JP2016008295A - Carbon fiber-reinforced composite molding and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carbon fiber-reinforced composite molding with which carbon fiber can be impregnated satisfactorily and which has high levels of flame retardancy and composite strength.SOLUTION: A carbon fiber-reinforced composite molding comprises a carbon fiber base material and a polycarbonate resin as matrix resin. The polycarbonate resin contains 15-40 pts. mass of a phosphazene compound based on 100 pts. mass of a polycarbonate resin with a viscosity average molecular weight of 18000-30000.

Description

  The present invention relates to a carbon fiber reinforced composite molded body and a method for producing the same, and more particularly, to a carbon fiber reinforced composite molded body having excellent impregnation into carbon fiber, high flame retardancy and high composite strength, and a method for producing the same. .

  Since carbon fiber reinforced composite materials are lightweight and have excellent mechanical properties, they are widely used in sports, architecture, aircraft, automobiles, electrical components, electrical and electronic equipment, and the like. In particular, in the fields of automobiles, electrical and electronic equipment, etc., weight reduction and miniaturization have been rapidly progressing in recent years, and it is expected that their use will further advance.

  Conventionally, the mainstream of carbon fiber reinforced composite moldings has been the use of thermosetting resins such as epoxy resins due to demands for high mechanical properties, but in recent years there has been active research using thermoplastic resins as matrix resins. Has been. A compound containing a thermoplastic resin is characterized in that it is easy to mold, does not require a storage load like a thermosetting resin, and has high toughness and excellent recyclability.

  As an example of using a thermoplastic resin, a carbon fiber reinforced composite molded article using a polypropylene resin that is lightweight, inexpensive, and excellent in solvent resistance as a matrix resin is expected to be applied to automobile applications. However, since polypropylene resin and carbon fiber have insufficient adhesion, it is difficult to obtain a satisfactory composite strength when made into a composite. For example, a terminal amino group polyamide resin is added (Patent Document 1). is necessary.

Compared to such a general-purpose thermoplastic resin, a material using an engineering plastic as a matrix has a problem in terms of productivity when the resin is impregnated (or injected) into a base material made of carbon fiber. Since the polycarbonate resin is excellent in strength and impact resistance, a carbon fiber reinforced composite molded body using the polycarbonate resin is highly expected, but the impregnation property into the carbon fiber substrate is inferior.
Moreover, when applying a carbon fiber reinforced composite molded article as a component of an electric / electronic device, a high degree of flame retardancy is required.

JP 2010-168526 A

  In view of the above circumstances, an object (issue) of the present invention is to provide a carbon fiber reinforced composite molded article that has excellent impregnation into a carbon fiber substrate, has high flame retardancy, and high composite strength, and a method for producing the same. It is in.

As a result of intensive studies to achieve the above-mentioned problems, the present inventor obtained a high degree of flame retardancy when the phosphazene compound was blended with the polycarbonate resin, and the impregnation property to the carbon fiber substrate was remarkably improved. I found out. Furthermore, by combining a polycarbonate resin having a specific viscosity average molecular weight with a specific amount of a phosphazene compound, it was found that a carbon fiber reinforced composite molded article having excellent composite strength, good appearance, and excellent design can be obtained. The invention has been reached.
The present invention is as follows.

(1) A carbon fiber reinforced composite molded body comprising a carbon fiber base material and a polycarbonate resin as a matrix resin,
The carbon fiber-reinforced composite molded article, wherein the polycarbonate resin contains 15 to 40 parts by mass of a phosphazene compound with respect to 100 parts by mass of a polycarbonate resin having a viscosity average molecular weight of 18,000 to 30,000.
(2) The molded article according to [1], which is a casing of an electric / electronic device.
(3) A carbon fiber substrate is placed in a mold cavity, and a polycarbonate resin containing 15 to 40 parts by mass of a phosphazene compound is supplied to 100 parts by mass of a polycarbonate resin having a viscosity average molecular weight of 18,000 to 30,000. A method for producing a carbon fiber reinforced composite molded article characterized by comprising:

  According to the present invention, it is possible to provide a carbon fiber reinforced composite molded article that is excellent in impregnation into a carbon fiber substrate, has high flame retardancy and high composite strength, has a good appearance, and is excellent in design. it can.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples and the like, and is within the scope of the present invention. Any change can be made.
The carbon fiber reinforced composite molded article of the present invention is a carbon fiber reinforced composite molded article comprising a carbon fiber base material and a polycarbonate resin as a matrix resin, and the viscosity average molecular weight of the polycarbonate resin is 18000 to 30000, and is a phosphazene compound. It is characterized by containing 15-40 mass parts with respect to 100 mass parts of polycarbonate resin.

[Polycarbonate resin]
There is no restriction | limiting in the kind of polycarbonate resin used in this invention, A polycarbonate resin may use 1 type and may use 2 or more types together by arbitrary combinations and arbitrary ratios.

  As the polycarbonate resin, any of an aromatic polycarbonate resin, an aliphatic polycarbonate resin, and an aromatic-aliphatic polycarbonate resin can be used. Of these, aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.

  Although there is no restriction | limiting in the specific kind of polycarbonate resin, For example, the polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. The polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

  Examples of the aromatic dihydroxy compound among the monomers used as the raw material for the aromatic polycarbonate resin include the following. In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl;

2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

2,2′-dihydroxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxy diaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,1-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

9,9-bis (4-hydroxyphenyl) fluorene,
Cardio structure-containing bisphenols such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

4,4′-dihydroxydiphenyl sulfide,
Dihydroxydiaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide;

Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

4,4′-dihydroxydiphenyl sulfone,
Dihydroxydiaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone;
Etc.

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are particularly preferable, and 2,2-bis (4-hydroxyphenyl) propane (especially from the viewpoint of impact resistance and heat resistance). That is, bisphenol A) is preferred.
In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

  The method for producing the polycarbonate resin is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.

In the present invention, the polycarbonate resin used is a polycarbonate resin having a viscosity average molecular weight [Mv] of 18,000 to 30,000. By combining a polycarbonate resin having a viscosity average molecular weight within such a range with a phosphazene compound in a specific amount, the impregnation property to carbon fibers can be improved, and the physical properties and appearance of the composite molded product can be improved. .
The viscosity average molecular weight is preferably 19000 or more, more preferably 20000 or more, and preferably 27000 or less, more preferably 25000 or less.

For the viscosity average molecular weight [Mv], methylene chloride was used as a solvent, and the intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. was determined using an Ubbelohde viscometer. Schnell's viscosity formula: η = It is a value calculated from 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

  Moreover, in order to further improve the appearance and fluidity of the molded product, the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and is usually 9500 or less, preferably 9000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

[Carbon fiber substrate]
The carbon fiber base material in the present invention includes a carbon fiber fabric or a laminate thereof, and those obtained by shaping carbon fibers into a predetermined shape in advance. Examples of the form of the fabric-like material include all forms such as a carbon fiber woven base material and a non-woven fabric, and further may be a hybrid structure with glass fiber or other fibers. Moreover, in the case of the base material which has a laminated body structure, the cloth-like thing which consists of glass fiber, an aramid fiber, a boron fiber, an alumina fiber etc. other than the cloth-like thing containing carbon fiber may be included.
The present invention is mainly directed to a so-called dry carbon fiber base material in which the base material is not impregnated with the resin, but the base material in which the base material is impregnated with the resin, the so-called prepreg is also a carbon fiber base material in the present invention. include.

  Preferable forms of the carbon fiber substrate include, for example, a sheet in which a large number of reinforcing fibers are aligned in one direction, a bi-directional woven fabric such as plain weave and twill, multi-axial woven fabric, non-woven fabric, mat, and knit. . The thickness in the case of a sheet is preferably from 0.01 to 3 mm, more preferably from 0.1 to 1.5 mm.

  As the carbon fiber, any of pitch-based, PAN-based (polyacrylonitrile-based), rayon-based and the like can be used, but PAN-based carbon fibers are preferable.

  The carbon fiber is preferably subjected to a surface treatment, and the tensile strength and bending strength as the resin composition are improved. Any commonly used surface treating agent can be used, and examples thereof include epoxy sizing agents, urethane sizing agents, epoxy-urentane sizing agents, polyamide sizing agents, and olefin sizing agents. Among these, epoxy-based, polyamide-based, and urethane-based materials are preferable because of their good dispersibility with respect to the polycarbonate resin.

  Although there is no restriction | limiting in particular in the mass ratio of the carbon fiber base material and polycarbonate resin in the carbon fiber reinforced composite molded object of this invention, Preferably it is carbon fiber base material / polycarbonate resin = 0.1-10 (mass ratio).

[Phosphazene compounds]
The phosphazene compound used in the present invention is an organic compound having a —P═N— bond in the molecule, preferably a cyclic phosphazene compound represented by the following general formula (1), and represented by the following general formula (2). And a chain phosphazene compound selected from the group consisting of a crosslinked phosphazene compound obtained by crosslinking at least one phosphazene compound selected from the group consisting of the following general formula (1) and the following general formula (2) with a crosslinking group At least one compound.

In the formula (1), a is an integer of 3 to 25, R ¹ and R ² may be the same or different, and an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an allyloxy group, an amino group, A hydroxy group, an aryl group or an alkylaryl group is shown.

In the formula (2), b is an integer of ^{3 to} 10,000, and R ³ and R ⁴ may be the same or different, and an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an allyloxy group, an amino group A group, a hydroxy group, an aryl group or an alkylaryl group;
R ⁵ is selected from -N = P (OR ³ ) ₃ groups, -N = P (OR ⁴ ) ₃ groups, -N = P (O) OR ³ groups, and -N = P (O) OR ⁴ groups. It represents at least one, ^{R 6} is, -P ^(OR _{3) 4} group, -P ^(OR ₄₎ 4 ^{group, -P (O) (OR 3} ) 2 ^{group, -P (O) (OR 4} ) 2 At least one selected from the group is shown.

  Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group. C1-C6 alkyl groups, such as a group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, are preferable, and a carbon number of 1 such as a methyl group, an ethyl group, a propyl group, etc. ˜4 alkyl groups are particularly preferred.

  Examples of the cycloalkyl group include cycloalkyl groups having 5 to 14 carbon atoms such as a cyclopentyl group and a cyclohexyl group, among which a cycloalkyl group having 5 to 8 carbon atoms is preferable.

  Examples of the alkenyl group include alkenyl groups having 2 to 8 carbon atoms such as vinyl group and allyl group. Examples of the cycloalkenyl group include cycloalkenyl groups having 5 to 12 carbon atoms such as cyclopentyl group and cyclohexyl group. Etc.

  As an alkynyl group, aryls, such as C2-C8 alkynyl groups, such as an ethynyl group and a propynyl group, an ethynylbenzene group, etc. are mentioned, for example.

  Examples of the aryl group include aryl groups having 6 to 20 carbon atoms such as a phenyl group, a methylphenyl (that is, tolyl) group, a dimethylphenyl (that is, xylyl) group, a trimethylphenyl group, and a naphthyl group. Among them, an aryl group having 6 to 10 carbon atoms is preferable, and a phenyl group is particularly preferable.

  Examples of the alkylaryl group include aralkyl groups having 6 to 20 carbon atoms such as benzyl group, phenethyl group, and phenylpropyl group. Among them, aralkyl groups having 7 to 10 carbon atoms are preferable, and benzyl group is particularly preferable. preferable.

Among them, ^{R 1} and ^{R 2} in the general formula (1), ^{R 3} and ^{R 4} in the general formula (2) is an aryl group, or arylalkyl group. By using such an aromatic phosphazene, the thermal stability of the polycarbonate resin composition of the present invention can be effectively enhanced. From such a viewpoint, R ¹ , R ² , R ³ and R ⁴ are more preferably aryl groups, and particularly preferably phenyl groups.

  Examples of the cyclic and / or chain phosphazene compounds represented by the general formulas (1) and (2) include poly such as phenoxyphosphazene, o-tolyloxyphosphazene, m-tolyloxyphosphazene, and p-tolyloxyphosphazene). (Poly) xylyloxyphosphazenes such as tolyloxyphosphazene, o, m-xylyloxyphosphazene, o, p-xylyloxyphosphazene, m, p-xylyloxyphosphazene, o, m, p-trimethylphenyloxyphosphazene (Poly) phenoxytolyloxyphosphazene such as phenoxy o-tolyloxyphosphazene, phenoxy m-tolyloxyphosphazene, phenoxy p-tolyloxyphosphazene, phenoxy o, m-xylyloxyphosphazene, phenoxy o, p-xyl (Poly) phenoxytolyloxyxylyloxyphosphazene, phenoxy o, m, p-trimethylphenyloxyphosphazene and the like can be exemplified, preferably cyclic and / or chain phenoxyphosphazene Etc.

As the cyclic phosphazene compound represented by the general formula (1), cyclic phenoxyphosphazene in which R ¹ and R ² are phenyl groups is particularly preferable. Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene, octachlorocyclohexane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group. . The cyclic phenoxyphosphazene compound is preferably a compound in which a in the general formula (1) is an integer of 3 to 8, and may be a mixture of compounds having different a.

  The average a is preferably 3-5, more preferably 3-4. Among them, a mixture of compounds in which a = 3 is 50% by mass or more, a = 4 is 10 to 40% by mass, and a = 5 or more is 30% by mass or less is preferable.

As the chain phosphazene compound represented by the general formula (2), a chain phenoxyphosphazene in which R ³ and R ⁴ are phenyl groups is particularly preferable. Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above-mentioned method to reversion polymerization at a temperature of 220 to 250 ° C., and obtaining a linear dichlorophosphazene having a polymerization degree of 3 to 10,000. Examples include compounds obtained by substitution with a phenoxy group. B in the general formula (2) of the linear phenoxyphosphazene compound is preferably 3 to 1000, more preferably 3 to 100, and still more preferably 3 to 25.

Examples of the crosslinked phosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue) and a compound having a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. A compound having a 4,4′-oxydiphenylene group cross-linking structure, a compound having a 4,4′-thiodiphenylene group cross-linking structure, and the like. Can be mentioned.
In addition, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound in which a cyclic phenoxyphosphazene compound in which R ¹ and R ² are phenyl groups in the general formula (1) is crosslinked by the crosslinking group, or in the general formula (2) A cross-linked phenoxyphosphazene compound in which a chain phenoxyphosphazene compound in which R ³ and R ⁴ are phenyl groups is cross-linked by the cross-linking group is preferable from the viewpoint of flame retardancy, and a cyclic phenoxy phosphazene compound is cross-linked by the cross-linking group. Cross-linked phenoxyphosphazene compounds are more preferred.
The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (1) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (2) and Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  In the present invention, the phosphazene compound is a crosslinked phenoxy obtained by crosslinking the cyclic phenoxyphosphazene compound represented by the general formula (1) and the cyclic phenoxyphosphazene compound represented by the general formula (1) with a crosslinking group. In view of flame retardancy and mechanical properties, at least one selected from the group consisting of phosphazene compounds is preferable.

  Content of this phosphazene compound is 15-40 mass parts with respect to 100 mass parts of polycarbonate resin, 4-20 mass parts is preferable, and 16-35 mass parts is more preferable. By containing in such a range, the carbon fiber reinforced composite molded article which is excellent in the impregnation property to carbon fiber and has high flame retardancy and high composite strength becomes possible.

  The polycarbonate resin may further contain other components other than those described above as long as the desired physical properties are not significantly impaired. Examples of other components include other resins other than polycarbonate resins, various resin additives other than those described above, and the like. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

Other resins Examples of the other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin;
Polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin) ), Styrene resins such as acrylonitrile-butadiene-styrene copolymer (ABS resin); polyolefin resins such as polyethylene resins and polypropylene resins; polyamide resins; polyimide resins; polyetherimide resins; polyurethane resins; polyphenylene ether resins; Resin; Polysulfone resin etc. are mentioned.
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.
When other resins are contained, it is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and more preferably 20 parts by mass or less, in a total of 100 parts by mass of the polycarbonate resin and other resins. More preferably.

-Resin additives Examples of resin additives include flame retardants other than phosphazene compounds, anti-dripping agents, mold release agents, thermal stabilizers, antioxidants, ultraviolet absorbers, dyes and pigments (including carbon black), and antistatic agents. Agents, antifogging agents, lubricants, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.

  The phosphazene compound and other components to be blended in the polycarbonate resin, if necessary, are mixed in advance using various mixers such as a tumbler and a Henschel mixer. It is usually melt-kneaded with a mixer such as a shaft kneading extruder or a kneader, and is usually made into resin composition pellets.

[Carbon fiber reinforced composite molded body]
The carbon fiber reinforced composite molded body of the present invention is molded by a known molding method such as injection molding, blow molding, extrusion molding, press molding, compression molding, or insert molding.
For example, a method in which the polycarbonate resin composition is impregnated with heat and pressure using a double belt press or a flat plate press on a carbon fiber substrate, and the polycarbonate resin composition melted in a carbon fiber substrate is extruded using an extruder. And a method of heating and impregnating in a plate shape and a sheet shape, and a method of sandwiching a carbon fiber base material and a sheet of a polycarbonate resin composition and heating and impregnating.

  More preferable methods include injection molding and insert molding. A carbon fiber substrate is placed in the mold cavity, and a phosphazene compound is added to 100 parts by mass of a polycarbonate resin having a viscosity average molecular weight of 18,000 to 30,000. The method of supplying and shape | molding the polycarbonate resin containing 15-40 mass parts is mentioned.

  The shape of the molded product is not particularly limited and can be appropriately selected according to the use and purpose of the molded product. For example, a plate shape, a plate shape, a rod shape, a sheet shape, a film shape, a cylindrical shape, an annular shape, Examples include a circular shape, an elliptical shape, a polygonal shape, an irregular shape, a hollow shape, a frame shape, a box shape, and a panel shape.

  Since the carbon fiber reinforced composite molded article of the present invention is excellent in flame retardancy and impact resistance, and has a good appearance and excellent design, it can be used for various portable terminals such as personal computers, digital cameras, smart phones and mobile phone devices. It can be particularly suitably used for parts and housings.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
The polycarbonate resins and phosphazene compounds used in the following examples and comparative examples are as shown in Table 1 below.

Example 1
After blending 33.3 parts by mass of the phosphazene compound (B1) with 100 parts by mass of the polycarbonate resin (A1) described in Table 1, the mixture was uniformly mixed with a tumbler mixer, and then a twin-screw extruder (manufactured by Nippon Steel Works). TEX30HSST) was melt kneaded at a cylinder temperature of 280 ° C., a screw speed of 200 rpm, and a discharge rate of 20 kg / hr to obtain a pellet of a polycarbonate resin composition.

MVR of the obtained polycarbonate resin composition ^was 82cm 3 / 10min.
The MVR was measured (unit :) at a temperature of 300 ° C. and a load of 11.8 N in accordance with JIS K7210. MVR is an indicator of fluidity, and a higher value indicates better fluidity and impregnation into a carbon fiber substrate.

The pellets were dried at 100 ° C. for 5 hours and then injected with an injection molding machine (“J55-60H” manufactured by Nippon Steel) under conditions of a cylinder set temperature of 340 ° C., a mold temperature of 120 ° C., and a molding cycle of 30 seconds. Three types of UL test specimens each having a length of 125 mm and a width of 13 mm and a thickness of 1 mm were molded. The obtained specimens were conditioned for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity, and UL94 test (combustion of plastic materials for equipment parts) was established by US Underwriters Laboratories (UL). The flame retardancy was evaluated according to (Test).
The result of the flame retardancy test was V-0.

After using a mold for insert molding (100 mm x 100 mm x 1 mmt, 1-point gate), setting a carbon fiber plain weave sheet (thickness 0.2 mm) on the core side of the mold, and clamping the mold, the above polycarbonate resin Using the composition pellets as a raw material, a composite molded product was manufactured by injection molding into a mold at a resin temperature of 300 ° C. and a resin pressure of 100 MPa.
In the composite molded article, the polycarbonate resin uniformly penetrated into the carbon fiber sheet, and the appearance was excellent, the flame retardancy was good, and the elastic modulus and breaking strength were also good.

(Example 2)
In Example 1, it carried out similarly except having changed the compounding quantity of the phosphazene compound (B1) into 25 mass parts.
MVR of the obtained polycarbonate resin ^composition, 69cm 3 / ^10min, flame retardancy was V-0. Further, the obtained composite molded article had a polycarbonate resin uniformly infiltrated into the carbon fiber sheet, had an excellent appearance, had good flame retardancy, and had a good elastic modulus and breaking strength. .

(Example 3)
In Example 1, it carried out similarly except having changed the compounding quantity of the phosphazene compound (B1) into 20.3 mass parts.
MVR of the obtained polycarbonate resin ^composition, 61cm 3 / ^10min, flame retardancy was V-0. Further, the obtained composite molded article had a polycarbonate resin uniformly infiltrated into the carbon fiber sheet, had an excellent appearance, had good flame retardancy, and had a good elastic modulus and breaking strength. .

Example 4
In Example 1, it carried out similarly except having changed the compounding quantity of the phosphazene compound (B1) into 17.6 mass parts.
MVR of the obtained polycarbonate resin ^composition, 55cm 3 / ^10min, flame retardancy was V-0. Further, the obtained composite molded article had a polycarbonate resin uniformly infiltrated into the carbon fiber sheet, had an excellent appearance, had good flame retardancy, and had a good elastic modulus and breaking strength. .

(Comparative Example 1)
In Example 1, it carried out similarly except having changed the compounding quantity of the phosphazene compound (B1) into 11.1 mass parts.
MVR of the obtained polycarbonate resin composition ^has poor and 41cm 3 / 10min, flame retardancy was V-1. Further, in the obtained composite molded article, the polycarbonate resin was poor in impregnation into the carbon fiber sheet and did not form a uniform matrix, and the appearance was poorer than that of Example 1.

(Comparative Example 2)
In Example 1, it carried out similarly except having changed the compounding quantity of the phosphazene compound (B1) into 42.9 mass parts.
MVR of the obtained polycarbonate resin ^composition, 94cm 3 / ^10min, flame retardancy was V-0. Further, the obtained composite molded article was inferior in elasticity and breaking strength to those of Example 1.

(Comparative Example 3)
In Example 1, it carried out similarly except not having mix | blended the phosphazene compound (B1).
MVR of the obtained polycarbonate resin ^composition, 14cm 3 / ^10min, flame retardancy was V-2. Further, in the obtained composite molded article, the polycarbonate resin was poor in impregnation into the carbon fiber sheet and did not form a uniform matrix, and the appearance was poorer than that of Example 1.

  The carbon fiber reinforced composite molded article of the present invention is excellent in flame retardancy and impact resistance, has a good appearance and is excellent in design, and therefore can be suitably used for parts and casings of various electric and electronic devices.

Claims (3)

A carbon fiber reinforced composite molded body comprising a carbon fiber substrate and a polycarbonate resin as a matrix resin,
The carbon fiber-reinforced composite molded article, wherein the polycarbonate resin contains 15 to 40 parts by mass of a phosphazene compound with respect to 100 parts by mass of a polycarbonate resin having a viscosity average molecular weight of 18,000 to 30,000.   The molded article according to claim 1, which is a casing of an electric / electronic device.   A carbon fiber base material is arranged in a mold cavity, and a polycarbonate resin containing 15 to 40 parts by mass of a phosphazene compound is supplied to 100 parts by mass of a polycarbonate resin having a viscosity average molecular weight of 18000 to 30000. A method for producing a carbon fiber reinforced composite molded article.