KR20180008602A - A polycarbonate resin composition, and a polycarbonate resin prepreg - Google Patents

Abstract

A polycarbonate resin composition excellent in impregnation property and flame retardancy of continuous fiber reinforcement, and a polycarbonate prepreg excellent in flame retardancy. A polycarbonate resin composition comprising 60 to 88 mass% of a polycarbonate resin (A) and 12 to 40 mass% of a phosphorus flame retardant (B), wherein the flow rate of the polycarbonate resin composition at 240 캜 is 9 to 120 x 0.01 cc / sec, the above problems have been solved.

Description

A polycarbonate resin composition, and a polycarbonate resin prepreg

The present invention relates to a polycarbonate resin composition, a polycarbonate prepreg, and the like. More specifically, the present invention relates to a polycarbonate resin composition containing a flame retardant and a polycarbonate prepreg obtained by impregnating a polycarbonate resin composition with a continuous fiber reinforcement.

BACKGROUND ART [0002] A continuous fiber reinforced composite material (hereinafter sometimes referred to as "FRTP") composed of a thermoplastic resin as a matrix and a continuous fiber reinforced material is already well known. Such FRTP is usually used in the production of a prepreg impregnated with a resin in a reinforcing fiber in the form of a single strand, a unidirectional sheet (UD sheet), a woven fabric, or a nonwoven fabric, and the prepreg is subjected to press forming or filament winding forming Molded) to produce a product such as a structural member or various parts.

Examples of the use of the FRTP include a prepreg made from a thermoplastic resin and a unidirectionally aligned fiber sheet or a woven fabric using continuous fibers such as glass fiber or carbon fiber. These prepregs are advantageous in that the volume fraction of the fibers can be increased, and have excellent properties of the elastic modulus and strength in the fiber orientation direction.

In the preparation of the prepreg using FRTP, the impregnation property of the matrix resin into the continuous fiber is important and greatly affects mechanical properties such as strength and appearance. As a method of producing the prepreg of FRTP, a solution method, a hot-melt method, a slurry method, a fluidized bed method, and the like are generally known. Among them, the hot pressing method in which the resin component is melted and impregnated with the continuous fiber is simple, but in the case of the polycarbonate having low resin melt fluidity, impregnation with the continuous fiber is poor, and good products can not be obtained.

Patent Document 1 relates to a stranded prepreg using a thermoplastic resin having a melt viscosity of 1,000 to 15,000 poise in a thermoplastic resin. However, since the FRTP plate is cut into a single piece, a large-sized molded article is molded There is a problem that sufficient rigidity can not be obtained. Furthermore, in Patent Document 1, it is not suggested that the prepreg has flame retardancy.

Patent Document 2 discloses a composite material comprising a thermoplastic resin and carbon fiber. However, since the thermoplastic resin used has a high viscosity and poor impregnation with carbon fibers, dispersing the resin on the powder obtained by freezing and pulverizing pellets . Since the resin on the powder has a low bulk density and contains air, the removal of bubbles in the composite material becomes insufficient, resulting in a problem that appearance and strength are inferior. Further, in Patent Document 2, it is described that a flame retardant may be included in the composite material, but no specific disclosure concerning the flame retardancy of the flame retardant and the composite material is disclosed.

Patent Document 3 describes a carbon continuous fiber reinforced polycarbonate resin prepreg in which carbon fibers are aligned in one direction using a polycarbonate having a melt viscosity of 1 to 100 Pa · s at 250 ° C. However, in the prepreg described in Patent Document 3, since the molecular weight of the polycarbonate is low, mold contamination by a low-molecular component is liable to occur at the time of heat-forming, and the strength at the time of bending is insufficient. Further, in Patent Document 3, since the polycarbonate resin has a low viscosity, the resin tends to sag with flames at the time of burning, which is not suitable for softening, and it is not suggested to secure flame retardancy.

Japanese Patent No. 2507565 Japanese Patent Application Laid-Open No. 2011-178890 Japanese Patent Application Laid-Open No. 2014-91825

It is an object of the present invention to provide a polycarbonate resin composition excellent in impregnation property and flame retardancy of a continuous fiber reinforcement, and a polycarbonate prepreg excellent in flame retardancy.

As a result of intensive studies to solve the above problems, the present inventors have found that by using a mixture of a polycarbonate and a flame retardant adjusted to a specific melt viscosity as an impregnant for a continuous fiber reinforced material, A polycarbonate resin composition excellent in flame retardancy and a polycarbonate prepreg having high flame retardancy using the resin composition having such excellent performance can be provided.

That is, the present invention is as follows.

1. A polycarbonate resin composition containing 60 to 88 mass% of a polycarbonate resin (A) and 12 to 40 mass% of a phosphorus flame retardant (B), wherein the flow rate of the polycarbonate resin composition at 240 deg. 120 x 0.01 cc / sec.

2. The polycarbonate resin composition according to the above 1, wherein the phosphorus flame retardant (B) comprises at least one of a condensed phosphoric acid ester and a phosphazene flame retardant.

Wherein the condensed phosphoric acid ester comprises at least one of triphenyl phosphate, bisphenol A tetraphenyl phosphate, resorcinol tetraphenyl phosphate, and resorcinol tetra-2,6-xylenol phosphate,

The polycarbonate resin composition according to (2) above, wherein the phosphazene-based flame retardant comprises at least one of phenoxyphosphazene, (poly) tolyloxyphosphazene, and (poly) phenoxytoluyloxyphosphazene.

4. Wherein the polycarbonate resin composition is a polycarbonate resin composition.

5. Wherein the continuous fiber reinforcing material (C) is a polycarbonate prepreg containing 25 to 60% by volume (Vf value), wherein the continuous fiber reinforcing material (C) is a polycarbonate prepreg obtained by impregnating the continuous polycarbonate resin composition Legs.

6. A polycarbonate prepreg impregnated with the continuous fiber reinforcing material (C) as described in 4 above, wherein the continuous fiber reinforcing material (C) is a polycarbonate prepreg having a poly Carbonate prepreg.

7. A laminate containing the polycarbonate prepreg according to 5 or 6 above.

8. A formed article in which the laminate according to the above item 7 is formed into a column shape.

The polycarbonate resin composition of the present invention has high resin-impregnated properties as a fiber and excellent flame retardancy, and therefore, the prepreg made of the continuous fiber-reinforced flame retardant polycarbonate resin of the present invention is also excellent in flame retardancy. Therefore, the prepreg made of the continuous fiber-reinforced flame retardant polycarbonate resin of the present invention can be suitably used as a heat-shrinkable sheet and film for electric and electronic appliance cases.

Hereinafter, the present invention will be described in detail.

[Polycarbonate resin (A)]

The polycarbonate resin (A) used in the present invention (hereinafter sometimes referred to as "component (A)") is not particularly limited, but polycarbonate resin is preferable, and use of an aromatic polycarbonate resin is particularly preferable desirable. The polycarbonate resin is a thermoplastic polymer or copolymer which may be branched, obtained by reacting a dihydroxy compound or a small amount of a polyhydroxy compound with a phosgene or a carbonate diester. The method for producing the polycarbonate resin is not particularly limited, and those produced by the conventionally known Phosgene method (interfacial polymerization method) or the melting method (ester exchange method) can be used. When the melting method is used, a polycarbonate resin in which the amount of OH groups in the terminal group is adjusted can be used.

Examples of the dihydroxy compound as the raw material include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, Quinone, resorcinol, 4,4-dihydroxydiphenyl, and the like, preferably bisphenol A. Further, a compound having at least one tetraalkylphosphonium sulfonate bonded to the above aromatic dihydroxy compound may be used.

To obtain the branched polycarbonate resin, a part of the above-mentioned dihydroxy compound is reacted with the following branching agents, namely, fluoroglucine, 4,6-dimethyl-2,4,6-tri (4-hydroxy Phenyl) heptene, 2,4-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6- Polyhydroxy compounds such as 3-heptene, 1,3,5-tri (4-hydroxyphenyl) benzene and 1,1,1-tri (4-hydroxyphenyl) -Hydroxyaryl) oxyindole (= Isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. The amount of these substituting compounds is usually 0.01 to 10 mol%, preferably 0.1 to 2 mol%, based on the dihydroxy compound.

As the polycarbonate resin (A), a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane or a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) Polycarbonate copolymers derived from other aromatic dihydroxy compounds are preferred. Further, a copolymer mainly composed of a polycarbonate resin such as a copolymer with a polymer or oligomer having a siloxane structure may be used.

The above-mentioned polycarbonate resins may be used singly or in combination of two or more kinds.

In order to control the molecular weight of the polycarbonate resin (A), a monohydric hydroxy compound such as an aromatic hydroxy compound may be used. As the monohydric aromatic hydroxy compound, for example, m- and p-methylphenol , m- and p-propylphenol, p-tert-butylphenol, and p-long-chain alkyl-substituted phenol.

The molecular weight of the polycarbonate resin (A) used in the present invention is arbitrary depending on the application, and may be appropriately selected and determined. From the viewpoints of moldability and the strength of the molded article, the polycarbonate resin (A), preferably an aromatic polycarbonate The molecular weight of the resin (A) is preferably 15,000 to 40,000, particularly 15,000 to 30,000 in terms of the viscosity average molecular weight [Mv]. When the viscosity average molecular weight of the polycarbonate resin (A) is 15,000 or more, the mechanical strength tends to be further improved, and it is more preferable when the polycarbonate resin (A) is used for applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight of the polycarbonate resin (A) is 40,000 or less, the lowering of the fluidity tends to be further suppressed and improved, which is more preferable from the viewpoint of ease of molding processability and flame retardancy. The viscosity average molecular weight [Mv] here is the viscosity-average molecular weight [Mv] converted from the solution viscosity, and the intrinsic viscosity [η] (unit: dl / g) to obtain the viscosity formula of Schnell, that is, η = 1.23 × 10 ^-4 Mv value calculated from ^0.83 (viscosity average molecular weight means the Mv). Herein, the intrinsic viscosity [?] Is a value calculated by the following formula by measuring the specific viscosity [? _Sp ] at each solution concentration [C] (g / dl).

[Phosphorus flame retardant (B)]

The polycarbonate resin composition of the present invention contains a phosphorus-based flame retardant (B) in order to improve the impregnation property and the flame retardancy at the time of heat melting to the fiber, which will be described later in detail.

As the phosphorus flame retardant (B), phosphoric acid ester flame retardants and phosphazene flame retardants can be used.

The phosphorylated flame retardant (B) may be used alone or in combination of two or more. As the phosphorus flame retardant (B), a phosphoric acid ester flame retardant is preferably used since it has a high flame retardant effect, has an effect of improving fluidity, and hardly causes mold corrosion.

<Phosphoric acid ester flame retardant>

The phosphoric ester-based flame retardant used as the phosphorus flame retardant (B) is not particularly limited, but phosphoric acid ester-based flame retardants represented by the following formula (II) are preferable as the phosphate ester flame retardant.

(In the formula (II), R ¹ , R ² , R ³ and R ⁴ each independently represent an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group, r and s are each independently 0 or 1, t is an integer of 1 to 5, and X is an arylene group.

In the above formula (II), examples of the aryl group of R ¹ to R ⁴ include a phenyl group and a naphthyl group. Examples of the arylene group of X include a phenylene group and a naphthylene group. When t is 0, the compound represented by the formula (II) is a phosphate ester, and when t is greater than 0, the compound is a condensed phosphoric acid ester (including a mixture). In the present invention, condensed phosphate esters are particularly preferably used.

Specific examples of the phosphate ester flame retardant represented by the above formula (II) include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, tri (Chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromo propyl) phosphate, dibutylphosphoryl phosphate, Bis (2,3-dibromopropyl) -2,3-dichlorophosphate, bis (chloropropyl) monooctyl phosphate, bisphenol A tetraphenyl phosphate, bisphenol A tetracresyl diphosphate, bisphenol A tetrazyl diphosphate, Hydroquinone tetraphenyldipo But are not limited to, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, . Of these, preferred are triphenyl phosphate, bisphenol A tetraphenyl phosphate, resorcinol tetraphenyl phosphate, resorcinol tetra-2,6-xylenol phosphate and the like.

<Phosphazene-based flame retardant>

The phosphazene-based flame retardant is used as the phosphorus flame retardant most effective in the present invention because the lowering of the heat resistance is lower than that of the condensed phosphoric acid ester. The phosphazene-based flame retardant is an organic compound having a P═N bond in the molecule, and the phosphazene-based flame retardant is preferably a cyclic phosphazene compound represented by the following formula (IIIa), a chain phosphor represented by the following formula (IIIb) A crosslinked phosphazene compound crosslinked by a crosslinking group, and the like. Particularly, it is preferable to use a crosslinked product of at least one phosphazene compound selected from the group consisting of the following formula (IIIa) and the following formula (IIIb). As the crosslinking group for forming the crosslinked phosphazene compound, a crosslinking group represented by the following formula (IIIc) is preferable in view of the flame retardancy of the resulting crosslinked phosphazene compound.

(In the formula (IIIa), m is an integer of 3 to 25, and R ⁵ may be the same or different and represents an aryl group or an alkylaryl group.)

(OR ⁵ ) ₃ group or -N = P (O) OR ⁵ group, and Y is -P (OR ⁵ ) ₄ (in the formula (IIIb), n is an integer of 3 to 10,000, (O) (OR ⁵ ) ₂ group, and R ⁵ may be the same or different and represents an aryl group or an alkylaryl group.

(In the formula (IIIc), A is -C (CH ₃ ) ₂ -, -SO ₂ -, -S-, or -O-, and l is 0 or 1.

As the cyclic phosphazene compound represented by the formula (IIIa), cyclic phenoxyphosphazene in which R ⁵ is a phenyl group is particularly preferable. As such cyclic phenoxyphosphazene compounds, there can be mentioned, for example, compounds obtained by reacting ammonium chloride and phosphorus pentachloride in the presence of a cyclic and straight chain chlorophosphazene mixture obtained by reacting at a temperature of 120 to 130 ° C to obtain hexachlorocyclotriphosphazene, (Chlorine) is replaced with a phenoxy group after the cyclic chlorophosphazene such as chlorocyclotetrafluoroethane, chlorocyclotetrafosphene, decachlorocyclopentaphosphazene and the like is taken out and then phenoxy cyclotriphosphazene, octaphenoxycyclotetrafos Phachen, decaphenoxycyclopentaphosphane, and the like. The cyclic phenoxyphosphazene compound is preferably a compound represented by the formula (IIIa) wherein m is an integer of 3 to 8, and may be a mixture of compounds having different m. Among them, a mixture of compounds in which m = 3 is 50% by mass or more, m = 4 is 10-40% by mass, and m = 5 or more is 30% by mass or less is preferable.

Specific examples of the cyclic phenoxyphosphazene compound represented by the formula (IIIa) include phenoxyphosphazene, (poly) tolyloxyphosphazene (e.g., o-tolyloxyphosphazene, m- m, p-tolyloxyphosphazene, o, m-tolyloxyphosphazene, o, p-tolyloxyphosphazene, m, p- Cyclic C _1-6 alkyl C _6-20 aryloxy phosphazene such as xylyl _{oxyphosphazene} , (poly) phenoxy tolyloxy phosphazene (for example, phenoxy o-tolyloxyphosphazene, phenoxy m- Tolyloxyphosphazene, phenoxy p-tolyloxyphosphazene, phenoxy o, m-tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o (poly) phenoxy xylyl oxyphosphazene, (poly) phenoxy tolyloxyoxyallyphosphazene, and the like, C _6-20 aryl C _1-10 alkyl C _{6 -20} aryloxyphosphazene etc. And preferably, cyclic phenoxyphosphazenes, cyclic C _1-3 alkyl C _6-20 aryloxyphosphazenes, C _6-20 aryloxy C _1-3 alkyl C _6-20 aryloxyphosphazenes ( For example, cyclic tolyloxyphosphazene, cyclic phenoxytolyl phenoxyphosphazene, etc.).

On the other hand, the description of "C _1-6 " means "having 1 to 6 carbon atoms", and the same applies to "C _6-20 ", "C _1-10 " and the like. Further, the description of "(poly) phenoxy" refers to one or both of "phenoxy" and "polyphenoxy".

As the chain phosphazene compound represented by the formula (IIIb), a chain phenoxyphosphazene in which R ⁵ is a phenyl group is particularly preferable. As such a chain phenoxyphosphazene compound, for example, hexachlorocyclo-triphosphazene obtained by the above-mentioned method can be subjected to ring-opening polymerization at a temperature of 220 to 250 ° C, and the resulting linear dichlorsophosphazene having a degree of polymerization of 3 to 10,000 And a compound obtained by substituting a chloro group (chlorine) with a phenoxy group. The n in the formula (IIIb) of the corresponding linear phenoxyphosphazene compound is preferably 3 to 1,000, more preferably 3 to 100, and still more preferably 3 to 25. [

Specific examples of the chain phenoxyphosphazene compound represented by the formula (IIIb) include phenoxyphosphazene, (poly) tolyloxyphosphazene (for example, o-tolyloxyphosphazene, m- m, p-tolyloxyphosphazene, o, m-tolyloxyphosphazene, o, p-tolyloxyphosphazene, m, p- Chain C _1-6 alkyl C _6-20 aryloxyphosphazenes such as xylyl _{oxyphosphazene} , (poly) phenoxytoluyloxyphosphazenes (for example, phenoxy o-tolyloxyphosphazene, phenoxy m- Tolyloxyphosphazene, phenoxy p-tolyloxyphosphazene, phenoxy o, m-tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o (poly) phenoxy xylyl oxyphosphazene, (poly) phenoxy tolyloxy oxyl xylyl oxyphosphazene, etc., C _6-20 aryl C _1-10 alkyl C _{6 -20} aryloxyphosphazene etc. May be exemplified, and preferable examples thereof include chain phenoxyphosphazene, chain C _1-3 alkyl C _6-20 aryloxy phosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20 aryloxyphosphazene ( For example, chain tolyloxyphosphazene, chain phenoxytolyl phenoxyphosphazene, etc.).

Examples of the crosslinked phosphazene compound include a crosslinked phenoxyphosphazene compound in which a cyclic phenoxyphosphazene compound in which R ⁵ is a phenyl group in the formula (IIIa) is crosslinked by a crosslinking group represented by the above formula (IIIc) (IIIb), a crosslinked phenoxyphosphazene compound in which a chain phenoxyphosphazene compound in which R ⁵ is a phenyl group is crosslinked by a crosslinking group represented by the above formula (IIIc) is preferable from the viewpoint of flame retardancy, and a cyclic phenoxyphosphazene Is a crosslinked phenoxyphosphazene compound in which the compound is crosslinked by a crosslinking group represented by the above formula (IIIc).

Examples of the crosslinking phenoxyphosphazene compound include compounds having a crosslinking structure of 4,4'-sulfonyldiphenylene (bisphenol S residue), 2,2- (4,4'-diphenylene) isopropyl A compound having a crosslinking structure of a 4,4'-thiodiphenylene group, a compound having a crosslinking structure of a 4,4'-thiodiphenylene group, and a compound having a crosslinking structure of a 4,4'- And a compound having a crosslinked structure of a phenylene group.

The content of the phenylene group in the crosslinked phenoxyphosphazene compound is preferably such that the total phenyl group and phenylene group number in the cyclic phosphazene compound represented by the formula (IIIa) and / or the chain phenoxyphosphazene compound represented by the formula (IIIb) 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 thereof.

In the present invention, the phenoxyphosphazene compound is a compound in which the cyclic phenoxyphosphazene compound represented by the formula (IIIa) and the cyclic phenoxyphosphazene compound represented by the formula (IIIa) are cross-linked by a cross- Is preferably at least one member selected from the group consisting of a cyclic phenoxyphosphazene compound and a cyclic phenoxyphosphazene compound in terms of flame retardancy and mechanical properties. As a commercially available cyclic phosphazene-based flame retardant, for example, "RABITOL FP110" manufactured by FUSHIMI Pharmaceuticals Co., Ltd. and "SPS100" manufactured by Otsuka Chemical Co., Ltd. can be mentioned.

[Polycarbonate resin composition]

The polycarbonate resin composition of the present invention contains 60 to 88 mass% of the polycarbonate resin (A) and 12 to 40 mass% of the phosphorus flame retardant (B).

The preferable content of the polycarbonate resin (A) is 70 to 85% by mass, and more preferably 75 to 85% by mass.

Further, the polycarbonate content of the phosphorus-based flame retardant (B) in the resin composition, the flow value of the polycarbonate resin composition ^{(240 ℃, 160kg / cm 2} ) is 9~120 × 0.01 (cc / sec) , preferably 10 To 60 x 0.01 (cc / sec). The amount of the phosphorus flame retardant (B) to be added is preferably 12 to 40% by mass, more preferably 15 to 30% by mass in view of flame retardancy and heat resistance. When the addition amount of the phosphorylated flame retardant (B) is 12 mass% or more, the flame retardant effect and the fiber impregnation property are good and the desired physical properties of the composition are obtained. Further, when the addition amount of the phosphorus-containing flame retardant (B) is 40 mass% or less, heat resistance and deterioration of the toughness of the matrix resin can be suppressed.

In the polycarbonate resin composition is as described above, the flow value is 9~120 × 0.01cc / sec in the ^{240 ℃ (160kg / cm 2)} . By adjusting the flow rate of the polycarbonate resin composition in this way, the impregnation property of the resin composition to the fiber, the heat resistance of the resin composition, and the flame retardant effect of the prepreg produced using the resin composition are both excellent And excellent balance of these physical properties can be realized.

· Flame retardant · anti-drop agent

The aromatic polycarbonate resin composition of the present invention may further contain a flame retardant and an anti-dripping agent other than the component (B) of the present invention.

Examples of the flame retardant other than the component (B) include halogenated flame retardants such as polycarbonate of halogenated bisphenol A, brominated bisphenol-based epoxy resin, brominated bisphenol-based phenoxy resin and brominated polystyrene, Organic metal salt flame retardants such as dipotassium 3'-disulfonate, potassium diphenylsulfon-3-sulfonate, and potassium perfluorobutane sulfonate; and polyorganosiloxane-based flame retardants.

Examples of the anti-drip agent include fluorinated polyolefins such as polyfluoroethylene, and polytetrafluoroethylene preferably having fibril forming ability. This shows a tendency to be easily dispersed in the polymer and to bind the polymers together to form a fibrous material. Polytetrafluoroethylene having fibril forming ability is classified as type 3 in the ASTM standard. As the polytetrafluoroethylene, in addition to a solid form, an aqueous dispersion type can also be used. As the polytetrafluoroethylene having fibril forming ability, there can be used, for example, Teflon (registered trademark) 6J or Teflon (registered trademark) 30J from Mitsui DuPont Fluorochemical Co., (Trade name).

When the aromatic polycarbonate resin composition of the present invention contains the anti-drip agent, the content of the anti-drip agent is preferably 100 parts by mass or less based on 100 parts by mass of the total of the aromatic polycarbonate resin (A), phosphorus flame retardant (B) Preferably 0.02 to 4 parts by mass, and more preferably 0.03 to 3 parts by mass. If the compounding amount of the anti-drip agent exceeds the upper limit, the appearance of the molded article may be deteriorated.

· Other resin components

The aromatic polycarbonate resin composition of the present invention may contain a resin component other than the aromatic polycarbonate resin (A) as the resin component so long as the object of the present invention is not impaired. As other resin components that can be blended, for example, polystyrene resin, high impact polystyrene resin, hydrogenated polystyrene resin, polyacrylic styrene resin, ABS resin, AS resin, AES resin, ASA resin, SMA resin, A polycarbonate resin other than the component (A), an amorphous polyalkylene terephthalate resin, a polyester resin, an amorphous polyamide resin , Poly-4-methylpentene-1, cyclic polyolefin resin, amorphous polyarylate resin, and polyethersulfone.

[Continuous fiber reinforcement (C)]

The continuous fiber reinforced polycarbonate resin prepreg of the present invention may be referred to as a continuous fiber reinforcing material (hereinafter sometimes referred to as &quot; component (C) &quot;) in order to enhance the flexural properties such as the flexural modulus and the bending strength of the molded product. Is impregnated into the polycarbonate resin composition containing the components (A) and (B).

Examples of the continuous fiber reinforcement (C) used in the present invention include glass fibers and carbon fibers. Since the reinforcing effect of the polycarbonate resin composition is excellent, as the form of the continuous fiber reinforcement (C), a fibrous fabric such as cloth or a fiber which is opened and drawn in one direction is preferable. (Vf value) of the continuous fiber reinforcement is used as an index of the content of fibers in the prepreg.

<Glass fiber>

The glass composition of the glass fiber used in the present invention is not particularly limited, and glass compositions such as A glass, C glass and E glass can be used. In particular, E glass which is an alkali- It does not adversely affect the aromatic polycarbonate resin (A).

(E glass composition:% by mass)

SiO ₂ : 52-56

Al ₂ O ₃ : 12 to 16

Fe ₂ O ₃ : 0 to 0.4

   CaO: 16-25

   MgO: 0-6

B ₂ O ₃ : 5-13

TiO ₂ : 0 to 0.5

R ₂ O (Na ₂ O + K ₂ O): 0 to 0.8

The glass fiber may be surface-treated with a surface treatment agent described later. By such surface treatment, adhesion between the resin component and glass can be improved and high mechanical strength can be achieved.

<Carbon fiber>

The carbon fiber is not particularly limited and known carbon fibers such as polyacrylonitrile (PAN), petroleum and coal pitch can be used.

In the present invention, in particular, in order to enhance the adhesion between the continuous fiber reinforcement (C) and the resin component, the decomposition of the aromatic polycarbonate resin (A) by the contact between the glass fiber and the aromatic polycarbonate resin (A) , It is preferable to use a continuous fiber reinforcement (C) whose surface has been treated with a surface treatment agent. Examples of suitable surface treating agents include silane coupling agents such as amino silane and epoxy silane, and silicone compounds.

[Other components]

The continuous fiber-reinforced polycarbonate resin composition of the present invention may contain other components as necessary in addition to the aromatic polycarbonate resin (A), phosphorus-based flame retardant (B), and continuous fiber reinforcement (C). Other components that the aromatic polycarbonate resin composition of the present invention can contain include, for example, the following.

<Other additives>

The aromatic polycarbonate resin composition of the present invention may further contain various additives insofar as the effect of the present invention is not impaired. Examples of such additives include additives such as stabilizers, antioxidants, mold release agents, ultraviolet absorbers, salt pigments, antistatic agents, flame retardants, anti-drop agents, impact strength improvers, plasticizers, dispersants, antibacterial agents, (A), Other resins, and the like. These resin additives may contain one kind or two or more kinds in any combination and ratio.

[Other inorganic components]

By adding short staple fibers or short staple fibers having an average fiber length of 10 mm or less as an inorganic component other than the continuous fiber reinforcement (C) component at the time of preparing the aromatic polycarbonate resin-made continuous fiber reinforced prepreg of the present invention, mechanical properties Can be further increased. Examples of the short fiber filler include glass short fibers, carbon short fibers, wollastonite, various inorganic whiskers, and the like.

In addition, anisotropy at the time of shrinkage can be improved by adding a plate-like or spherical filler. Examples of the plate-shaped filler include glass flakes, mica and talc. Examples of the spherical filler include glass beads and silica beads.

&Lt; Production method of continuous fiber-reinforced polycarbonate resin prepreg &gt;

A method for producing a continuous fiber-reinforced polycarbonate resin prepreg is a method in which a molten resin is flowed from a T die of an extruder and is then impregnated with a fiber sheet laid out or laid in one direction, A method in which the resin is laminated on a fiber layer, and then the laminate is heated, and the like. Since the polycarbonate used in the continuous fiber-reinforced polycarbonate resin prepreg of the present invention is excellent in flowability, a method of impregnating a molten resin by discharging it from an extruder, or a method of heat-laminating a resin into a film is preferably used .

The process of impregnating the fiber with a specific polycarbonate in the melting process may be a method of solidifying the prepreg after melt infiltration by a combination of a hot press and a cold press in addition to the method using the extruder, A method of providing a cooling zone, and the like.

<Shape, shape and characteristic of prepreg>

The thickness of the fiber-reinforced polycarbonate resin prepreg of the present invention is usually 50 to 500 m, preferably 150 to 350 m, per one sheet. For example, 170 to 305 mu m. If the thickness of one prepreg is thinner than 50 탆, it is impossible to sufficiently impregnate the resin component, so that the resulting prepreg is carded, making handling difficult. When the thickness of one prepreg is more than 500 mu m, the content of the reinforcing fibers is lowered, so that sufficient physical properties can not be obtained.

In addition, the prepreg of the present invention produced by the above-mentioned production method, that is, the prepreg obtained by impregnating the polycarbonate resin composition of the present invention with the continuous fiber reinforcement (C), or the polycarbonate resin film, In the laminated prepreg, the volume content (Vf value) of the continuous fiber reinforcement is preferably 25 to 60%, more preferably 35 to 50%. By setting the Vf value to 25% or more, the reinforcement reinforcement becomes a sufficient level. By setting the Vf value to 60% or less, impregnation of the resin into the reinforcement material is facilitated and a prepreg excellent in appearance and strength can be realized have.

<Laminate and molded article>

The laminate of the present invention contains the aforementioned polycarbonate prepreg of the present invention. Specifically, the laminate of the present invention is obtained by laminating a plurality of the polycarbonate prepregs of the present invention or a polycarbonate prepreg and a film. The laminate of the present invention is produced, for example, by laminating a film of the polycarbonate prepreg of the present invention and a thermoplastic resin, and heating or further pressing.

Further, the molded article of the present invention has the above-described laminate of the present invention in the form of a column. The molded article of the present invention can be produced by a process of laminating a polycarbonate prepreg of the present invention and a film or sheet such as a film or sheet of a thermoplastic resin and pressing in a heated state. As the thermoplastic resin, for example, polycarbonate such as aromatic polycarbonate is used. The molded article of the present invention can be produced, for example, by alternately laminating a polycarbonate prepreg and a thermoplastic resin film and pressing the sheet for a few seconds to 180 seconds while heating the sheet to a temperature of 150 ° C or more and 250 ° C or less .

Example

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily changed without departing from the gist of the present invention.

&Lt; Measurement of flow value of resin composition &gt;

The flow value (Q value) of the pellets of the resin composition was evaluated by the method described in Annex C of JIS K7210. The flow value (Q value) was measured using a flow tester CFD500D manufactured by Shimadzu Corporation. Specifically, the hole diameter of 1.0mm, using a die test temperature of 240 ℃ of length 10mm, test force 160kg / cm ^2, the amount of the molten resin discharged from the condition of the warm-up time 420sec flow value (× 0.01cc / sec) of And used for measurement.

&Lt; Evaluation of fiber impregnability &

The impregnation property of the aromatic polycarbonate into the fiber was evaluated by microscopic observation (× 50) of the fractured surface in the thickness direction of the fiber resin sheet having a width of 20 mm of the prepreg. Those having almost no air bubbles between the resin and the fiber and excellent in adhesion were good, those having a small amount of air bubbles between the resin and the fibers and excellent in adhesion were found to have poor air bubbles and poor adhesion.

&Lt; Evaluation of flame retardancy &

The evaluation of the flame retardancy of the resin prepreg was carried out using a UL-94 / VTM test evaluation device for a prepreg having a width of 40 mm, a length of 150 mm, and a thickness of 100 to 370 μm, which was prepared by the method described later. A mark was placed at a distance of 100 mm from the contact portion of the test piece. The position of the flushing position and the size of the flame were determined in accordance with the UL-94 / VTM test. The flushing was carried out two times for 3 seconds, and the sum of the combustion continuation times after each flame was measured. The case where the sum of the combustion times is less than 5 seconds and the combustion is not reached to the mark line is good and the sum of the combustion times is 5 to 7 seconds and the combustion does not reach the curve, , Or when the resin has fallen off during the combustion, or when the combustion has reached the line, it is judged to be defective.

&Lt; Evaluation of heat resistance &

As an evaluation of the heat resistance of the resin prepreg, the glass transition temperature of the resin composition constituting the resin prepreg was measured. The glass transition temperature was measured by sampling about 10 mg of the resin on the surface of the prepreg using a differential scanning calorimeter ("DSC220" manufactured by S-Ai Nanotechnology Co., Ltd.). In DSC (measurement of differential scanning calorimetry), first, the sample was heated from room temperature to 280 deg. C at a temperature raising rate of 20 deg. C / min, and then heated at 280 deg. C for 3 minutes to sufficiently melt the resin component. And then cooled to 0 占 폚 at a cooling rate of 30 占 폚 / min. Thereafter, the glass transition point was calculated using a curve measured by heating again at a heating rate of 20 캜 / min. The glass transition point was measured in accordance with JIS-K7121 (1987). In the measurement of the glass transition point, in the point where the gradient of the curve on the straight line extending toward the high temperature side on the low-temperature side and the curve on the step-change portion of the glass transition becomes the maximum, Temperature.

&Lt; Measurement of Fiber Volume Containing Value (Vf Value) &gt;

First, the density of the test piece for bending test was calculated by the method according to JIS K7112 as the value of the fiber volume of the polycarbonate resin-made fiber prepreg. Subsequently, in accordance with JIS K7075, the thermoplastic resin was burned by using a burner to calculate the content of fiber mass. Finally, the Vf value of the test piece was calculated from the obtained density and the content of the fiber mass and the density of the carbon fiber. More specifically, the Vf value was calculated based on the following formula (I).

Vf (%) = Wf x? C /? F (I) Vf: content value of fiber volume (%)

Wf: Fiber mass content (%)

ρc: Density (g / cm ³ ) of the entire test piece (prepreg)

ρf: densities of the fiber (g / cm ³⁾

[Materials used]

&Lt; Aromatic polycarbonate resin (A) &gt;

(a-1) "YuPiron (registered trademark) S-3000F" manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight of 23,000

(a-2) "Eupiron (registered trademark) E-2000F" manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight of 28,000

<Phosphorus flame retardant (B)>

(b-1) Resorcinolbis-2,6-xylenylphosphate ("PX-200" manufactured by Daihachi Chemical Industry Co., Ltd.)

(b-2) Phenoxyphosphazene ("Rabitol FP-110" manufactured by Fushimi Pharmaceutical Co., Ltd.)

&Lt; Continuous fiber reinforcement (C) &gt;

(c-1) Glass fiber: Nitto Spun Yarn RS240QR-483AS (2400 tex)

(c-2) Carbon fiber: PAN-based carbon fiber Pirofil TRH50 60M RJ (60k) manufactured by Mitsubishi Rayon Co.,

(c-3) Glass fiber cloth: 258 (thickness 0.093 mm, 106.5 g / m ² , twilled) manufactured by Asahi Glass Co.,

(c-4) Carbon fiber cloth: CFP3110 (30k, 160 g / m ² , plain weave) manufactured by ARISAWA Co.,

[Examples 1 to 16, Comparative Examples 1 to 4]

&Lt; Production of resin composition pellets &gt;

The aromatic polycarbonate resin composition was produced by a kneading method using the following melt extruder. First, components (A) and (B) were weighed according to the mixing ratio shown in Table 1 and mixed in a tumbler for 15 minutes or more. And the mixture was melt-kneaded by a melt extruder to obtain pellets of the resin composition. That is, in the present embodiment and the comparative example, the screw rotation speed is 200 rpm, the discharge amount is 20 kg / h, the cylinder temperature is 270 DEG C using a twin screw extruder TEX30 alpha (C18 block, L / D = 63) manufactured by Nippon Steel Mill Co., , The resin and the like were kneaded, and the molten resin extruded into a strand shape was rapidly cooled in a water bath and pelletized using a pelletizer.

&Lt; Production of Resin Film &

Using the resin composition pellets described above, a film for fiber impregnation was produced. The film of the resin composition shown in Table 1 was produced using a film extruder having a screw diameter of 26 mm. The glass transition temperature (Tg) of the resin composition (Tg) -20 占 폚, the temperature of the first cooling roll (R2), the temperature of the barrel temperature 250 占 폚, (R3) was set at a glass transition temperature (Tg) of the resin composition of -30 占 폚 to obtain a film having a thickness of 100 to 150 占 퐉.

<Preparation of continuous fiber-reinforced polycarbonate prepreg>

A cloth made of cloth, and a reinforcing fiber layer which was previously pulled and aligned and pulled and aligned, were set on the upper and lower surfaces in the order of the above-mentioned resin film and releasing paper. Then, the laminate such as the reinforcing fiber layer and the resin film was heated for 3 minutes under the setting conditions of the following heating press apparatus, that is, at a heating temperature of 240 DEG C and 1 MPa for 3 minutes, By cooling, a prepreg of 130 to 250 mu m was obtained.

&Lt; Preparation of flame retardancy evaluation sheet &

The fiber prepreg having a thickness of 130 to 250 mu m was cut into a width of 40 mm, a length of 150 mm and a thickness of 130 to 250 mu m to obtain a test piece for a combustion test.

The compositions of the prepregs of the above Examples and Comparative Examples, the properties of prepregs and test pieces are summarized in the following table.

As shown in Table 1, the polycarbonate resin composition of the Example contains 60 to 88 mass% of the polycarbonate resin (A) and 12 to 40 mass% of the phosphorus flame retardant (B), and the flow rate at 240 캜 9 to 120 x 0.01 cc / sec. All of the polycarbonate resin compositions of these Examples were confirmed to be excellent in impregnation with fibers at the time of preparing prepregs. Further, the prepregs of the examples prepared using the above polycarbonate resin composition were all excellent in flame retardancy and heat resistance.

On the other hand, as shown in Table 2, in Comparative Example 1 in which the content of the phosphorus-based flame retardant (B) in the polycarbonate resin composition is low and the value of the flow value is 7 x 0.01 cc / sec, which is lower than the lower limit value of the range of the above- , The impregnation property with the fiber, and the flame retardancy of the prepreg were inferior. Further, it was confirmed that the heat resistance of the prepreg was poor in Comparative Example 2, which was impossible to measure because the phosphorus-based flame retardant (B) in the polycarbonate resin composition was excessive and the flow value was higher than the upper limit of the range of the above example.

On the other hand, in the prepregs of Examples 1 to 14, the volume containing value (Vf value) of the continuous fiber reinforcing material (C) was adjusted within the range of 25 to 60% In the prepreg of Example 15, which was lower than the lower limit of the range, the resin was slackened from the test piece and the flame retardancy was slightly lower. In the prepreg of Example 16 in which the volume inclusion value (Vf value) was higher than the upper limit value of the above range, the impregnation properties of the resin composition to the fibers were slightly inferior to those of the other examples. However, also in these examples, a prepreg which can be used without any problem was obtained.

From the above, according to the polycarbonate resin composition containing the polycarbonate resin (A) and the phosphorus-based flame retardant (B) in a predetermined range and having the flow values adjusted as described above, the impregnation property and the flame retardancy It is possible to realize a polycarbonate prepreg having excellent flame retardancy and heat resistance. Further, it was confirmed that the impregnating property and flame retardancy can be further improved by adjusting the volume inclusion value (Vf value) in the prepreg to within a predetermined range.

Claims (8)

A polycarbonate resin composition containing 60 to 88 mass% of a polycarbonate resin (A) and 12 to 40 mass% of a phosphorus flame retardant (B), wherein the flow rate of the polycarbonate resin composition at 240 캜 is 9 to 120 0.0 &gt; cc / sec. &Lt; / RTI &gt; The method according to claim 1,
Wherein the phosphorus flame retardant (B) comprises at least one of a condensed phosphoric acid ester and a phosphazene flame retardant. 3. The method of claim 2,
Wherein the condensed phosphoric acid ester comprises at least one of triphenyl phosphate, bisphenol A tetraphenyl phosphate, resorcinol tetraphenyl phosphate, and resorcinol tetra-2,6-xylene oxide,
Wherein the phosphazene-based flame retardant comprises at least one of phenoxyphosphazene, (poly) tolyloxyphosphazene, and (poly) phenoxytoluyloxyphosphazene. A polycarbonate resin film obtained by molding the polycarbonate resin composition according to any one of claims 1 to 3. A polycarbonate prepreg obtained by impregnating a continuous fiber reinforcing material (C) with the polycarbonate resin composition according to any one of claims 1 to 3, wherein the continuous fiber reinforcing material (C) has a volume content value (Vf value) Polycarbonate prepreg containing 60%. A polycarbonate prepreg obtained by laminating the polycarbonate resin film according to claim 4 on a continuous fiber reinforcement (C), wherein the continuous fiber reinforcement (C) is a polycarbonate prepreg containing 25 to 60% Legs. A laminate containing the polycarbonate prepreg according to claim 5 or 6. A formed article in which the laminate according to claim 7 is formed into a column shape.