metal fiber such as aluminum fiber and brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, oxidized fiber Fibrous materials such as titanium fibers, silicon carbide fibers, rock wool, potassium titanate whiskers, barium titanate whiskers, aluminum borate whiskers, silicon nitride whiskers, whisker-like fillers, mica, talc, kaolin, silica, calcium carbonate, glass beads , Glass flakes, glass microballoons, clay, molybdenum disulfide, wollastenite, titanium oxide, zinc oxide,
Examples include powdery, granular or plate-like fillers such as calcium polyphosphate and graphite.

The above-mentioned fillers can be used in combination of two or more kinds. The filler used in the present invention may be used after its surface is treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, or the like) or another surface treatment agent. .

The amount of the filler is 0.5 to 300 parts by weight based on 100 parts by weight of the resin composition (the total of the components (A) and (B)) comprising the polycarbonate (A) and the liquid crystal resin (B). Parts by weight, preferably 10 to 250 parts by weight.
Parts by weight, more preferably 20 to 150 parts by weight.

In the present invention, red phosphorus and / or a phosphoric ester represented by the following general formula (1) can be used for imparting properties such as thin flame retardancy to the fiber reinforced resin composition.

The red phosphorus used in the present invention is unstable as it is, and has the property of gradually dissolving in water or reacting with water gradually. Is preferably used. As a method for treating such red phosphorus, as described in JP-A-5-229806, the red phosphorus is not pulverized and a crushed surface having high reactivity with water or oxygen is not formed on the red phosphorus surface. A method of finely dividing red phosphorus, a method of catalytically suppressing oxidation of red phosphorus by adding a small amount of aluminum hydroxide or magnesium hydroxide to red phosphorus, coating red phosphorus with paraffin or wax,
A method of suppressing contact with moisture, a method of stabilizing by mixing with ε-caprolactam or trioxane, and coating red phosphorus with a thermosetting resin such as a phenolic, melamine, epoxy, or unsaturated polyester. To stabilize red phosphorus with copper, nickel, silver, iron,
A method of treating with an aqueous solution of a metal salt such as aluminum and titanium to precipitate and stabilize a metal phosphorus compound on the surface of red phosphorus, using red hydroxide with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc. Coating method, iron, cobalt, nickel, manganese on red phosphorus surface,
Examples include a method of stabilizing by coating with electroless plating with tin and the like, and a method of combining them.Preferably, red phosphorus is formed without forming a crushed surface on the red phosphorus surface without crushing the red phosphorus. A method of forming fine particles, a method of stabilizing red phosphorus by coating it with a thermosetting resin such as a phenol-based, melamine-based, epoxy-based or unsaturated polyester-based resin. Titanium, a method of stabilizing by coating with zinc hydroxide, etc., particularly preferably,
A method of pulverizing red phosphorus without pulverizing red phosphorus and forming a crushed surface on the surface, coating red phosphorus with a thermosetting resin such as phenolic, melamine, epoxy, and unsaturated polyester This method is a method of stabilizing by combining the two methods, or a method of combining these two methods. Among these thermosetting resins, phenol-based thermosetting resin, red phosphorus coated with epoxy-based thermosetting resin can be preferably used from the viewpoint of moisture resistance, and phenol-based thermosetting resin is particularly preferable. Red phosphorus coated with resin.

[0058] Unmilled red phosphorus, which is a preferred red phosphorus as the red phosphorus used in the present invention, refers to red phosphorus produced without forming a crushed surface.

The average particle size of red phosphorus before being mixed with the resin is 35 from the viewpoints of flame retardancy, mechanical properties, wet heat resistance, and chemical and physical deterioration of red phosphorus due to pulverization during recycling. The thickness is preferably from 0.01 to 0.01 μm, and more preferably from 30 to 0.1 μm.

The average particle size of red phosphorus can be measured by a general laser diffraction type particle size distribution analyzer. There are two types of particle size distribution analyzers: wet method and dry method.
Either one may be used. In the case of the wet method, water can be used as a dispersion solvent for red phosphorus. At this time, red phosphorus surface treatment may be performed with an alcohol or a neutral detergent. It is also possible to use phosphates such as sodium hexametaphosphate and sodium pyrophosphate as the dispersant. It is also possible to use an ultrasonic bath as a dispersing device.

The average particle diameter of red phosphorus used in the present invention is as described above. However, red phosphorus having a large particle diameter contained in red phosphorus, that is, red phosphorus having a particle diameter of 75 μm or more is difficult. In order to significantly reduce the flammability, mechanical properties, wet heat resistance, and recyclability, red phosphorus having a particle size of 75 μm or more is preferably removed by classification. 75μm particle size
The above red phosphorus content is flame retardant, mechanical properties, wet heat resistance,
From the viewpoint of recyclability, it is preferably at most 10% by weight, more preferably at most 8% by weight, particularly preferably at most 5% by weight.
It is as follows. The lower limit is not particularly limited, but is preferably as close to 0 as possible.

Here, the particle diameter contained in red phosphorus is 75 μm.
The above-mentioned red phosphorus content can be measured by classification using a 75 μm mesh. That is, red phosphorus 100
g (g) when g is classified with a 75 μm mesh
Thus, the content of red phosphorus having a particle size of 75 μm or more is (A / 10
0) × 100 (%).

The conductivity of the red phosphorus (B) used in the present invention when it is extracted in hot water (the conductivity is determined by adding 100 mL of pure water to 5 g of red phosphorus, and adding, for example, Extraction at 100 ° C. for 100 hours, and diluting the filtrate after red phosphorus filtration to 250 mL, and measure the conductivity of the extracted water) is the moisture resistance, mechanical strength, tracking resistance, and recyclability of the obtained molded product. 0.1 ~
1000 μS / cm is preferred, and more preferably 0.1 μS / cm.
８００800 μS / cm, more preferably 0.1 to 500
μS / cm.

Examples of such preferred commercial products of red phosphorus include “NOVA EXCEL” 140 and “NOVA EXCEL” F5 manufactured by Rin Kagaku Kogyo KK.

The phosphoric ester used in the present invention is represented by the following formula (1).

[0066]

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First, the structure of the flame retardant represented by the formula (1) will be described. In the formula (1), n is an integer of 0 or more, preferably 0 to 10, particularly preferably 0 to 5
It is. The upper limit is preferably 40 or less from the viewpoint of flame retardancy.

K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. Preferably, k and m are each an integer of 0 or more and 1 or less;
Particularly preferably, k and m are each 1.

In the formula (1), R ^{3 to} R ¹⁰ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-
Butyl group, n-isopropyl, neopentyl, tert
A pentyl group, 2-isopropyl, neopentyl, te
rt-pentyl group, 3-isopropyl, neopentyl,
a tert-pentyl group, neoisopropyl, neopentyl, tert-pentyl group and the like.
A methyl group and an ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ represent the same or different aromatic groups or aromatic groups substituted with halogen-free organic residues. As the aromatic group, an aromatic group having a benzene skeleton, a naphthalene skeleton, an indene skeleton, or an anthracene skeleton is preferable, and an aromatic group having a benzene skeleton or a naphthalene skeleton is preferable. These may be substituted with an organic residue containing no halogen (preferably an organic residue having 1 to 8 carbon atoms), and the number of substituents is not particularly limited, but may be 1 to 3. preferable. Specific examples include a phenyl group,
Examples thereof include aromatic groups such as a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a naphthyl group, an indenyl group, and an anthryl group.A phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable, and a phenyl group is particularly preferable. , A tolyl group and a xylyl group are preferred.

Y is a direct bond, O, S, SO ₂ , C
(CH ₃ ) ₂ , CH ₂ , and CHPh, and Ph represents a phenyl group.

Examples of such a phosphoric acid ester include PX-200, PX-201, PX-130, and PX-130 manufactured by Daihachi Chemical Co., Ltd.
R-733S, TPP, CR-741, CR747, T
One or more selected from CP, TXP and CDP can be used, and preferably PX-200, TP
One or more selected from P, CR-733S, CR-741 and CR747, particularly preferably PX-20
0, CR-733S and CR-741 can be used, and among them, PX-200 is particularly preferable.

In the present invention, any one of red phosphorus and a phosphoric ester or a mixture of two or more thereof may be used.

The amount of the red phosphorus and / or the phosphoric acid ester is 0.1 to 30 parts by weight per 100 parts by weight of the total of the components (A) and (B).
Preferably from 0.1 to 25 parts by weight, more preferably from 1 to 2 parts by weight.
0 parts by weight, more preferably 2 to 20 parts by weight. Particularly, 4 to 15 parts by weight is particularly preferable.

If the amount of red phosphorus is too small, the effect of imparting flame retardancy by addition is too small. If the amount is too large, it tends to act as a combustion promoter or reduce mechanical properties. .

If the amount of the phosphoric acid ester is too large, the mechanical properties are deteriorated and biting failure due to gas generation or gas burning tends to occur. Low effect of imparting properties.

In addition, when red phosphorus is added, the effect of improving the heat stability at the time of molding as well as flame retardancy is simultaneously exhibited, and when the phosphoric ester is added, the fluidity is further improved. .

The fiber reinforced resin composition of the present invention further improves the stability and strength during extrusion and molding, heat resistance, terminal corrosion of molded articles, etc. by adding a metal oxide as a stabilizer for red phosphorus. Can be done. Specific examples of such a metal oxide include cadmium oxide, zinc oxide, cuprous oxide, cupric oxide, ferrous oxide, ferric oxide, cobalt oxide, manganese oxide, molybdenum oxide, tin oxide and Titanium oxide and the like can be mentioned, among which cadmium oxide, cuprous oxide, cupric oxide, metal oxides other than Group I and / or II metals such as titanium oxide are preferable, and particularly cuprous oxide, Cupric oxide and titanium oxide are preferred, but may be Group I and / or II metal oxides. Titanium oxide is most preferable in order to further improve non-coloring properties in addition to stability and strength during extrusion and molding, heat resistance, and terminal corrosion of molded articles.

The amount of the metal oxide to be added is determined from the viewpoint of mechanical properties and moldability from the polycarbonate resin (A) and the liquid crystal resin (B).
(Total of components (A) and (B))
The amount is preferably 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight, per 100 parts by weight.

In order to further improve the electromagnetic wave shielding property of the fiber reinforced resin composition of the present invention, a conductive filler and / or
Or it is possible to use a conductive polymer, it is not particularly limited, as the conductive filler, there is no particular limitation as long as it is a conductive filler that is usually used for resin conductivity, as a specific example Examples include metal powder, metal flakes, metal ribbons, metal fibers, metal oxides, inorganic fillers coated with a conductive substance, carbon powder, graphite, carbon flakes, and flaky carbon.

Specific examples of the metal species of the metal powder, metal flake, and metal ribbon include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

Specific examples of the metal species of the metal fiber include iron,
Examples thereof include copper, stainless steel, aluminum, and brass.

The metal powder, metal flake, metal ribbon, and metal fiber may be subjected to a surface treatment with a titanate-based, aluminum-based, or silane-based surface treatment agent.

Specific examples of the metal oxide include SnO ₂ (antimony doped), In ₂ O ₃ (antimony doped), Z
Examples thereof include nO (aluminum dope), and these may be subjected to a surface treatment with a surface treating agent such as a titanate, aluminum, or silane.

The inorganic filler coated with the conductive substance
Aluminum, nickel, etc.
, Silver, carbon, SnO_Two(Antimony dope), I
n_TwoO _Three(Antimony dope) and the like. In addition,
Mica, glass bee
Size, glass fiber, potassium titanate whisker, sulfuric acid bath
Lium, zinc oxide, titanium oxide, aluminum borate
Whisker, zinc oxide whisker, titanic acid whisker
Scars and silicon carbide whiskers can be exemplified. Coating method
Methods include vacuum deposition, sputtering, and electroless
Printing method and baking method. These are also
Surface with surface treatment agent such as nate, aluminum, silane, etc.
Processing may be performed.

The carbon powder is classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disk black and the like according to its raw material and production method. The raw material and the production method of the carbon powder that can be used in the present invention are not particularly limited, but acetylene black and furnace black are particularly preferably used. Various carbon powders having different properties such as particle diameter, surface area, DBP oil absorption, and ash content are produced. The carbon powder that can be used in the present invention is not particularly limited in these properties, but from the viewpoint of strength and electrical conductivity, the average particle size is 500 nm or less, particularly 5 to 100 nm,
Further, the thickness is preferably 10 to 70 nm. The surface area (BET
Method) is preferably at least 10 m2 / g, more preferably at least 30 m2 / g. The DBP lubrication amount is preferably 50 ml / 100 g or more, particularly preferably 100 ml / 100 g or more. The ash content is preferably 0.5% or less, particularly preferably 0.3% or less.

The carbon powder may be subjected to a surface treatment with a surface treating agent such as a titanate, aluminum or silane. It is also possible to use those granulated for improving the workability of the melt-kneading.

The resulting molded article often requires a smooth surface. From such a viewpoint, the conductive filler used in the present invention has a length / diameter ratio of 200 or less in powdery, granular, plate-like, scaly, or resin composition, compared to the fibrous filler having a high aspect ratio. It is preferable that any one of the fibrous forms is used.

Specific examples of the conductive polymer used in the present invention include polyaniline, polypyrrole, polyacetylene, poly (paraphenylene), polythiophene, and polyphenylenevinylene.

The conductive filler and / or the conductive polymer may be used in combination of two or more. Among such conductive fillers and conductive polymers, carbon black is particularly preferably used in terms of strength and cost.

The conductive filler used in the present invention and / or
Alternatively, since the content of the conductive polymer varies depending on the type of the conductive filler and / or the conductive polymer used, it cannot be unconditionally specified. However, from the viewpoint of the balance between conductivity, fluidity, mechanical strength, and the like, ( The range of 1 to 250 parts by weight, preferably 3 to 100 parts by weight, is preferably selected with respect to 100 parts by weight of the total of the components (a) and (b).

Further, the fiber reinforced resin composition of the present invention contains an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and the like) and an ultraviolet absorber (for example, resorcinol, Coloring agents, such as salicylates, benzotriazoles, benzophenones), phosphites, hypophosphites, etc .; Release agents (montanic acid and its salts, esters thereof, half esters thereof, stearyl alcohol, stearamide, polyethylene wax, etc.), carbon black as a coloring agent, crystal nucleating agent, plasticizer, and red phosphorus and / or phosphoric acid as a flame retardant Esters are preferably used Other flame retardants (eg, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, magnesium hydroxide, melamine and cyanuric acid or a salt thereof), flame retardant aids, sliding property improvers (graphite, fluororesin), Conventional additives such as an antistatic agent can be added to further impart predetermined characteristics.

Further, according to the necessity of further property improvement, an acid-modified olefin polymer such as maleic anhydride, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene may be used. Copolymer, ethylene / ethyl acrylate copolymer, ethylene /
Glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene /
A propylene-g-maleic anhydride copolymer, an olefinic copolymer such as ABS, a polyester polyether elastomer, a polyester polyester elastomer, and one or more mixtures selected from elastomers are added to obtain predetermined characteristics. It can be further provided.

The fiber reinforced resin composition of the present invention can further impart flame retardancy by using a phenolic resin, a silicone resin, or a fluororesin as an agent for suppressing dropping (drip) of droplets during combustion. Particularly, a fluorine-based resin exerts its effect preferably. Examples of such a fluororesin include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer,
(Tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride /
Ethylene) copolymers, among which polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene ) Copolymers and polyvinylidene fluorides are preferred, especially polytetrafluoroethylene, (tetrafluoroethylene /
Ethylene) copolymers are preferred.

The amount of the dropping (drip) inhibitor is 0.01 to 30 parts by weight, preferably 0.05 to 25 parts by weight, based on 100 parts by weight of the total of the components (A) and (B).
The amount is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight when a fluorine-based resin is used.

The method for producing the fiber reinforced resin composition of the present invention is not particularly limited as long as the range specified in the present invention is obtained. For example, when melt-kneading with a twin-screw extruder, a polycarbonate resin and a liquid crystalline resin are supplied from a resin raw material feeder, and an inorganic filler is supplied from a side feeder at a tip portion of the extruder to check a shear history received by the inorganic filler. A control method may be used.

When red phosphorus and / or a phosphoric acid ester is added, for example, carbon fiber, red phosphorus and other optional phosphorus are used in the polycarbonate resin (A) and the liquid crystal resin (B) component. It is prepared by premixing and / or premixing other additives such as phosphoric acid esters and fillers and supplying them to an extruder or the like without or with sufficient mixing and kneading. In addition, it is preferable that the carbon fiber be blended and manufactured by preparing a master chip in advance by a so-called master chip method. In the case of the carbon fiber master chip method, a longer fiber length distribution range is set in advance in the fiber length distribution range of the present invention, and other additives such as red phosphorus and / or a phosphoric acid ester used as necessary and filling are used. When the material is further kneaded or dry-blended into a molded product, it is necessary to control the fiber length so that the fiber length distribution of the present invention can be realized. Further, when red phosphorus and / or a phosphoric acid ester are blended, it is preferable that a master chip is also prepared in advance by a master chip method and provided for blending. Adopting these master chip methods is preferable in terms of handling and productivity. Specific examples of such a method are described below.

A part of the polycarbonate resin (A) and the liquid crystal resin (B) (for example, part or all of (A),
(B) Part or all of the component, or part of (A) and (B) finally contained) is once melt-kneaded and red phosphorus to be actually blended into the fiber-reinforced resin composition. And / or a resin composition (D) having a higher concentration than the phosphate ester addition amount is produced, and the remaining polycarbonate resin (A) or the liquid crystal resin (B) has a red phosphorus and / or phosphate ester concentration in the remaining components. It is prepared by melt-kneading the high resin composition (D), carbon fiber and other optional additives and fillers.

Alternatively, a polycarbonate resin (A),
Part of the liquid crystalline resin (B) (for example, part or all of (A), part or all of component (B), or part of components (A) and (B) finally contained) Is melt-kneaded to produce a carbon fiber high-concentration product (C) higher than the amount of carbon fiber to be actually incorporated into the fiber-reinforced resin composition, and red phosphorus and / or a phosphate ester and any other It is prepared by melt-kneading additives and fillers that can be used in the present invention.

Alternatively, a polycarbonate resin (A),
Part of the liquid crystalline resin (B) (for example, part or all of (A), part or all of component (B), or part of components (A) and (B) finally contained) Is melt-kneaded to produce a fiber-reinforced resin composition (C) higher than the amount of carbon fiber to be actually blended into the fiber-reinforced resin composition, and separately from the polycarbonate resin (A) and the liquid crystal. (A), part or all of (A), part or all of component (B), or part of components (A) and (B) finally contained. The resin composition (D) having a higher concentration than the amount of red phosphorus and / or phosphate ester to be actually blended into the fiber-reinforced resin composition by melt-kneading to produce the remaining polycarbonate resin (A) or Liquid crystalline resin (B)
Melt-kneading a fiber-reinforced resin composition having a high amount of carbon fiber added therein, a resin composition (D) having a high red phosphorus and / or phosphate ester concentration, and other optional additives and fillers. It is prepared by

Alternatively, a part or all of the polycarbonate resin (A), a part or all of the component of the liquid crystal resin (B), or a part of the components (A) and (B) finally contained and carbon The fiber and other optional additives can be melt-kneaded once to produce a carbon fiber high concentration product (C) higher than the amount of carbon fiber to be actually blended, and red phosphorus and / or Phosphoric acid ester, optionally used in the remaining polycarbonate resin (A) or liquid crystal resin (B) component and at the stage of carbon fiber high concentration product (C) higher than the added amount of carbon fiber to be actually blended It is prepared by melt-kneading additives and fillers other than the possible additives.

Alternatively, part or all of the polycarbonate resin (A), part or all of the component of the liquid crystal resin (B), or a part of the components (A) and (B) to be finally contained and red Once the phosphorus and / or phosphate ester and any other optional additives are melt-kneaded, the concentration is higher than the amount of red phosphorus and / or phosphate ester to be actually incorporated into the fiber reinforced resin composition. Production of high resin composition (D), carbon fiber, remaining polycarbonate resin (A) or liquid crystal resin (B)
By melting and kneading additives and fillers other than optional additives added in the resin composition (D) at a higher concentration than the added amount of red phosphorus and / or phosphate ester in the components and the components. Prepared.

[0103] As described above, in the stage of producing a carbon fiber high concentration product (C) having a higher concentration than the amount of carbon fiber to be actually incorporated into the fiber reinforced resin composition, it can be used arbitrarily. When the additives are blended, it is preferable that these optional additives are previously mixed with a polycarbonate resin or a liquid crystal resin. In addition, at the stage of producing the resin composition (D) having a higher concentration than the amount of red phosphorus and / or phosphate ester to be actually incorporated into the fiber-reinforced resin composition, other optional additives can be used. When an agent is blended, it is preferable that these optional additives be mixed in advance with red phosphorus and / or a phosphoric ester.

Among the additives that can be used arbitrarily, when a metal oxide used as a stabilizer for red phosphorus, particularly titanium oxide is added, titanium oxide is used in the step of producing a high-concentration product of red phosphorus. It is preferable to mix red phosphorus and titanium oxide in advance using a mechanical mixing device such as a Henschel mixer, so that the stability of red phosphorus, the dispersibility of red phosphorus and the obtained resin composition The non-coloring property can be improved.

As the carbon fiber high concentration product (C) and the red phosphorus and / or phosphate ester high concentration product (D),
(1) a high-concentration product consisting only of the polycarbonate resin (A), (2) a high-concentration product consisting only of the liquid crystalline resin (B),
(3) Both of the high-concentration products composed of the polycarbonate resin (A) and the liquid crystal resin (B) exhibit this effect. Red phosphorus and / or phosphate ester high concentration product (D)
In the case of (1), the use of a high-concentration product of red phosphorus and / or phosphate ester preferably consisting only of the liquid crystalline resin (B) results in dispersibility of red phosphorus and / or phosphate ester in the fiber reinforced resin composition. , High flame retardancy and heat resistance.

The blending amount of the polycarbonate resin (A) and the liquid crystal resin (B) of the carbon fiber high concentration product (C) or the red phosphorus and / or phosphate ester high concentration product (D) is as follows. In the production of high-concentration products or high-concentration products of red phosphorus and / or phosphate ester, in terms of dispersibility, and flame retardancy of the finally obtained resin composition,
From the viewpoint of mechanical properties, moldability, and heat resistance, the amount is preferably 0.5 to 250 parts by weight, more preferably 1 to 220 parts by weight, based on 100 parts by weight of the polycarbonate resin (A) and the liquid crystal resin (B). More preferably, it is 2 to 200 parts by weight.

In producing the fiber-reinforced resin composition, for example, a single-screw extruder, a twin-screw, a triple-screw extruder or a kneader-type kneader equipped with a “unimelt” type screw, preferably a side feeder is used. The composition can be melt-kneaded at 180 to 350 ° C. with a twin-screw extruder attached to the composition.

The fiber reinforced resin composition thus obtained is
Fluidity, impact resistance and warpage deformability, it is a composition excellent in electromagnetic wave shielding properties, especially in thin-walled flame retardant,
In most cases, even 1/32 inch (0.8mm) thick UL-
It is possible to achieve the 94 standard V-0.

[0109] The molding method for molding the molded article may be a conventional molding method (injection molding, extrusion molding, blow molding, press molding, injection press molding, etc.) by using a three-dimensional molded article, sheet, film, container pipe or the like. And any other shaped articles. Among them, it is particularly suitable for use in injection molded products, and is suitable for various mechanical mechanism parts, electric and electronic parts, or automobile parts. In particular, a molded article having a thin portion (for example, a plate-shaped molded article or a box-shaped molded article), particularly 1.2 mm
It can be preferably applied to molded articles having the following thin portions. Specifically, a molded article having a portion having a thickness of 1.2 mm or less with respect to the total surface area of the molded article of 10% or more, more preferably a molded article having a portion of 1.2 mm or less with 15% or more, still more preferably It is effective for a molded article having a portion of 1.0 mm or less and 10% or more. As a molding method, injection molding or injection press molding is preferred.

[0110] The molded article thus obtained is composed of various gears,
Various cases, sensors, LED lamps, connectors, sockets, paper separating claws, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickup parts, oscillators, various terminal boards, transformers, plugs, printed wiring Board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, housing, IC baking tray, semiconductor, liquid crystal display parts, FDD carriage, FDD chassis, HDD parts, motor brush holder, parabolic antenna, computer related Electric / electronic parts such as parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, audio parts, audio laser discs, compact discs Audio equipment parts, such as disk, lighting parts, refrigerator parts, air conditioner parts, typewriter parts,
Home and office electrical product parts such as word processor parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, oilless bearings, stern bearings, underwater bearings, etc. Machine-related parts such as bearings, motor parts, lighters, typewriters, etc., optical equipment such as microscopes, binoculars, cameras, clocks, etc., precision machine-related parts, alternator terminals, alternator connectors, IC regulators, light regulators Various valves such as potentiometer base and exhaust gas valve for
Various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, throttle position sensor, Crankshaft position sensor,
Air flow meter, brake butt wear sensor,
Thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, parts related to wiper motor, dust distributor,
Starter switch, starter relay, wire harness for transmission, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, connector for fuse, horn terminal, electrical component insulation board, step motor rotor, lamp socket, lamp reflector, lamp It is useful for automotive and vehicle related parts such as housings, brake pistons, solenoid bobbins, engine oil filters, power seat gear housings, ignition coil parts, ignition device cases, and other various uses. In particular, it is particularly useful when the molded product has a thin portion such as a housing such as various cases, switches, bobbins, connectors, socket connectors, a housing for a mobile phone, and a housing of various devices such as a personal computer housing. Particularly, it is extremely useful when the molded article has a thin portion of 1.2 mm or less that is 10% or more of the entire surface area of the molded article.

[0111]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the gist of the present invention is not limited to the following Examples. Reference Example 1 (LCP1) 932 parts by weight of p-hydroxybenzoic acid, 419 parts by weight of 4,4'-dihydroxybiphenyl, 292 parts by weight of naphthalenedicarboxylic acid, 150 parts by weight of terephthalic acid and 1263 parts by weight of acetic anhydride were distilled with a stirring blade. A reaction vessel equipped with a tube was charged and polycondensation was performed. Melting point 313 consisting of 75 molar equivalents of aromatic oxycarbonyl units, 25 molar equivalents of aromatic dioxy units, and 25 molar equivalents of aromatic dicarboxylic acid units
° C, 22Pa · s (323 ° C, orifice 0.5mm diameter x 10
mm, and a shear rate of 1,000 (1 / second)) were obtained. Reference Example 2 (LCP2) 746 parts by weight of p-hydroxybenzoic acid, 168 parts by weight of 4,4'-dihydroxybiphenyl, 99 parts by weight of hydroquinone, 117 parts by weight of 2,6-naphthalenedicarboxylic acid,
As a result of charging 209 parts by weight of terephthalic acid and 808 kg of acetic anhydride into a reaction vessel equipped with a stirring blade and a distilling tube, polymerization was carried out. As a result, 60 mole equivalents of an aromatic oxycarbonyl unit, 20 mole equivalents of an aromatic dioxy unit, and 337 ° C., 24 Pa · s (347) consisting of 20 molar equivalents of acid units
° C, orifice 0.5mmφ × 10mm, shear rate 1,00
0 (1 / sec)). Reference Example 3 (LCP3) 995 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4'-dihydroxybiphenyl, 112 terephthalic acid
Parts by weight, 216 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 969 parts by weight of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distilling tube to perform polycondensation. Melting point 314 ° C., 13 Pa · s (324 ° C., consisting of 80 molar equivalents of aromatic oxycarbonyl units, 7.5 molar equivalents of aromatic dioxy units, 12.5 molar equivalents of ethylenedioxy units, and 20 molar equivalents of aromatic dicarboxylic acid units) Orifice 0.5mmφ × 10mm, Shear speed 1,000 (1 /
S)).

Each evaluation was measured according to the method described below. (1) Fluidity 1.2 m under the conditions of an injection speed of 99% using the following molding machine.
m Filling pressure of square plate of thickness x 150 mm x 150 mm (M
Pa) was measured. (2) Impact resistance A 5-point pin gate box-formed product (1.
0mm thickness, outer dimension 70mm x 130mm x height 20m
m) was molded, a 500 g weight was placed in the box, and the height at which the box-shaped article broke was measured. (3) Warp deformability (flat portion) A 8-mm gate box forming product having a thickness of 1.0 mm and an outer dimension of 120 mm x 120 mm x a height of 20 mm was charged at a minimum filling pressure +0.
It was molded at 3 MPa, and the dent at the center of the square plate was measured. (4) Warp deformability (wall portion) 1.0 mm thick, outer dimension 30 mm × 30 mm × height 30
mm box with one point gate box at minimum filling pressure +0.
Molding was performed at 98 MPa, and the amount of inside sled between the gate side wall and the opposite side wall was measured. (5) Electromagnetic Wave Shielding Property A square plate having a thickness of 150 mm × 150 mm × 1 mm was injection-molded, and the shielding property of an electric wave was measured based on the Advantest method using the obtained molded product. Specifically, Advantest's shield material evaluator TR1730
By using 1A and a spectrum analyzer and using a probe antenna, the attenuation rate when an electromagnetic wave is transmitted through this flat plate is measured in a frequency band of 10 to 1000 MHz, and the electric field shielding property at a frequency of 300 MHz is read from a measurement chart. Was. (6) Evaluation of Flame Retardancy In accordance with UL-94, a 1/32 inch (0.8 mm) thick test piece was evaluated for flame retardancy. (7) Fiber length distribution About 5 g of pellets were treated in a crucible at 550 ° C. for 7 hours and incinerated, and then 100 mg of the remaining filler was collected and dispersed in 100 cc of soapy water. Then, one to two drops of the dispersion are placed on a slide glass using a dropper, observed under a microscope, and photographed. The fiber length of the filler photographed is measured. The measurement was performed 500 times,
The fiber length distribution was determined.

Examples 1 to 6 and Comparative Examples 1 to 6 Using a TEX-30 type twin screw extruder (manufactured by Nippon Steel Works), polycarbonate resin (Iupilon S-3000 (manufactured by Mitsubishi Engineering-Link Plastics)) was prepared as shown in Table 1. At the indicated ratio, the liquid crystalline resin (B) was dry-blended and supplied from the resin feeder, and the PAN-based carbon fiber (6 mm length) was fed to the resin feeder (Comparative Example 6) or the weight side feeder (Examples 1 to 6, Comparative Examples 1 to 5) were added and melt-kneaded with the extruder temperature shown in Table 1 as the cylinder temperature to obtain pellets. Then, the pellets were subjected to JSW150EII-
P (manufactured by Japan Steel Works, Ltd.), and a test piece was formed by a method for each evaluation item at a mold temperature of 90 ° C. with a molding temperature shown in Table 1 as a cylinder temperature.

As is evident from Table 1, the composition of the present invention has excellent fluidity and impact resistance, has reduced warp deformation of molded articles, and has high electromagnetic wave shielding properties as compared with Comparative Examples. It can be seen from the results that the molded article having a thin portion is particularly excellent in obtaining a molded article for housing use.

[0115]

[Table 1]

Examples 7 to 9, Comparative Examples 7 and 8, Reference Example 4,
5 100 parts by weight of LCP1 was dry-blended with 100 parts by weight of red phosphorus (Nova Excel 140), and 30 mmφ
Melting point of liquid crystalline polyester +15 using a twin screw extruder
The mixture was melted and kneaded at ℃ to obtain a red phosphorus high concentration product (D1). Also,
In the same manner as in the above method, a red phosphorus-rich product (D2) was obtained with LCP2.

Next, the liquid crystal resin (B) and the red phosphorus high-concentration products (D1, D
2) Or a phosphoric ester (Resorcin-type bisphosphate “PX-200” manufactured by Daihachi Chemical Co., Ltd.), polytetrafluoroethylene (“Teflon 6J” manufactured by DuPont-Mitsui Fluorochemicals, Inc.), and carbon fiber (6 mm length) were used in Example 1. Next, the pellets were subjected to JSW150EII-P (manufactured by Nippon Steel Works) in the same manner as described above, and the method for each evaluation item was carried out at a cylinder temperature of Table 2 and a mold temperature of 90 ° C. The test piece was molded by

From Table 2, it can be seen that the addition of red phosphorus or a phosphoric acid ester newly provides the present composition with excellent thin-walled flame retardancy and has almost no deterioration in properties as compared with the reference example.

[0119]

[Table 2]

[0120]

The fiber-reinforced resin composition of the present invention is required to have excellent properties such as excellent fluidity, impact resistance, low warpage, electromagnetic shielding and thin flame retardancy. It is a material suitable for various other uses such as electric / electronic related devices, precision machine related devices, office equipment, automobiles, etc., especially for housing applications.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 67:00)

Claims (5)

[Claims] 1. A polycarbonate resin (A) of 99.5 to 7
A fiber reinforced resin composition comprising 100 parts by weight of a resin composition comprising 0% by weight and 0.5 to 30% by weight of a liquid crystalline resin (B) and 5 to 300 parts by weight of carbon fibers, wherein the carbon fibers in the composition are 60% or more of the fiber length is in the range of 0.15 to 6 mm. 2. A liquid crystalline resin (B) comprising the following structural unit (I):
The fiber-reinforced resin composition according to claim 1, which is a liquid crystalline polyester comprising (II) and (III). Embedded image (Where R ₁ in the formula is And R ₂ represents one or more groups selected from And at least one group selected from In the formula, X represents a hydrogen atom or a chlorine atom. ) 3. Red phosphorus having a conductivity of 0.1 to 1000 .mu.S / cm with respect to 100 parts by weight of the total of the components (A) and (B) (provided that the conductivity is 5 g of red phosphorus and 100 m of pure water.
L was added thereto, and the mixture was extracted at 121 ° C. for 100 hours. 3) and / or 0.1 to 30 parts by weight of a phosphoric ester represented by the following general formula (1). Embedded image (In the above formula, R ^{3 to} R ¹⁰ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
r ¹ , Ar ² , Ar ³ , and Ar ⁴ represent the same or different aromatic groups or aromatic groups substituted with halogen-free organic residues. Y is a direct bond, O, S, S
O ₂ , C (CH ₃ ) ₂ , CH ₂ , and CHPh, and Ph represents a phenyl group. N is an integer of 0 or more. K and m are each an integer of 0 or more and 2 or less, and k +
m is an integer of 0 or more and 2 or less. ). 4. A part or all of the polycarbonate resin (A), a part or all of the liquid crystal resin (B), or a part of (A) and (B) finally contained and red phosphorus. And / or once melt-kneading the phosphate ester to produce a resin composition having a concentration higher than the amount of red phosphorus and / or phosphate ester to be actually blended into the thermoplastic resin composition. A method for producing a fiber-reinforced resin composition, comprising producing the fiber-reinforced resin composition according to any one of the preceding claims. 5. A molded article obtained by molding the fiber reinforced resin composition according to claim 1, wherein the molded article is a plate-shaped or box-shaped thin portion having a thickness of 1.2 mm or less. Characterized by having at least 10% of the total surface area of the molded article.