JP6520256B2 - Carbon fiber reinforced thermoplastic, housing for electric and electronic devices - Google Patents

Description

  BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a carbon fiber reinforced thermoplastic plastic and a housing for electric and electronic devices. More specifically, the carbon fiber reinforced thermoplastic plastic having excellent flame retardancy, excellent in light weight, excellent in mechanical properties, and excellent in short formability to complex shapes, and having excellent flame retardancy, The present invention relates to a housing for electric and electronic devices which is lightweight and excellent in mechanical properties.

A carbon fiber reinforced plastic consisting of carbon fiber and a matrix resin is excellent in mechanical properties, so it can be used for sports and leisure applications such as golf shafts and fishing rods, structural materials such as aircraft and vehicles, and reinforcing materials for concrete structures. It is used in a wide range of fields. Among them, carbon fiber reinforced thermoplastics having a thermoplastic resin as a matrix resin are excellent in impact resistance, and can reduce the molding time even in a complicated shape as compared with the case where a thermosetting resin is used as a matrix resin. Because it can, it is excellent in mass productivity. (Patent Document 1)
In addition, carbon fibers have electrical conductivity, and their composite materials have excellent electromagnetic wave shielding properties and excellent mechanical properties, so they are used in the housings of electric and electronic devices such as notebook computers, etc. Helps to reduce the thickness of equipment and reduce the weight of equipment. Among them, structural materials such as aircraft and vehicles, building materials, etc., fires and burns structural materials due to fire and it is extremely dangerous to generate toxic gas etc. Therefore, the materials have flame retardant performance There is a strong demand for materials, and even in electrical and electronic equipment applications, in order to prevent an accident caused by ignition of a case or part due to heat generation from the inside of the device or an external heat source, the material is required to be flame retardant It is done.

(Patent Document 2)
In the past it was common to add a halogen-based flame retardant and a flame retardant auxiliary such as antimony trioxide to flame-retarding resins, but halogen-based compounds have the problem of generating harmful substances during combustion. For this reason, in recent years, studies on flame-retarding methods not containing halogen compounds have been actively conducted, and methods of blending phosphorus compounds such as condensed phosphates as a flame retardant in resin have become mainstream. (For example, Patent Document 3)
However, the method of blending the phosphorus compound into the resin as a flame retardant is 1) mechanical properties are greatly reduced if the addition amount is large, 2) the phosphorus compound oozes out to the surface over a long period (blooming or bleed out) And 3) there is a problem that the phosphorus compound is easily hydrolyzed. Generally, the higher the phosphorus atom content, the higher the flame retardancy performance, but due to the above problems, there is a limit in increasing the phosphorus content in the prior art, and the phosphorus content is high (that is, the flame retardancy performance is high) ) Fiber reinforced thermoplastics have been difficult. In particular, in a carbon fiber reinforced thermoplastic plastic, mechanical properties are improved as the content of carbon fiber is higher, but it is also difficult to impart flame retardancy as the content of carbon fiber is higher It has been extremely difficult to simultaneously achieve high mechanical properties and flame retardant performance in plastic plastics.

  In order to solve the above problems, Patent Document 4 discloses a phosphorus-containing polymer having a high phosphorus atom content. In general, carbon fibers are (1) handleability improvement by imparting convergence of carbon fiber bundle, (2) impregnation improvement by imparting wettability with matrix resin, and (3) interfacial adhesion imparting with matrix resin and carbon fiber A sizing agent is attached for the purpose of improving mechanical properties. However, when the phosphorus-containing polymer disclosed in Patent Document 4 is used as a matrix resin, a carbon fiber reinforced thermoplastic plastic consisting of carbon fibers to which a general sizing such as epoxy resin is attached is an interface between reinforcing fibers and the matrix resin. There is a problem that excellent mechanical properties are not expressed because the adhesion is very weak.

JP-A-9-155862 WO 2005/08292 pamphlet JP-A-2-155262 Special table 2010-533777

  The present invention has been made in view of the above circumstances, and has excellent flame retardancy, carbon fiber reinforced thermoplastic resin which is light in weight, excellent in mechanical properties, and excellent in short-time shaping to complex shapes. Intended to provide plastic.

  In order to solve the above-mentioned subject, in the present invention, the following means are used. That is, the gist of the present invention resides in the following [1] to [8].

[1] A thermoplastic resin composition containing a phosphorus-containing polymer containing a structural unit represented by the following (formula 1), and a carbon fiber, wherein the carbon fiber is subjected to sizing treatment with the following sizing agent (1) Carbon fiber reinforced thermoplastics.

(Formula 1)

  Sizing agent (1): an ester of an epoxy compound having two or more epoxy groups in the molecule and an unsaturated monobasic acid, wherein the compound (A) has at least one epoxy group in the molecule, and a cured product Containing a bifunctional urethane acrylate oligomer (B) having a tensile elongation of 40% or more, and the ratio (mass ratio) of the content of the compound (A) to the urethane acrylate oligomer (B) is The ratio of the total amount of the compound (A) and the urethane acrylate oligomer (B) in the total sizing component is 20 in the range of acrylate oligomer (B) / compound (A) = 1/3 to 2/1 is 20 Sizing agent which is% by mass or more.

[2] The carbon fiber-reinforced heat according to the above [1], wherein the phosphorus-containing polymer containing the structural unit represented by (Formula 1) is a phosphorus-containing polymer having a partial structure represented by the following (Formula 2) Plastic.

(Formula 2)

(X and y in (Formula 2) are integers of 1 to 19)

  [3] The carbon fiber reinforced thermoplastic plastic according to the above [1] or [2], wherein the weight average molecular weight Mw of the phosphorus-containing polymer is 10,000 or more and 160,000 or less.

  [4] The carbon fiber reinforced thermoplastic plastic according to any one of the above [1] to [3], wherein the proportion of the phosphorus-containing polymer in the thermoplastic resin composition is 20% by mass or more.

  [5] The carbon fiber reinforced thermoplastic plastic according to any one of the above [1] to [4], wherein the thermoplastic resin composition contains a bisphenol A polycarbonate resin.

  [6] The carbon fiber reinforced thermoplastic plastic according to the above [5], wherein the proportion of the total amount of the bisphenol A polycarbonate and the primary phosphorus-containing polymer in the thermoplastic resin composition is 70% by mass or more.

  [7] A sizing agent (1) is an ester of an alkylene oxide adduct of a bisphenol and a dicarboxylic acid compound, containing an ester compound (C) having an acid value of 50 or more, [1] to [1] The carbon fiber reinforced thermoplastic resin according to any one of 6).

  [8] Any of [1] to [7], wherein the sizing agent (1) contains an anionic surfactant (D) having an ammonium ion as a counter ion, and a nonionic surfactant (E) Carbon fiber reinforced thermoplastic described in.

  [9] The carbon fiber reinforced thermoplastic plastic according to any one of the above [1] to [8], having a thickness of 0.4 mm or more and 1.6 mm or less, and a flame retardant performance based on UL 94 of V-0 Molding material that meets

  [10] A casing for electric and electronic equipment, which is partially or entirely composed of the molding material as described in [9] above.

  Moreover, the following [9] is another embodiment of the present invention.

  [9] (i) A step of arranging a plurality of carbon fiber bundles sized by the following sizing agent (1) into a sheet

(Ii) A method for producing a carbon fiber-reinforced thermoplastic plastic, comprising the step of impregnating the sheet material with a thermoplastic resin composition containing a phosphorus-containing polymer containing a structural unit represented by the following (formula 1) The phosphorus content in the thermoplastic resin composition is 2.6% by mass or more and 10.8% by mass or less, and the volume content of carbon fibers in the carbon fiber-reinforced thermoplastic plastic is 20% by volume or more and 65%. The manufacturing method of the carbon fiber reinforced thermoplastics which is volume% or less.

(Formula 1)

  Sizing agent (1): an ester of an epoxy compound having two or more epoxy groups in the molecule and an unsaturated monobasic acid, wherein the compound (A) has at least one epoxy group in the molecule, and a cured product Containing a bifunctional urethane acrylate oligomer (B) having a tensile elongation of 40% or more, and the ratio (mass ratio) of the content of the compound (A) to the urethane acrylate oligomer (B) is The ratio of the total amount of the compound (A) and the urethane acrylate oligomer (B) in the total sizing component is 20 in the range of acrylate oligomer (B) / compound (A) = 1/3 to 2/1 is 20 Sizing agent which is% by mass or more.

  According to the present invention, a carbon fiber-reinforced thermoplastic plastic having excellent flame retardancy, excellent in light weight and mechanical properties, and excellent in short-time shaping to complex shapes, and having excellent flame retardancy It is possible to provide a lightweight housing having excellent mechanical properties for electrical and electronic devices.

  Hereinafter, the present invention will be described in detail.

The carbon fiber-reinforced thermoplastic plastic of the present invention comprises a thermoplastic resin composition containing a phosphorus-containing polymer containing a structural unit represented by the following (formula 1), and a carbon fiber sized with the following sizing agent (1) Is contained as an essential ingredient.

(Formula 1)

  Sizing agent (1): an ester of an epoxy compound having two or more epoxy groups in the molecule and an unsaturated monobasic acid, wherein the compound (A) has at least one epoxy group in the molecule, and a cured product Containing a bifunctional urethane acrylate oligomer (B) having a tensile elongation of 40% or more, and the ratio (mass ratio) of the content of the compound (A) to the urethane acrylate oligomer (B) is The ratio of the total amount of the compound (A) and the urethane acrylate oligomer (B) in the total sizing component is 20 in the range of acrylate oligomer (B) / compound (A) = 1/3 to 2/1 is 20 Sizing agent which is% by mass or more.

  In the carbon fiber-reinforced thermoplastic plastic of the present invention, the volume content (Vf) of carbon fibers in the carbon fiber-reinforced thermoplastic plastic is preferably 20% by volume or more and 65% by volume or less. If it is 25 volume% or more, good mechanical properties can be obtained as a carbon fiber reinforced thermoplastic plastic. If the content is 70% by volume or less, good flame retardancy can be obtained. Preferably, it is 33% by volume or more and 60% by volume or less.

  The carbon fiber-reinforced thermoplastic plastic of the present invention preferably has a thickness of 0.4 mm or more and 1.6 mm or less, and preferably has a flame retardant performance based on UL 94 satisfying V-0. When used as a housing for electric and electronic devices, it is preferable that the flame retardancy performance based on UL 94 satisfy V-0, and if the thickness is 0.4 mm or more and 1.6 mm or less, the housing for electric and electronic devices At the same time, it is possible to achieve both light weight and thin wall effect and flame retardant performance. More preferably, the thickness is 0.45 mm or more and 1.0 mm or less, and the flame retardancy performance based on UL 94 satisfies V-0

[Thermoplastic resin composition]
The thermoplastic resin composition used by this invention needs to contain the phosphorus containing polymer containing the structural unit represented by following (Formula 1).

(Formula 1)

  In the thermoplastic resin composition used in the present invention, the proportion of the phosphorus-containing polymer in the thermoplastic resin composition is preferably 20% by mass or more. If it is 20 mass% or more, when it is set as a carbon fiber reinforced thermoplastic resin and a case for electric and electronic equipment, the outstanding flame-retardant performance will be expressed.

<Phosphorus-containing polymer>
The phosphorus-containing polymer used in the present invention is not particularly limited as long as it contains the structural unit represented by the above (formula 1), and is represented by the above (formula 1) in the main chain or side chain in the molecular structure. It may be a homopolymer or a copolymer as long as it contains a structural unit. The phosphorus-containing polymer used in the present invention may be used alone or in combination of two or more.

The phosphorus-containing polymer used in the present invention is preferably a phosphorus-containing polymer having a partial structure represented by the following (Formula 2): If it is a phosphorus-containing polymer having a partial structure represented by the following (Formula 2), excellent mechanical properties can be obtained when it is made a carbon fiber reinforced thermoplastic plastic, and also in the thermoplastic resin composition described later In the case where a bisphenol A type polycarbonate resin is contained as Component (B), the compatibility in the thermoplastic resin composition becomes good, and as a carbon fiber-reinforced thermoplastic plastic, excellent mechanical properties are developed.

(Formula 2)
(X and y in the formula (2) are integers of 1 to 19)

  The molecular weight of the phosphorus-containing polymer used in the present invention is preferably 10,000 or more in weight average molecular weight (Mw). If it is 10,000 or more, blooming or bleed out can be suppressed. More preferably, the weight average molecular weight (Mw) is 20,000 or more, and when it is 20,000 or more, the mechanical properties of the carbon fiber reinforced thermoplastic plastic and the housing for electric and electronic devices are good. The upper limit of the molecular weight is not particularly limited, but if it is 160,000 or less in weight average molecular weight (Mw), it can be manufactured by a known method.

  The phosphorus atom content of the phosphorus-containing polymer used in the present invention is preferably 2.0% by mass or more and 10.8% by mass or less. If it is 2.6 mass% or more, when it is set as a carbon fiber reinforced thermoplastic resin and a housing for electric and electronic devices, both excellent flame retardancy performance and mechanical physical properties can be achieved. If it is 10.8 mass% or less, it can manufacture easily by the well-known manufacturing method mentioned later.

  A commercial item may be used for the phosphorus containing polymer used for this invention, and what was superposed | polymerized by the well-known manufacturing method may be used for it. As a commercial item of the homopolymer of the phosphorus containing polymer used for this invention, NOFA HM1100 by FRAX polymers company is mentioned, for example. The method of polymerizing the homopolymer of the phosphorus-containing polymer used in the present invention includes a method of polymerizing diphenyl methyl phosphonate and bisphenol A in the presence of a catalyst under high temperature and reduced pressure. As a commercial item of the copolymer of the phosphorus containing polymer used for this invention, NOFA CO3000 made by F-RAX Polymers company, Nokia CO6000 etc. are mentioned, for example. The method of polymerizing the copolymer of the phosphorus-containing polymer used in the present invention includes a method of polymerizing diphenyl methyl phosphonate, diphenyl carbonate and bisphenol A in the presence of a catalyst under high temperature and reduced pressure.

<Other ingredients>
The thermoplastic resin composition used in the present invention may consist only of the above-mentioned phosphorus-containing polymer, or may contain other than the above-mentioned phosphorus-containing polymer. For example, as components other than the above-mentioned phosphorus content polymer, polycarbonate resin, polyester resin, polyamide resin, liquid crystal polymer resin, polyether sulfone resin, polyether ether ketone resin, polyarylate resin, polyphenylene ether resin, polyphenylene sulfide resin, polyacetal Resin, polysulfone resin, polyimide resin, polyolefin resin, polystyrene resin, modified polystyrene resin, ABS resin, modified ABS resin, MBS resin, polymethyl methacrylate resin, epoxy resin, modified resins thereof, and polymer alloy resins thereof It can be mentioned. One of these may be used alone, or two or more may be used in combination. Among them, polycarbonate resins having good compatibility with the phosphorus-containing polymer are preferable, and they exhibit excellent mechanical properties when used as a carbon fiber-reinforced thermoplastic plastic and a case for electric and electronic devices. As a polycarbonate resin, bisphenol A polycarbonate resin is particularly preferable.

  In the thermoplastic resin composition used in the present invention, the proportion of the bisphenol A polycarbonate resin and the phosphorus-containing polymer is preferably 70% by mass or more. By 70% by mass or more, due to the action with the below-mentioned sizing agent (1), excellent mechanical properties are exhibited when it is made a fiber-reinforced thermoplastic plastic and a case for electric and electronic devices.

[Method for producing thermoplastic resin composition]
Arbitrary methods are employ | adopted as a manufacturing method of the thermoplastic resin composition of this invention. For example, after the phosphorus-containing polymer and any other components are sufficiently mixed using pre-mixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, an extrusion kneader, etc. Granulation is carried out using a ketting machine or the like, followed by melt-kneading using a melt-kneader represented by a vent-type twin-roder, and pelletizing using equipment such as a pelletizer.

  As a method of supplying each component to the melt kneader, a method of supplying each component independently to the melt kneader, a method of pre-mixing a part of each component, and a method of independently supplying the remaining components to the melt kneader Are illustrated. In addition, when there is a liquid thing as a component to mix | blend, what is called a liquid pouring apparatus or a liquid addition apparatus can be used for the supply to a melt-kneading machine.

  As the extruder, one having a vent capable of degassing the water in the raw material and the volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed to efficiently discharge generated water and volatile gases out of the extruder from the vent. As the melt-kneader, in addition to a twin-screw extruder, a Banbury mixer, a kneading roll, a single-screw extruder, a multi-screw extruder having three or more shafts, and the like can be mentioned.

  The resin extruded as described above is directly cut and pelletized or, after forming the strands, such strands are cut and pelletized with a pelletizer. When it is necessary to reduce the influence of external dust and the like at the time of pelletization, it is preferable to clean the atmosphere around the extruder. The shape of the obtained pellet may be a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

[Carbon fiber]
In the present invention, carbon fiber is an essential component from the viewpoint of mechanical properties and electromagnetic wave shielding properties. The carbon fiber used in the present invention is not particularly limited, and may be PAN-based carbon fiber using polyacrylonitrile as a raw material or pitch-based carbon fiber using pitch as a raw material, but the strands measured according to JIS R7601 (1986) The tensile strength is preferably 1.0 GPa or more and 9.0 GPa or less, and the strand tensile elastic modulus is preferably 150 GPa or more and 1000 GPa or less. More preferably, it has a strand tensile strength of 1.5 GPa to 9.0 GPa, and a strand tensile elastic modulus of 200 GPa to 1000 GPa.

  The form of the carbon fiber used in the present invention may be aligned in one direction, or may be cut into a woven fabric, a non-crimp fabric, or a short fiber.

[Sizing agent (1)]
As described above, the sizing agent (1) used in the present invention is “an ester of an epoxy compound having two or more epoxy groups in the molecule and an unsaturated monobasic acid, which comprises at least one epoxy group in the molecule A compound (A) (hereinafter sometimes referred to as a component (A)) having a “a bifunctional urethane acrylate oligomer (B) (hereinafter referred to as a component (B)) having a tensile elongation of 40% or more of the cured product And the ratio (mass ratio) of the content of the component (A) to the component (B) is (B) component / (A) component = 1/3 to 2/1. It is a sizing agent which is within the range and in which the proportion of the total amount of the (A) component and the (B) component in all the sizing components is 20% by mass or more.

<Component (A): an ester of an epoxy compound having two or more epoxy groups in the molecule and an unsaturated monobasic acid, wherein the compound (A) has at least one epoxy group in the molecule>
The sizing agent (1) used in the present invention needs to contain the component (A). In the present invention, an epoxy group means a group having in its structure a three-membered ring whose ring skeleton is composed of two carbon atoms and one carbon atom. Examples of the epoxy group include a group represented by the following formula (e1), a group (glycidyl group) represented by the following formula (e2), and other cyclic aliphatic epoxy groups. Examples of other cyclic aliphatic epoxy groups include groups having a cyclic structure formed by the three-membered ring and a monocyclic or polycyclic aliphatic ring in the structure, and examples thereof include, for example, the following formula (e3) ] The group represented by-(e5) can be illustrated.

  In the component (A) used in the present invention, the "epoxy compound having two or more epoxy groups in the molecule" which forms an ester is not particularly limited. For example, epoxy compounds of bisphenols, addition of alkylene oxides of bisphenols The epoxy compound, the epoxy compound of hydrogenated bisphenols, the alkylene oxide addition epoxy compound of hydrogenated bisphenols, etc. are mentioned.

  The bisphenols are not particularly limited, and compounds such as bisphenol F type, bisphenol A type and bisphenol S type can be mentioned. Epoxy resins such as phenol novolac type, cresol novolac type, diphenyl type, dicyclopentadiene type, and naphthalene skeleton type other than epoxy compounds of bisphenols can also be used as "epoxy compound having a plurality of epoxy groups in the molecule" .

  The “epoxy compound having two or more epoxy groups in the molecule” may have a linear aliphatic skeleton.

  In the component (A) used in the present invention, the "unsaturated monobasic acid" constituting the ester is not particularly limited as long as it is a compound having one unsaturated group and one carboxyl group. The unsaturated group is not particularly limited, but is preferably a vinyl group or a propenyl group, more preferably a vinyl group, because the molecular structure is not bulky and the rigidity of the main chain of the formed ester is not reduced. It is. Particularly preferred as unsaturated monobasic acids are acrylic acid or methacrylic acid. That is, it is preferable that (A) component is ester of the said epoxy compound and acrylic acid or methacrylic acid.

The component (A) used in the present invention is an ester obtained by reacting a compound having two or more epoxy groups with an unsaturated monobasic acid, and in this reaction, an epoxy group of a compound having a plurality of epoxy groups Among them, at least one epoxy group remains unreacted, and at least one epoxy group is opened by unsaturated monobasic acid to form a so-called half ester having an unsaturated group. In the molecule, it has an epoxy group derived from a compound having a plurality of epoxy groups, and an unsaturated group derived from an unsaturated monobasic acid (for example, CH ₂ = CH-COO- derived from acrylic acid) By this, the coupling function between the carbon fiber surface and the resin molecule is exhibited, and the interfacial adhesion between the carbon fiber and the matrix resin is greatly improved.

  The component (A) used in the present invention is, in particular, an ester of a compound having an epoxy group at both ends of the molecule and an unsaturated monobasic acid, because it is excellent in the above-mentioned effects. Preferred are compounds having an unsaturated group at one end and an epoxy group at the other end. By using the compound as the component (A), the matrix resin and the carbon fiber can be strongly bonded, and excellent interfacial adhesion can be exhibited.

  As a compound having an epoxy group at both ends of the molecule, in particular, either one or both of a diepoxy compound of bisphenol and an alkylene oxide adduct diepoxy compound of bisphenol are preferable. That is, the component (A) is an ester of an unsaturated monobasic acid with one or both of a diepoxy compound of bisphenols and an alkylene oxide-added diepoxy compound of bisphenols, and one end of the main chain of the molecule It is preferable that it is a compound which has an unsaturated group in part, and has an epoxy group in the other end, respectively.

  As the component (A) used in the present invention, one type may be used alone, or two or more types may be used in combination.

<(B) Component: Bifunctional Urethane Acrylate Oligomer (B) having a Tensile Elongation of 40% or More of a Cured Product>
The sizing agent (1) used in the present invention needs to contain the (B) component.

  The component (B) used in the present invention has an effect of forming an interfacial phase excellent in flexibility at the interface between the matrix resin and the carbon fiber. By forming an interfacial phase with excellent flexibility at the interface between the matrix resin and the carbon fiber, the interfacial adhesion between the matrix resin and the carbon fiber is improved.

  In addition, when complexing the carbon fiber to which the sizing agent is applied and the matrix resin, the sizing agent component on the surface of the carbon fiber diffuses into the matrix resin, and in particular in the matrix resin near the interface, the sizing agent component is high. An area including the concentration is formed. This area affects the mechanical properties of the composite material.

  In the component (B) used in the present invention, the tensile elongation of the cured product needs to be 40% or more, and 45% or more is more preferable because it is excellent in the effect of making the interfacial phase tough. 50% or more is more preferable. The upper limit of the tensile elongation percentage (%) is preferably 900% or less, more preferably 700% or less, in consideration of a significant reduction in the elastic modulus of the resin in the vicinity of the interface.

  The component (B) used in the present invention needs to be bifunctional. If the type is trifunctional or higher, the crosslink density becomes too high, and sufficient toughening does not occur. On the other hand, in the monofunctional type, the crosslinking reaction is only on one side, and a sufficient toughening effect can not be obtained.

  As the component (B) used in the present invention, in particular, the viscosity improvement effect at 60 ° C. is 10,000 mPa · s or more, and the tensile strength of the cured product is 6 MPa or more because the toughness improvement effect of the interfacial phase is very large. Is preferred. The high viscosity of the component (B) indicates that the molecular weight of the oligomer is high or the cohesion between the oligomer molecules is high. When the molecular weight is large or the cohesion between the molecules is large, the component (B) is unevenly distributed in the interfacial phase between the carbon fiber surface and the matrix resin without being diffused to the matrix resin, and as a result, the effect of the interfacial phase Flexibility can be achieved. 20,000 or more are more preferable, and, as for the viscosity of (B) component, 40,000 or more is further more preferable. As the upper limit of the viscosity, it is better from the viewpoint of the preparation of the sizing agent and the temporal stability of the sizing agent to be not solid at 60 ° C.

  -5 degreeC or more is preferable and, as for the glass transition temperature (Tg) of the hardened | cured material of (B) component used by this invention, 5 degreeC or more is more preferable. If the Tg of the cured product is -5 ° C. or more, not only the appropriate softening can be achieved by the interfacial phase, but also the value of the stress leading to breakage is increased, so that a stronger interfacial phase can be formed, and the above effect improves. In other words, the interfacial phase has the function of supporting the reinforcing fibers, and excessive softening may impair the mechanical properties of the composite material. As an upper limit of Tg of hardened | cured material, when the function as a soft component is considered, 100 degrees C or less is preferable, and 80 degrees C or less is more preferable.

  The measurement of the tensile elongation percentage of the cured product of the urethane acrylate oligomer is carried out as follows. 3.0 g of Darocure # 1173 manufactured by Merck Japan Ltd. as a curing agent is added to 97 g of urethane acrylate oligomer and thoroughly mixed, and then the obtained mixture is applied on a glass plate to obtain a film having a thickness of 100 μm. The film is cured by irradiation with ultraviolet light from a position 10 cm high using an ozone type lamp (80 W / cm). The tensile elongation percentage of the obtained cured film is measured at a tensile speed of 300 mm / min in accordance with JIS K7113. In addition, the Tg of the cured product is raised at a rate of 2 ° C./min using the cured film obtained in the same manner as above as a test piece, and the dynamic viscoelasticity and loss tangent of the test piece are measured with a viscoelasticity measuring apparatus And can be determined from the loss tangent peak temperature (tan δMAX).

  Here, in the present invention, “urethane acrylate oligomer” is a compound having a urethane bond and an acryloyl group (CH 2 CHCH—CO—) in the molecule. The structure of the urethane acrylate oligomer can be roughly classified into an aromatic type having an aromatic group in its structure and an aliphatic type not having an aromatic group. The structure of the urethane acrylate oligomer used in the present invention is not particularly limited, and may be aromatic or aliphatic. From the viewpoint of a good balance between the tensile elongation and the tensile strength of the cured product, an aliphatic type is preferable.

  As the component (B) used in the present invention, a commercially available urethane acrylate oligomer may be used, and as such a urethane acrylate oligomer, for example, CN-965, CN-981, CN-9178, CN-9788 manufactured by Sartomer. CN- 9893, CN-971, CN-973, CN-9782, UE-8001 manufactured by Kyoeisha Chemical, UA-122P manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

  As the component (B) used in the present invention, one type may be used alone, or two or more types may be used in combination.

<Content of (A) component and (B) component>
In the sizing agent (1) used in the present invention, the ratio (mass ratio) of the content of the component (A) to the component (B) is: (B) component / (A) component = 1/3 to 2/1 It is necessary to be within the range of When the content of the component (B) is less than 1/3 of the content of the component (A), softening and toughening of the interfacial phase become insufficient, while when it exceeds 2/1, (A The effect of developing good adhesion, which is the function of the component), is inhibited, and the effect of improving the adhesion of the carbon fiber to the matrix resin is not sufficiently obtained. The ratio of the content of the component (A) to the component (B) is preferably (B) component / (A) component = 1/2 to 3/2, and more preferably 2/3 to 1/1. . Moreover, in the sizing agent (1) of this invention, it is required for the ratio of the total amount of (A) component and (B) component to occupy in all the sizing components to be 20 mass% or more. If the amount is less than 20% by mass, the functions of the two components are not sufficiently exhibited, and the effects of the present invention can not be obtained. Here, “total sizing component” is the total amount of all components to be applied to carbon fiber after sizing processing among the components contained in the sizing agent, and is removed after sizing, for example, water, organic solvent, etc. Component represents an active ingredient not included. That is, “total sizing component” is a total amount of the above-mentioned components (A) and (B) and components (C), (D), (E) and other components described later as optional components. Desired. 25 mass% or more is preferable in all the sizing components, and, as for the ratio of the total amount of (A) component and (B) component, 30 mass% or more is more preferable.

<An ester of an alkylene oxide adduct of a bisphenol and a dicarboxylic acid compound and having an acid value of 50 or more (hereinafter, referred to as component (C))>
The sizing agent (1) used in the present invention preferably further contains a component (C) in addition to the components (A) and (B).

  When the acid value is 50 or more, the ester of the alkylene oxide adduct of bisphenol and the dicarboxylic acid compound has a molecular weight of about 1000 and a compound having a carboxyl group at one end of the molecule as a main component. Such component (C) exhibits excellent compatibility with the matrix resin. Therefore, the wettability of the sized carbon fiber to the resin is improved, and the resin impregnation property is further improved.

  The “alkylene oxide adduct of bisphenol” forming the component (C) is preferably a compound obtained by adding 2 to 4 moles of ethylene oxide or propylene oxide to a bisphenol. When five or more moles of ethylene oxide or propylene oxide are added to bisphenols, the rigidity of the molecular chains inherent in bisphenols is lost, and the affinity to the matrix resin may be deteriorated. More preferably, it is obtained by adding 2 mol of ethylene oxide or propylene oxide to bisphenols. The alkylene oxide adducts of bisphenols may be used alone or in combination of two or more compounds.

  The “dicarboxylic acid compound” which forms an ester with an alkylene oxide adduct of a bisphenol is preferably an aliphatic compound having 4 to 6 carbon atoms. When an aromatic compound is used as the dicarboxylic acid compound, the melting point of the obtained ester compound is high, and there is a possibility that the compatibility with the matrix resin may be deteriorated, whereby good wettability may not be expressed. On the other hand, when an aliphatic compound having 7 or more carbon atoms is used as the dicarboxylic acid compound, the rigidity of the obtained ester compound may be lost, and the affinity to the matrix resin may be reduced. Examples of dicarboxylic acid compounds include fumaric acid, maleic acid, methylfumaric acid, methylmaleic acid, ethylfumaric acid, ethylmaleic acid, glutaconic acid, itaconic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid and the like Be

  As the component (C) of the sizing agent (1) used in the present invention, one type may be used alone, or two or more types may be used in combination. In the present invention, the content of the component (C) is preferably 2.0 times or less by mass with respect to the total of the component (A) and the component (B). If it exceeds 2.0 mass times, interaction between the component (A) and the surface of the carbon fiber is caused by the interaction between the epoxy group of the component (A) and the acid group (carboxy group etc.) of the component (C). The action is inhibited, and as a result, the coupling function of the carbon fiber and the matrix resin of the component (A) can not be sufficiently exhibited, and the adhesiveness may be lowered.

  The content of the component (C) in the sizing agent (1) used in the present invention is preferably 1.75 mass times or less, more preferably 1.55 mass, with respect to the total of the components (A) and (B). More preferably not more than twice. The lower limit of the content of the component (C) is not particularly limited, but for the effect of the component (C), 0.2 times the mass of the total of the component (A) and the component (B) The above is preferable, and 0.4 mass times or more is more preferable.

<Anionic surfactant (D) having an ammonium ion as a counter ion (hereinafter referred to as component (D))>
The sizing agent (1) used in the present invention preferably further contains the component (D) and a nonionic surfactant (E) described later.

  The component (D) has a hydrophobic group and an ammonium ion as a counter ion, thereby improving the stability when the sizing agent is an aqueous dispersion and the wettability of the carbon fiber surface to the resin. Moreover, (E) component has an effect which suppresses the reaction activity of the ammonium ion of (D) component, and the epoxy group of (A) component. Therefore, the impregnation property of various matrix resins is further improved by containing the (D) component and the (E) component in appropriate amounts.

  The component (D) is not particularly limited, and examples thereof include carboxylic acid salts, sulfuric acid ester salts, sulfonic acid salts, and phosphoric acid ester salts. Among these, sulfuric acid ester salts and sulfonic acid salts are preferable because they are particularly excellent in the emulsifying ability of the components (A) and (B).

  Examples of the sulfuric acid ester salts include higher alcohol sulfuric acid ester salts, higher alkyl polyethylene glycol ether sulfuric acid ester salts, alkyl benzene polyethylene glycol ether sulfuric acid ester salts, polycyclic phenyl ether polyethylene glycol ether sulfuric acid ester salts, and sulfated fatty acid ester salts. . In addition, propylene oxide units were randomly or blockly contained in part of the polyethylene oxide chain in higher alkyl polyethylene glycol ether sulfate, alkyl benzene polyethylene glycol ether sulfate, and polycyclic phenyl ether polyethylene glycol ether sulfate. One can also be used.

  As the sulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonate, polycyclic phenyl ether sulfonate, alkyl sulfonate, α-olefin sulfonate, α-sulfonated fatty acid salt, dialkyl sulfosuccinate and the like Can be mentioned.

  As the component (D), in particular, an anionic surfactant having a hydrophobic group represented by the following formula (3) or (4) is preferably used.

  A sizing agent (sizing agent solution) dispersed (emulsified) in a medium such as water is generally used for the sizing process of carbon fibers. The hydrophobic group represented by the following formula (3) or (4) has high affinity to an aromatic system, and thus an anionic surfactant having a hydrophobic group represented by formula (3) or (4) is used. By containing it, the emulsified state of the sizing agent solution is stabilized, and the storage property and the production and process at the time of carbon fiber production give good results. In addition, the compatibility between the sizing agent and the matrix resin is improved, and the effects of the present invention, in particular, the mechanical physical properties are further improved.

In addition, such surfactants are also required to avoid the use of anionic surfactants having phenol groups having a relatively long alkyl group such as nonylphenols and octylphenols from the viewpoint of extrinsic endocrine disrupting substance derivatives at present. It is also preferable because it is

In the formulas (3) and (4), R ₁ is a hydrogen atom or a monovalent linear hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a hydrogen atom Or a methyl group is more preferable, and a hydrogen atom is more preferable from the viewpoint of the exogenous endocrine disrupting substance derivative.

R ₂ and R ₃ are a hydrogen atom or a monovalent linear hydrocarbon group having 1 to 3 carbon atoms, which may be identical to or different from each other. Examples of the chain hydrocarbon group of R ₂ and R ₃ include the same chain hydrocarbon group of R 1.

R ₄ is a divalent aliphatic hydrocarbon group, and examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms.

  m is preferably an integer of 1 to 3, and more preferably 1 or 2. When m exceeds 3, the hydrophobic group itself has a bulky structure, and the affinity and compatibility with the (A) component, the (B) component, and the matrix resin decrease. As a result, the emulsion stability, the resin impregnation property, and the mechanical properties of the fiber-reinforced composite material may be deteriorated.

The group in parentheses with the subscript m is either a benzyl group (a group in which both R ₂ and R ₃ are hydrogen atoms) or a styrene group (R ₂ and R ₂ ) in view of the bulkiness of the hydrophobic base molecule. It is preferable that one of ₃ be a hydrogen atom and the other be a methyl group. In addition, when m is 2 or more, that is, when there are a plurality of groups in parentheses with the subscript m, those groups may be the same or different.

<Nonionic surfactant (E) (hereinafter referred to as component (E))>
The component (E) is not particularly limited, but in particular, an aliphatic nonionic surfactant is preferable because the reaction activity reducing action is very excellent. As aliphatic nonionic surfactants, higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid esters ethylene oxide adducts, glycerol fatty acid esters, sorbitol and sorbitan fatty acid esters, pentaerythritol fatty acid esters Etc. Among these ethylene oxide adducts, a type in which propylene oxide units are randomly or block-likely contained in part of the polyethylene oxide chain is also suitably used.

  As the higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, those containing propylene oxide units in a random or block form in part of these polyethylene oxide chains are more preferable. . The reason is that they are excellent in the ability to reduce the reaction activity of ammonium ion to epoxy group.

  As the fatty acid ethylene oxide adduct and polyhydric alcohol fatty acid ester ethylene oxide adduct, monoester type, diester type, triester and tetraester type can be used.

<Content of (D) component and (E) component>
When the sizing agent (1) used in the present invention contains the (D) component and the (E) component, the content ratio (mass ratio) of the (D) component to the (E) component is (E) It is preferable to exist in the range of component / (D) component = 1/10-1/5. When the content of the component (E) is 1/10 or more of the component (D), the reaction activity of the ammonium ion derived from the component (D) with respect to the epoxy group of the component (A) can be reduced. The time-dependent change in hardness of the carbon fiber to which the sizing agent is attached can be remarkably suppressed. When the content of the component (E) is 1⁄5 or less of the component (D), the effect of containing the component (D) is sufficiently exhibited, and when the sizing agent is emulsified using water or the like as a medium And the wettability of the sized carbon fiber surface to the resin is improved.

  Moreover, in the sizing agent (1) used by this invention, it is preferable that the ratio of the total amount of (D) component and (E) component which occupies in all the sizing components is 10-25 mass%. Within the above range, the emulsion stability of the sizing agent solution is good, and the effect of the sizing agent is not adversely affected.

  The more preferable lower limit of the total amount of the (D) component and the (E) component is 13% by mass, and the still more preferable upper limit is 20% by mass.

<Other ingredients>
The sizing agent (1) of the present invention may contain an epoxy resin, an epoxy acrylate compound, an epoxy methacrylate compound, an ester compound, a urethane compound, a polyamide compound, a polyimide compound, and the like, as long as the effects of the present invention are not impaired.

[Production of Sizing Agent (1) and Sizing Treatment of Carbon Fiber]
The sizing agent (1) of this invention can be manufactured by mixing and stirring each component by a conventional method. The sizing agent is usually applied to carbon fibers as a sizing agent liquid dispersed or dissolved in water or an organic solvent in the sizing process of carbon fibers. The sizing process of the present invention is to apply a sizing agent to the surface.

  The application of the sizing agent can be carried out by attaching the sizing agent or a dispersion of the sizing agent to carbon fibers by roller immersion method or roller contact method, and drying. 0.1-5 mass% is preferable with respect to the mass of carbon fiber, and, as for the quantity of the sizing agent provided to carbon fiber, 0.2-3.0 mass% is still more preferable. When the application amount is within this range, the carbon fiber can be sufficiently provided with convergence and scratch resistance, and the wettability with the resin and the interfacial adhesion can be improved, and the element fiber reinforced thermoplastic resin When used as a housing for electrical and electronic devices, it exhibits excellent mechanical properties.

[Method of producing carbon fiber reinforced thermoplastic plastic]
The method for producing a carbon fiber-reinforced thermoplastic plastic of the present invention is not particularly limited as long as it is a method capable of obtaining a carbon fiber-reinforced thermoplastic plastic having a structure in which carbon fibers are impregnated with the thermoplastic resin composition. The known methods can be applied. Specifically, for example, the following method can be used.

  (A) A method of impregnating a heated and melted thermoplastic resin (molten resin) into carbon fibers with an extruder.

  (B) A method of melting a powdery thermoplastic resin after the powdery thermoplastic resin is dispersed together in the inside and the outside of a sheet consisting of a large number of carbon fibers.

  (C) A method of forming a film of a thermoplastic resin, overlapping it with a sheet composed of many single fibers of carbon fiber, and heating and pressing it.

  (D) A method of dissolving a thermoplastic resin in a solvent and impregnating the carbon fiber in a solution state, and then evaporating the solvent.

  (E) A method of fiberizing a thermoplastic resin to form a mixed yarn of a fiberized thermoplastic resin and carbon fibers, and then heating to melt the fibers of the thermoplastic resin.

  Among them, the methods (a) and (c) are preferable. The method of (a) has the advantage that it can be manufactured by supplying carbon fibers to the steps described in the method of manufacturing a thermoplastic resin composition, and the method of (c) requires film processing of a thermoplastic resin. However, relatively good quality fiber reinforced thermoplastics are possible. In particular, when using a fiber-reinforced thermoplastic for applications requiring high specific strength and high specific modulus in a specific direction, it is usually most preferable to use carbon fibers aligned in a single direction ( The method c) is particularly preferred.

[Cases for electrical and electronic devices]
The housing for electric and electronic devices of the present invention is a part or the whole of the carbon fiber reinforced thermoplastic plastic of the present invention. "Electronics and electrical equipment" is a generic term for electronic equipment and electrical equipment, and as electrical and electronic equipment, for example, personal computers (notebook, desktop, tablet), mobile phones, electronic organizers, portable music players, electronic devices A book display etc. are mentioned.

  The housing for electric and electronic devices of the present invention may consist only of the carbon fiber reinforced thermoplastic plastic of the present invention, and the carbon fiber reinforced thermoplastic resin of the present invention and other materials (metal, injection, etc. It may be composed of a thermoplastic resin and the like.

  The invention will now be described in more detail by way of examples.

[Thermoplastic resin composition]
<Thermoplastic resin composition 1>
Nofia CO 3000: random copolymer of phosphonate and carbonate, weight average molecular weight (Mw) 30,000, phosphorus content 3.8% by mass, manufactured by F-R X Polymers <Production example 1: of thermoplastic resin composition 2 Production example>
A thermoplastic resin composition having a phosphorus content of 3.8% by mass is melt-kneaded using the same direction twin-screw extruder (Ikegai Co., Ltd .: PCM-30) under the following conditions and the compositions shown in Raw materials 1 to 3 I got object 2.

Cylinder temperature C1: 200 ° C, C2 to C8: 250 ° C
Screw formation: Install 2 kneading zones Screw speed: 250 rpm
Discharge amount: 20 kg / h
Raw materials 1: NFA HM1100 manufactured by FR X Polymers, polyphosphonate, weight average molecular weight (Mw) 80,000 to 120,000, phosphorus content 10.8% by mass, (28 parts by mass)
Raw materials 2: NF Co., Ltd. manufactured by Nokia CO 6000, random copolymer of phosphate and carbonate, weight average molecular weight (Mw) 50,000, phosphorus atom content rate 6.5 mass% (12 mass parts)
Raw materials 3: Mitsubishi Engineering Plastics Co., Ltd. NOVAREX M7022A, bisphenol A type polycarbonate (60 parts by mass)
[Production example of sizing solution and sizing agent-adhered carbon fiber bundle]
Using a mixer (manufactured by Tokushu Kika Kogyo Co., Ltd., trade name: Hibis Dispermix, Homomixer specification: Model 3D-5 type), a sizing solution was prepared by phase inversion emulsification according to the following procedure.

Production Example 2: Sizing solution 1 and sizing agent-adhered carbon fiber bundle 1
The components (A), (B) and (C) of the types and amounts described below were kneaded and mixed at 80 to 100 ° C. using a planetary mixer and a homomixer. Thereafter, the temperature was lowered to 80 ° C. while maintaining the kneading, and subsequently, an aqueous solution of the component (D) and the component (E) was added little by little. At this step, the viscosity of the contents gradually increased. After all the aqueous solutions of the component (D) and the component (E) were charged, the temperature was lowered to 60 ° C. while sufficiently kneading for 10 minutes. Next, deionized water was dropped little by little and after passing the phase inversion point, the amount of water dropped was increased. Finally, a sizing agent aqueous dispersion 1 having an active ingredient content of about 40% by mass was obtained. The obtained sizing agent aqueous dispersion 1 is adjusted to a solid content concentration of 2.0% by mass, and a carbon fiber bundle (Mitsubishi Rayon Co., Ltd. Pyrophyll TR 50S 15L) to which a resin composition etc. is not attached is immersed, After passing through the nip roll, it was dried by bringing it into contact with a heating roll whose surface temperature was 140 ° C. for 10 seconds, to obtain an ising agent-adhered carbon fiber bundle 1.

(A) Mitsubishi Rayon Co., Ltd., single-ended acrylic modified bisphenol A epoxy resin (28 parts by mass)
(B) CN 871 manufactured by Sartmar, aliphatic urethane acrylate oligomer (25 parts by mass)
(C) Mitsubishi Rayon Co., Ltd., ethylene oxide 2 mol adduct of bisphenol A fumaric acid anhydride anhydride ester (30 parts by mass)
(D) Nippon Emulsifying Material Co., Ltd., Newcol 723SF, polyoxyethylene polycyclic substituted phenyl ether sulfate ammonium salt (15 parts by mass)
(E) Aoki Yushi Kogyo Co., Ltd. product, ISEO, isostearyl alcohol ethylene oxide 6 molar adduct (2 parts by mass)

Production Example 3: Sizing solution 2 and sizing agent-adhered carbon fiber bundle 2
A mixture of 50 parts by mass of a 60 mol adduct of bisphenol A ethylene oxide (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) and 50 parts by mass of a 30 mol adduct of bisphenol A ethylene oxide (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) is added to deionized water The mixture was stirred to finally obtain a sizing solution 2 having a resin composition concentration of 70% by mass. The obtained sizing agent aqueous dispersion 2 is adjusted to a solid content concentration of 2.0% by mass, and a carbon fiber bundle (Pyrofil TR 50S15L manufactured by Mitsubishi Rayon Co., Ltd.) to which a resin composition etc. is not attached is immersed, After passing through the nip roll, it was dried by bringing it into contact with a heating roll whose surface temperature was 140 ° C. for 10 seconds, to obtain an ising agent-adhered carbon fiber bundle 2.

Production Example 4: Sizing solution 3 and sizing agent-adhered carbon fiber bundle 3
A mixture of 40 parts by mass of epoxy resin jER 828 (Mitsubishi Chemical Co., Ltd.), 40 parts by mass of epoxy resin jER 1001 (Mitsubishi Chemical Co., Ltd.) and 20 parts by mass of nonionic surfactant Pluronic F 88 (manufactured by BASF) at 90 ° C. The mixture was kneaded and mixed with a planetary mixer and a homomixer. Next, deionized water was dropped little by little into the kneaded and mixed mixture, and after passing through the phase inversion point, the amount of water dropped was increased. Finally, a sizing solution 3 having a resin composition concentration of 40% by mass was obtained. The obtained sizing agent aqueous dispersion 3 is adjusted to a solid content concentration of 2.0% by mass, and a carbon fiber bundle (Pyrofil TR 50S15L manufactured by Mitsubishi Rayon Co., Ltd.) to which a resin composition or the like is not attached is immersed. After passing through the nip roll, it was dried by bringing it into contact with a heating roll whose surface temperature was 140 ° C. for 10 seconds, to obtain an ising agent-adhered carbon fiber bundle 3.

[Manufacture of carbon fiber reinforced thermoplastic plastic]
Production Example 5 Production Example 1 of Carbon Fiber-Reinforced Thermoplastic
The thermoplastic resin composition was used to obtain a resin film having a thickness of 30 μm using a single screw extruder (manufactured by IKG Co., Ltd., product name: PMS30).

  A carbon fiber sheet with a basis weight of 100 g / m 2 is produced using a sizing agent-adhered carbon fiber bundle by a drum winding method, and the carbon fiber sheet is appropriately tensioned to obtain the above resin film and fluorine from both sides of the carbon fiber sheet. A plastic film (Nitto Denko Co., Ltd. product name: Nitroflon film 970-4UL) and a flat plate made of aluminum are held in this order, heated at 300 ° C. for 5 minutes, 100 kPa, with a heating plate of a heating / cooling two-stage press A fiber-reinforced thermoplastic plastic having a fiber volume content of about 48% by volume and a thickness of about 115 μm was obtained under the conditions of 20 ° C., 5 minutes, and 400 kPa. The resulting fiber-reinforced thermoplastic with a thickness of 115 μm is cut into a size of 308 mm square, and the fiber direction is [0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 18 sheets are stacked so that ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 °], and it is in a 310 mm square, 0.5 mm deep printing mold Using a compression molding machine (product name: SFA-50HH0, manufactured by Shinto Metal Industry Co., Ltd.), place, heat, and hold for 12 minutes under the conditions of 230 ° C and hydraulic pressure instruction 8MPa (press pressure 2.1MPa) with a high temperature side press The mold is moved to a cooling press and held for 4 minutes at 80 ° C., hydraulic instruction 15 MPa (press pressure 3.9 MPa) for a fiber-reinforced thermoplastic plastic with a fiber volume content of about 48 volume% and a thickness of 2 mm. Obtained.

Production Example 6 Production Example 2 of Carbon Fiber-Reinforced Thermoplastic
Similar to Production Example 5, except that six sheets were stacked so that the fiber direction was [0 ° / 90 ° / 0 ° / 0 ° / 90 ° / 0 °], and the fiber volume content was about 48% by volume, thickness A 0.7 mm fiber reinforced thermoplastic was obtained.

<Evaluation of carbon fiber reinforced thermoplastics>
[1] Flame retardancy test The obtained 0.7 mm thick carbon fiber reinforced thermoplastic plastic was measured in accordance with the UL 94 combustion test. The evaluation results were recorded.

[2] 90 ° bending test (adhesion evaluation) m
The obtained carbon fiber-reinforced thermoplastic plastic having a thickness of 2 mm was subjected to a bending test according to ASTM D 790 such that the fiber direction of the bending test piece became 90 ° with the longitudinal direction of the test piece. The 90 ° bending strength was calculated and recorded from the maximum load in the bending test.

Example 1
Using the thermoplastic resin composition 1 and the sizing agent-adhered carbon fiber bundle 1, a carbon fiber reinforced thermoplastic plastic having a thickness of 0.7 mm and a carbon fiber reinforced thermoplastic plastic having a thickness of 2 mm were obtained. The flame retardancy test and the 90 ° bending test were performed using the obtained carbon fiber reinforced thermoplastic plastic. The results of the evaluation are shown in Table 2. As a result of evaluation, excellent flame retardant performance and mechanical properties were shown.

(Comparative example 1)
Using the thermoplastic resin composition 1 and the sizing agent-adhered carbon fiber bundle 2, a carbon fiber reinforced thermoplastic resin having a thickness of 2 mm was obtained. A 90 ° bending test was carried out using the obtained carbon fiber reinforced thermoplastic plastic. The results of the evaluation are shown in Table 2. As a result of evaluation, adhesion was insufficient at 90 ° bending of less than 10 MPa.

(Comparative example 2)
A 90 ° bending test was conducted in the same manner as in Comparative Example 1 except that the sizing agent-adhered carbon fiber bundle 3 was used instead of the sizing agent-adhered carbon fiber bundle 2. The results of the evaluation are shown in Table 2. As a result of evaluation, adhesion was insufficient at 90 ° bending of less than 10 MPa.

(Example 2)
The flame retardancy test and the 90 ° bending test were conducted in the same manner as in Example 1 except that the thermoplastic resin composition 2 was used instead of the thermoplastic resin composition 1. The results of the evaluation are shown in Table 2. As a result of evaluation, excellent flame retardant performance and mechanical properties were shown.

Claims (10)

A thermoplastic resin composition containing a phosphorus-containing polymer containing a structural unit represented by the following (formula 1), and carbon fibers, the carbon fibers being sized with the following sizing agent (1) , unidirectional Carbon fiber reinforced thermoplastics that are aligned, woven, or non-crimp fabrics .
(Formula 1)
Sizing agent (1): an ester of an epoxy compound having two or more epoxy groups in the molecule and an unsaturated monobasic acid, wherein the compound (A) has at least one epoxy group in the molecule, and a cured product Containing a bifunctional urethane acrylate oligomer (B) having a tensile elongation of 40% or more, and the ratio (mass ratio) of the content of the compound (A) to the urethane acrylate oligomer (B) is The ratio of the total amount of the compound (A) and the urethane acrylate oligomer (B) in the total sizing component is 20 in the range of acrylate oligomer (B) / compound (A) = 1/3 to 2/1 is 20 Sizing agent which is% by mass or more. The carbon fiber reinforced thermoplastic resin according to claim 1, wherein the phosphorus-containing polymer containing the structural unit represented by the above (formula 1) is a phosphorus-containing polymer having a partial structure represented by the following (formula 2).
(Formula 2)
(X and y in (Formula 2) are integers of 1 to 19) Ri weight average molecular weight Mw of Der 10,000 160,000 following the phosphorus-containing polymer, 90 ° flexural strength of the carbon fiber reinforced thermoplastic plastic, carbon fiber according to claim 1 or 2 is greater than or equal to 30MPa Reinforced thermoplastics. In the thermoplastic resin composition, the carbon fiber-reinforced thermoplastics according to any one of claims 1 to 3 ratio of the said phosphorus-containing polymer is not less than 20 mass%. The thermoplastic resin composition, the carbon fiber-reinforced thermoplastics according to claim 1 containing bisphenol A polycarbonate resin.   The carbon fiber reinforced thermoplastic plastic according to claim 5, wherein the proportion of the total amount of the bisphenol A polycarbonate and the phosphorus-containing polymer in the thermoplastic resin composition is 70% by mass or more. The sizing agent (1) is an ester of an alkylene oxide adduct of a bisphenol and a dicarboxylic acid compound, and contains an ester compound (C) having an acid value of 50 or more. The carbon fiber reinforced thermoplastic resin according to item 1 . Sizing agent (1) is, it contains an anionic surfactant having an ammonium ion as a counter ion (D), and nonionic surfactant (E), according to any one of claims 1 to 6 Carbon fiber reinforced thermoplastics. Made of carbon fiber-reinforced thermoplastics according to any one of claims 1 to 8, is 1.6mm or less is 0.4mm or more thickness, the molding material flame retardancy based on UL94 satisfies V-0 .   The housing for electric and electronic devices which comprises a part or all by the molding material of Claim 9.