WO2016186100A1

WO2016186100A1 - Polycarbonate resin composition, and prepreg made from polycarbonate resin

Info

Publication number: WO2016186100A1
Application number: PCT/JP2016/064563
Authority: WO
Inventors: 黒川　晴彦; 翔平高萩
Original assignee: 三菱瓦斯化学株式会社; Ｍｇｃフィルシート株式会社
Priority date: 2015-05-18
Filing date: 2016-05-17
Publication date: 2016-11-24
Also published as: JP6716551B2; CN107614611A; CN107614611B; TW201706361A; JPWO2016186100A1; KR20180008602A

Abstract

Provided are a polycarbonate resin composition having excellent flame retardancy and ability to impregnate continuous fiber reinforcement materials, and a polycarbonate prepreg and the like having excellent flame retardancy. The above problem is solved by a polycarbonate resin composition containing 60-88 mass% of a polycarbonate resin (A) and 12-40 mass% of a phosphorous-based flame retardant (B) wherein the polycarbonate resin composition has a flow value at 240°C of 9 to 120×0.01cc/sec.

Description

Polycarbonate resin composition and 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, a polycarbonate prepreg obtained by impregnating a continuous fiber reinforcement with a polycarbonate resin composition, and the like.

2. Description of the Related Art A continuous fiber reinforced composite material (hereinafter sometimes referred to as “FRTP”) in which a thermoplastic resin is used as a matrix and is combined with a continuous fiber reinforcement is already widely known. Such FRTP is usually used for manufacturing a prepreg in which a reinforcing fiber in the form of a single strand, a unidirectional sheet (UD sheet), a woven fabric, or a non-woven fabric is impregnated with a resin, and the prepreg is formed by press molding or filament winding molding ( Products such as structural members and various parts are manufactured by FW molding.

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

In the manufacture of prepregs using FRTP, the impregnation property of the matrix resin into the continuous fibers is important and greatly affects the mechanical properties such as strength and the appearance. As a method for producing an FRTP prepreg, a solution method, a hot melt method, a slurry method, a fluidized bed method, and the like are generally known. Among them, a hot press method in which a resin component is melted and impregnated into continuous fibers is simple, but polycarbonate with low resin melt flowability has poor impregnation properties with continuous fibers, and a good product cannot be obtained.

Patent Document 1 relates to a chopped strand prepreg using a thermoplastic resin in which the melt viscosity of the thermoplastic resin is in the range of 1,000 to 15,000 poise, but uses a FRTP plate cut into strips. Therefore, there is a problem that sufficient rigidity cannot be obtained when molding a large molded product. Furthermore, Patent Document 1 does not suggest that the prepreg has flame retardancy.

Patent Document 2 describes a composite material composed of a thermoplastic resin and carbon fibers. However, since the thermoplastic resin used has a high viscosity and poor impregnation with carbon fibers, the pellets were freeze-ground. It is described that it is preferable to spray a powdery resin. Since the resin in powder form has a low bulk density and contains air, removal of bubbles in the composite material becomes insufficient, resulting in a problem of poor appearance and strength. Further, in Patent Document 2, although it is described that a flame retardant may be included in the composite material, there is no specific disclosure regarding the flame retardant of the flame retardant and the composite material.

Patent Document 3 describes a prepreg made of a carbon continuous fiber reinforced polycarbonate resin in which carbon fibers using polycarbonate having a melt viscosity at 250 ° C. of 1 to 100 Pa · s are aligned in one direction. However, in the prepreg described in Patent Document 3, there is a problem that mold contamination due to low molecular components is likely to occur at the time of heat forming due to the low molecular weight of polycarbonate, and the strength when bent is insufficient. Moreover, in patent document 3, since the polycarbonate resin is low-viscosity, it is easy to hang down with a fire kind at the time of combustion, and it is unsuitable for incombustibility, and to ensure incombustibility. Neither has been suggested.

Patent No. 2507565 JP 2011-178890 A JP 2014-91825 A

An object of the present invention is 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 repeated studies to solve the above problems, the present inventors have used a mixture of a polycarbonate and a flame retardant adjusted to a specific melt viscosity as an impregnating agent for continuous fiber reinforcement, which has not existed in the past. It has been found that a polycarbonate resin composition excellent in resin impregnation and flame retardancy and a highly flame retardant polycarbonate prepreg 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% by mass of a polycarbonate resin (A) and 12 to 40% by mass of a phosphorus-based flame retardant (B), wherein the flow rate at 240 ° C. of the polycarbonate resin composition is 9 to 120. X A polycarbonate resin composition of 0.01 cc / sec.

2. 1. The phosphorus-based flame retardant (B) includes at least one of a condensed phosphate ester and a phosphazene-based flame retardant. The polycarbonate resin composition described in 1.

3. The condensed phosphate ester includes at least one of triphenyl phosphate, bisphenol A tetraphenyl phosphate, resorcinol tetraphenyl phosphate, resorcinol tetra-2,6-xylenol phosphate;
2. The phosphazene flame retardant comprising at least one of phenoxyphosphazene, (poly) tolyloxyphosphazene, and (poly) phenoxytolyloxyphosphazene. The polycarbonate resin composition described in 1.

4). Above 1. ~ 3. A polycarbonate resin film obtained by molding the polycarbonate resin composition according to any one of the above.

5. Above 1. ~ 3. A polycarbonate prepreg obtained by impregnating a continuous fiber reinforcement (C) with the polycarbonate resin composition according to any of the above, wherein the continuous fiber reinforcement (C) is contained in a volume content (Vf value) of 25 to 60%. Polycarbonate prepreg.

6). 4. above. A polycarbonate prepreg obtained by impregnating a continuous fiber reinforcement (C) with the polycarbonate resin film described in 1 above, wherein the continuous fiber reinforcement (C) is contained in a volume content (Vf value) of 25 to 60%. .

7). 5. above. Or 6. A laminate containing the polycarbonate prepreg described in 1.

8). Above 7. A molded product obtained by thermally shaping the laminate described in 1.

The polycarbonate resin composition of the present invention has high resin impregnation into fibers and excellent flame retardancy, and therefore the prepreg made of continuous fiber reinforced flame retardant polycarbonate resin of the present invention is also excellent in flame retardancy. For this reason, the prepreg made of continuous fiber reinforced flame retardant polycarbonate resin of the present invention can be suitably used as a heat-forming sheet and film for electronic and electrical equipment casing applications.

Hereinafter, the present invention will be described in detail.

[Polycarbonate resin (A)]
The type of the polycarbonate resin (A) (hereinafter sometimes referred to as “component (A)”) used in the present invention is not particularly limited, but is preferably a polycarbonate resin, and particularly preferably an aromatic polycarbonate resin. preferable. The polycarbonate resin is an optionally branched thermoplastic polymer or copolymer obtained by reacting a dihydroxy compound or a small amount thereof with phosgene or a carbonic acid diester. The production method of the polycarbonate resin is not particularly limited, and a polycarbonate resin produced by a conventionally known phosgene method (interfacial polymerization method) or a melting method (transesterification method) can be used. Further, when the melting method is used, a polycarbonate resin in which the amount of OH groups of terminal groups is adjusted can be used.

Examples of the raw material dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4,4 -Dihydroxydiphenyl etc. are mentioned, Preferably bisphenol A is mentioned. In addition, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound can also be used.

In order to obtain a branched polycarbonate resin, a part of the above-mentioned dihydroxy compound is mixed with the following branching agents: phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene, 2, 4-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -3-heptene, 1,3,5-tri Polyhydroxy compounds such as (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5 -It may be substituted with a compound such as chlorisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. The amount of the compound to be substituted is usually 0.01 to 10 mol%, preferably 0.1 to 2 mol%, based on the dihydroxy compound.

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

The above-described polycarbonate resins may be used alone or in combination of two or more.

In order to adjust the molecular weight of the polycarbonate resin (A), a monovalent hydroxy compound such as an aromatic hydroxy compound may be used. Examples of the monovalent aromatic hydroxy compound include m- and p-methylphenol, m- and p-propylphenol, p-tert-butylphenol, p-long chain alkyl-substituted phenol and the like.

The molecular weight of the polycarbonate resin (A) used in the present invention is arbitrary depending on the use and may be appropriately selected and determined. From the viewpoint of moldability, strength of the molded product, etc., the polycarbonate resin (A), preferably aromatic The molecular weight of the polycarbonate resin (A) is preferably 15,000 to 40,000, particularly 15,000 to 30,000, in terms of 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 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, a decrease in fluidity tends to be suppressed and improved, and from the viewpoint of ease of molding processability and flame retardancy. preferable. The viscosity average molecular weight [Mv] here is the viscosity average molecular weight [Mv] converted from the solution viscosity, using methylene chloride as a solvent, and using an Ubbelohde viscometer, the intrinsic viscosity [η] (unit dl / g) is calculated and means a value (viscosity average molecular weight: Mv) calculated from Schnell's viscosity formula, that is, η = 1.23 × 10 ⁻⁴ Mv ^0.83 . Here, the intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

[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 at the time of hot-melting into fibers, which will be described in detail later, and to improve the flame retardancy.

As the phosphorus-based flame retardant (B), a phosphate ester-based flame retardant, a phosphazene-based flame retardant, or the like can be used.
As the phosphorus-based flame retardant (B), one type may be used alone, or two or more types may be mixed and used. As the phosphorus-based flame retardant (B), a phosphate ester-based flame retardant is preferably used because of its high flame retarding effect, fluidity improving effect, and resistance to mold corrosion.

<Phosphate ester flame retardant>
The phosphate ester flame retardant used as the phosphorus flame retardant (B) is not particularly limited, but the phosphate ester flame retardant is preferably a phosphate ester compound represented by the following general formula (II). .

(In the formula (II), R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group) P, q, 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 general formula (II), examples of the aryl group represented by R ¹ to R ⁴ include a phenyl group and a naphthyl group. Examples of the arylene group for X include a phenylene group and a naphthylene group. When t is 0, the compound represented by formula (II) is a phosphate ester, and when t is greater than 0, it is a condensed phosphate ester (including a mixture). In the present invention, a condensed phosphate ester is particularly preferably used.

Specific examples of the phosphate ester flame retardant represented by the general formula (II) include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate. Fate, tricresyl phosphate, tricresyl phenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichlorophosphate, bis (chloropropyl) monooctylphosphate, bis Enol A tetraphenyl phosphate, bisphenol A tetracresyl diphosphate, bisphenol A tetraxylyl diphosphate, hydroquinone tetraphenyl diphosphate, hydroquinone tetracresyl phosphate, hydroquinone tetraxyl diphosphate, resorcinol tetraphenyl phosphate, Examples thereof include resorcinol tetra-2,6-xylenol phosphate, resorcinol bisdixylenyl phosphate and the like. Of these, triphenyl phosphate, bisphenol A tetraphenyl phosphate, resorcinol tetraphenyl phosphate, resorcinol tetra-2,6-xylenol phosphate and the like are preferable.

<Phosphazene flame retardant>
The phosphazene flame retardant is used as the most effective phosphorus flame retardant in the present invention because it has a lower heat resistance than the condensed phosphate 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 general formula (IIIa) or a general formula (IIIb) below. Examples thereof include a chain phosphazene compound represented by the formula and a crosslinked phosphazene compound formed by crosslinking with a crosslinking group. In particular, it is preferable to use a crosslinked product of at least one phosphazene compound selected from the group consisting of the following general formula (IIIa) and the following general formula (IIIb). Moreover, as a crosslinking group which forms a bridge | crosslinking phosphazene compound, the crosslinking group represented by the following general formula (IIIc) is preferable from the flame retardance point of the bridge | crosslinking phosphazene compound obtained.

(In 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.)

(In the formula (IIIb), n is an integer of 3 to 10,000, Z represents a —N═P (OR ⁵ ) ₃ group or a —N═P (O) OR ⁵ group, and Y represents a — _{4 represents} P (OR ⁵ ) ₄ group or —P (O) (OR ⁵ ) ₂ group, 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 general formula (IIIa), cyclic phenoxyphosphazene in which R ⁵ is a phenyl group is particularly preferable. Examples of such cyclic phenoxyphosphazene compounds include hexachlorocyclotriphosphazene, octachlorochloromethane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Cyclic chlorophosphazenes such as cyclotetraphosphazene, decachlorocyclopentaphosphazene, etc. are taken out, and then obtained by substituting the chloro group (chlorine) with a phenoxy group. And compounds such as phosphazene. The cyclic phenoxyphosphazene compound is preferably a compound in which m in the general formula (IIIa) 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 to 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 general formula (IIIa) include phenoxyphosphazene, (poly) tolyloxyphosphazene (for example, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene, cyclic C _1-6 such as o, m-tolyloxyphosphazene, o, p-tolyloxyphosphazene, m, p-tolyloxyphosphazene, o, m, p-tolyloxyphosphazene, and (poly) xylyloxyphosphazene and alkyl C _6-20 aryloxy phosphazene, (poly) phenoxy tolyloxy phosphazene (e.g., phenoxy o- tolyloxy phosphazene, a phenoxy m- tolyloxyethyl phosphazene, a phenoxy p- tolyloxy phosphazene, a phenoxy o, -Tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o, m, p-tolyloxyphosphazene, etc.), (poly) phenoxysilyloxyphosphazene, (poly) phenoxytolyl Examples thereof include cyclic C _6-20 aryl C _1-10 alkyl C _6-20 aryloxy phosphazenes such as _oxyxyloxy phosphazene, preferably cyclic phenoxy phosphazenes, cyclic C _1-3 alkyl C _6-20 aryloxy phosphazenes, C _6-20 aryloxy C _1-3 _{alkylC 6-20} aryloxyphosphazene (for example, cyclic tolyloxyphosphazene, cyclic phenoxytolylphenoxyphosphazene, etc.).
Note that 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. The description of “(poly) phenoxy...” Indicates one or both of “phenoxy...” And “polyphenoxy.

As the chain phosphazene compound represented by the general formula (IIIb), chain phenoxyphosphazene in which R ⁵ is a phenyl group is particularly preferable. As such a chain phenoxyphosphazene compound, for example, hexachlorocyclotriphosphazene obtained by the above-described method is subjected to reversion polymerization at a temperature of 220 to 250 ° C., and the resulting linear chain having a polymerization degree of 3 to 10,000 is obtained. Examples include compounds obtained by substituting the chloro group (chlorine) of dichlorophosphazene with a phenoxy group. N in the general formula (IIIb) of the linear phenoxyphosphazene compound is preferably 3 to 1,000, more preferably 3 to 100, and further preferably 3 to 25.
Specific examples of the chain phenoxyphosphazene compound represented by the general formula (IIIb) include phenoxyphosphazene, (poly) tolyloxyphosphazene (for example, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene). , o, m-tolyl oxy phosphazene, o, p-tolyloxy phosphazene, m, p-tolyloxy phosphazene, o, m, p-tolyloxy phosphazene, etc.), (poly) key chain _{C 1} such silyloxy phosphazene _-6 and alkyl C _6-20 aryloxy phosphazene, (poly) phenoxy tolyloxy phosphazene (e.g., phenoxy o- tolyloxy phosphazene, a phenoxy m- tolyloxyethyl phosphazene, a phenoxy p- tolyloxy phosphazene, a phenoxy o, -Tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o, m, p-tolyloxyphosphazene, etc.), (poly) phenoxysilyloxyphosphazene, (poly) phenoxytolyl Examples thereof include chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxy phosphazene such as _oxyxyloxy phosphazene, preferably chain phenoxy phosphazene, chain C _1-3 alkyl C _6-20 aryl, etc. Oxyphosphazenes, C _6-20 aryloxy C _1-3 alkyl C _6-20 aryloxyphosphazenes (eg, chained tolyloxyphosphazenes, chained phenoxytolylphenoxyphosphazenes, etc.).

Moreover, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound in which R ⁵ is a phenyl group in the general formula (IIIa) with a crosslinking group represented by the general formula (IIIc), or A crosslinked phenoxyphosphazene compound obtained by crosslinking the chain phenoxyphosphazene compound in which R ⁵ is a phenyl group in the general formula (IIIb) with a crosslinking group represented by the general formula (IIIc) is preferable from the viewpoint of flame retardancy, A crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound with a crosslinking group represented by the general formula (IIIc) is more preferable.

Examples of the bridged phenoxyphosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue) and a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. Compounds having a 4,4′-oxydiphenylene group crosslinked structure, compounds having a 4,4′-thiodiphenylene group crosslinked structure, etc., compounds having a 4,4′-diphenylene group crosslinked structure, etc. Is mentioned.

The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (IIIa) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (IIIb) and Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

In the present invention, the phenoxyphosphazene compound is a crosslinked product obtained by crosslinking the cyclic phenoxyphosphazene compound represented by the general formula (IIIa) and the cyclic phenoxyphosphazene compound represented by the general formula (IIIa) with a crosslinking group. From the viewpoint of flame retardancy and mechanical properties, at least one selected from the group consisting of cyclic phenoxyphosphazene compounds of the type is preferred. Examples of the commercially available cyclic phosphazene-based flame retardant include “Ravitor FP110” manufactured by Fushimi Pharmaceutical Co., Ltd., which is phenoxyphosphazene, and “SPS100” manufactured by Otsuka Chemical Co., Ltd.

[Polycarbonate resin composition]
The polycarbonate resin composition of the present invention contains 60 to 88% by mass of the polycarbonate resin (A) and 12 to 40% by mass of the phosphorus flame retardant (B).
The content of the polycarbonate resin (A) is preferably 70 to 85% by mass, and more preferably 75 to 85% by mass.
The content of the phosphorus-based flame retardant (B) in the polycarbonate resin composition is preferably 9 to 120 × 0.01 (cc / sec), the flow value (240 ° C., 160 kg / cm ² ) of the polycarbonate resin composition. Must be controlled to be 10 to 60 × 0.01 (cc / sec). The specific amount of the phosphorus-based flame retardant (B) added is preferably 12 to 40% by mass, more preferably 15 to 30% by mass from the viewpoint of flame retardancy and heat resistance. When the addition amount of the phosphorus-based flame retardant (B) is 12% by mass or more, the flame retardant effect and the fiber impregnation property are good, and desired physical properties of the composition can be obtained. Moreover, when the addition amount of a phosphorus flame retardant (B) is 40 mass% or less, the heat resistance and the fall of the toughness of a matrix resin can be suppressed.

In the polycarbonate resin composition, as described above, the flow value at 240 ° C. is 9 to 120 × 0.01 cc / sec (160 kg / cm ² ). Thus, by adjusting the flow value of the polycarbonate resin composition, the impregnation property of the resin composition with respect to fibers, the heat resistance of the resin composition, and the flame retardance of the prepreg produced using the resin composition will be described in detail later. All the effects are good, and an excellent balance of these physical properties can be realized.

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

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

Also, examples of the anti-dripping agent include fluorinated polyolefins such as polyfluoroethylene, and preferably polytetrafluoroethylene having fibril forming ability. This shows the tendency to disperse | distribute easily in a polymer and to make a fibrous material by couple | bonding polymers. Polytetrafluoroethylene having fibril-forming ability is classified as type 3 according to the ASTM standard. As polytetrafluoroethylene, in addition to a solid form, those in the form of an aqueous dispersion can also be used. Examples of polytetrafluoroethylene having fibril-forming ability include, for example, Mitsui DuPont Fluorochemical Co., Ltd., Teflon (registered trademark) 6J or Teflon (registered trademark) 30J, or Daikin Industries, Ltd. Is commercially available.

When the aromatic polycarbonate resin composition of the present invention contains an anti-drip agent, the content of the anti-drip agent is that of the aromatic polycarbonate resin (A), the phosphorus flame retardant (B), or the continuous fiber reinforcement (C). The amount is preferably 0.02 to 4 parts by mass, more preferably 0.03 to 3 parts by mass with respect to 100 parts by mass in total. If the blending amount of the dripping inhibitor exceeds the above upper limit, the appearance of the molded product may be deteriorated.

Other resin components The aromatic polycarbonate resin composition of the present invention may contain other resin components other than the aromatic polycarbonate resin (A) as a resin component, as 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, polyacryl styrene resin, ABS resin, AS resin, AES resin, ASA resin, SMA resin, polyalkyl methacrylate resin, Polymethacryl methacrylate resin, polyphenyl ether resin, polycarbonate resin other than component (A), amorphous polyalkylene terephthalate resin, polyester resin, amorphous polyamide resin, poly-4-methylpentene-1, cyclic polyolefin resin, non Crystalline polyarylate resin, polyether sulfone, etc. are mentioned.

[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 (C) (hereinafter referred to as “component (C)”) in order to enhance bending properties such as bending elastic modulus and bending strength of the molded product. .) Is impregnated in a polycarbonate resin composition containing the components (A) and (B).

Examples of the continuous fiber reinforcing material (C) used in the present invention include glass fiber and carbon fiber. And since it is excellent in the reinforcement effect of a polycarbonate resin composition, as a form of a continuous fiber reinforcement (C), the fiber woven fabrics, such as cloth, or the fiber which opened the fiber bundle and was arranged in one direction is preferable. . The volume content value (Vf value) of the continuous fiber reinforcement is used as an index of the fiber content in the prepreg.

<Glass fiber>
There is no restriction | limiting in particular in the glass composition of the glass fiber used by this invention, What consists of glass compositions, such as A glass, C glass, E glass, etc. can be used, Especially, the alkali free glass of the following component compositions E glass is preferable because it does not adversely affect the aromatic polycarbonate resin (A).

(E glass composition: mass%)
SiO ₂ : 52 to 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 to 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 to be described later, and by such surface treatment, the adhesiveness between the resin component and the glass is improved, and high mechanical strength can be achieved. It becomes like this.

Especially in this invention, in order to improve the adhesiveness of a continuous fiber reinforcement (C) and a resin component, and aromatic polycarbonate resin (A) by contact with glass fiber and aromatic polycarbonate resin (A). In order to suppress decomposition, it is preferable to use a continuous fiber reinforcing material (C) whose surface is treated with a surface treatment agent. Examples of suitable surface treatment agents include silane coupling agents such as aminosilane and epoxysilane, and silicone compounds.

[Other ingredients]
The continuous fiber reinforced polycarbonate resin composition of the present invention contains other components as necessary in addition to the aromatic polycarbonate resin (A), the phosphorus-based flame retardant (B), and the continuous fiber reinforcing material (C). You may do it. Examples of other components that can be contained in the aromatic polycarbonate resin composition of the present invention include the following.

<Other additives>
The aromatic polycarbonate resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Such additives include stabilizers, antioxidants, mold release agents, UV absorbers, dyes and pigments, antistatic agents, flame retardants, anti-dripping agents, impact strength improvers, plasticizers, dispersants, antibacterial agents , (A), (B) and other resins other than the component (C). One of these resin additives may be contained, or two or more thereof may be contained in any combination and ratio.

[Other inorganic components]
When the continuous fiber reinforced prepreg made of the aromatic polycarbonate resin of the present invention is prepared, by adding glass short fibers, carbon short fibers and the like having a fiber length of 10 mm or less as inorganic components other than the continuous fiber reinforcing material (C) component, Mechanical properties can be improved. Examples of the short fiber filler include short glass fibers, short carbon fibers, wollastonite, various inorganic whiskers and the like.
Moreover, the anisotropy at the time of shrinkage can also be improved by adding a plate-like or spherical filler. Examples of the plate-like filler include glass flakes, mica and talc, and examples of the spherical filler include glass beads and silica beads.

<Method for producing prepreg made of continuous fiber reinforced polycarbonate resin>
The method for producing a prepreg made of continuous fiber reinforced polycarbonate resin is a method in which a molten resin is poured from a T-die of an extruder and joined with a drawn fiber sheet or opened unidirectionally aligned fibers, and impregnated with a powder resin. There are a method of dispersing on a fiber and heating and melting, a heat laminating method in which a resin is formed into a film and laminated on a fiber layer and then heated. Since the polycarbonate used in the prepreg made of continuous fiber reinforced polycarbonate resin of the present invention is excellent in fluidity, a method of discharging and impregnating a molten resin from an extruder, and a method of thermally laminating a resin into a film are particularly preferably used.

In the step of impregnating fibers with a specific polycarbonate by the melting method, in addition to the method using the extruder, a method of solidifying the prepreg after melting and penetration by a combination of a heating press and a cooling press, a double belt press is used. A method of providing a heating zone or a cooling zone may be included.

<Prepreg shape, form and features>
The thickness of the fiber-reinforced polycarbonate resin prepreg of the present invention is usually 50 to 500 μm, preferably 150 to 350 μm per sheet. For example, it is 170 to 305 μm. If the thickness of one prepreg is less than 50 μm, the resin component cannot be sufficiently impregnated, so that the obtained prepreg is opened and difficult to handle. Further, if the thickness of one prepreg exceeds 500 μm, sufficient physical properties cannot be obtained because the content of reinforcing fibers decreases.
Moreover, the prepreg of the present invention produced by the above-described manufacturing method, that is, the prepreg impregnated with the polycarbonate resin composition of the present invention in the continuous fiber reinforcement (C), or the polycarbonate resin film as the continuous fiber reinforcement (C). In the laminated prepreg, the volume content value (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 reinforcing reinforcement becomes a sufficient level, and by setting the Vf value to 60% or less, it is possible to easily impregnate the resin with the reinforcing material and realize a prepreg excellent in appearance and strength. .

<Laminated body and molded body>
The laminate of the present invention contains the above-described 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 the polycarbonate prepreg of the present invention and a thermoplastic resin film and heating or further pressing.

Moreover, the molded object of this invention heat-forms the above-mentioned laminated body of this invention. The molded article of the present invention can be produced by a process of laminating the polycarbonate prepreg of the present invention and a film or sheet, for example, a thermoplastic resin film or sheet, and pressing in a heated state. As the thermoplastic resin, for example, polycarbonate such as aromatic polycarbonate is used. The molded body of the present invention is obtained by, for example, laminating polycarbonate prepregs and thermoplastic resin films alternately, and pressing for about several seconds to 180 seconds in a state where the temperature is 150 ° C. or higher and 250 ° C. or lower. Can be manufactured.

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

<Measurement of flow value of resin composition>
The flow value (Q value) of the pellets of the resin composition was evaluated by the method described in JIS K7210 Appendix C. For the measurement of the flow value (Q value), a flow tester CFD500D manufactured by Shimadzu Corporation was used. Specifically, using a die having a hole diameter of 1.0 mm and a length of 10 mm, the amount of molten resin discharged under the conditions of a test temperature of 240 ° C., a test force of 160 kg / cm ² , and a preheating time of 420 seconds is a flow value (× 0. 01 cc / sec).

<Fiber impregnation evaluation>
Evaluation of the impregnation property to the fiber of the aromatic polycarbonate was evaluated by observing the fracture surface in the thickness direction of the fiber resin sheet having a width of 20 mm of the prepreg with a microscope (× 50 times). Good if there is almost no air bubbles between the resin and the fiber and has good adhesion, good if there are few air bubbles between the resin and the fiber, and good adhesion, acceptable if there are many air bubbles and low adhesion did.

<Flame retardance evaluation>
The flame retardant evaluation of the resin prepreg was performed using a UL-94 / VTM test evaluation apparatus for a prepreg having a width of 40 mm, a length of 150 mm, and a thickness of 100 to 370 μm produced by the method described below. A marked line was placed in a portion 100 mm away from the flame contact portion of the test piece. The flame contact position and the flame size were determined in accordance with the UL-94 / VTM test. The flame contact was set to 2 degrees for 3 seconds, and the total combustion duration after each flame-off was measured. Good when the total combustion time is less than 5 seconds and the combustion does not reach the marked line, or when the total combustion time is 5 to 7 seconds and the combustion does not reach the marked line, the combustion time is 7 More than a second, or when the resin dropped during combustion, or when the combustion reached the marked line was judged as defective.

<Heat resistance evaluation>
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 resin on the surface of the prepreg using a differential scanning calorimeter (“DSC220” manufactured by SII Nano Technology). In DSC (measurement of differential scanning calorific value), the resin component was first melted sufficiently by heating from room temperature to 280 ° C. at a rate of temperature increase of 20 ° C./min, and maintaining the temperature for 3 minutes after reaching 280 ° C. Next, it was cooled to 0 ° C. at a cooling rate of 30 ° C./min. Thereafter, the glass transition point was calculated using a curve measured by heating again at a heating rate of 20 ° C./min. The glass transition point was measured according to JIS-K7121 (1987). In the measurement of the glass transition point, the temperature at the intersection of the straight line obtained by extending the base line on the low temperature side to the high temperature side and the tangent line drawn at the point where the slope of the curve at the stepwise change part of the glass transition is maximized. A certain extrapolated glass transition start temperature was set.

<Measurement of fiber volume content (Vf value)>
As the fiber volume content value of the polycarbonate resin fiber prepreg, first, the density of the test piece for the bending test was calculated by a method according to JIS K7112. Subsequently, in accordance with JIS K7075, the thermoplastic resin was burned off using a burner, and the fiber mass content was calculated. Finally, the Vf value of the test piece was calculated from the obtained density and fiber mass content and the density of the carbon fiber. Specifically, the Vf value was calculated based on the following formula (I).

Vf (%) = Wf × ρc / ρf (I) Vf: Fiber volume content value (%)
Wf: Fiber mass content (%)
ρc: density of the entire test piece (prepreg) (g / cm ³ )

ρf: Fiber density (g / cm ³ )

[Materials used]
<Aromatic polycarbonate resin (A)>
(A-1) “Iupilon (registered trademark) S-3000F” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 23,000
(A-2) “Iupilon (registered trademark) E-2000F” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 28,000
<Phosphorus flame retardant (B)>
(B-1) Resorcinol bis-2,6-xylenyl phosphate (“PX-200” manufactured by Daihachi Chemical Industry)
(B-2) Phenoxyphosphazene ("Ravitor FP-110" manufactured by Fushimi Pharmaceutical)
<Continuous fiber reinforcement (C)>
(C-1) Glass fiber: manufactured by Nitto Boseki Co., Ltd. RS 240QR-483AS (2400 tex)
(C-2) Carbon fiber: PAN-based carbon fiber Pyrofil TRH50 60M RJ (60k) manufactured by Mitsubishi Rayon Co., Ltd.
(C-3) Glass fiber cloth: 258 manufactured by Asahi Glass Co., Ltd. (thickness 0.093 mm, 106.5 g / m ² , twill)
(C-4) Carbon fiber cloth: CFP3110 (30 k, 160 g / m ² , plain weave) manufactured by Arisawa Manufacturing Co., Ltd.

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

<Manufacture of resin composition pellets>
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 blending ratios shown in Table 1, and mixed with a tumbler for 15 minutes or longer. The mixture was melt kneaded with a melt extruder to obtain resin composition pellets. That is, in this example and a comparative example, using a twin screw extruder TEX30α (C18 block, L / D = 63) manufactured by Nippon Steel Works with one vent, a screw rotation speed of 200 rpm, a discharge amount of 20 kg / h, A resin or the like was kneaded under a cylinder temperature of 270 ° C., and the molten resin extruded into a strand shape was rapidly cooled in a water tank and pelletized using a pelletizer.

<Production of resin film>
A fiber-impregnated film was prepared using the above-described resin composition pellets. The film of the resin composition described in Table 1 was produced using a film extruder having a screw diameter of 26 mm. That is, the barrel temperature is 250 ° C., the die (D) temperature is 250 ° C., the pressure roll (R1) temperature is 40 ° C., the first cooling roll (R2) temperature is the glass transition temperature (Tg) −20 ° C. of the resin composition, and the second cooling is performed. The resin composition was extruded under the condition that the roll (R3) temperature was the glass transition temperature (Tg) of the resin composition-30 ° C., and a film having a thickness of 100 to 150 μm was obtained.

<Creation of continuous fiber reinforced polycarbonate prepreg>
Centering on a cloth cloth and a reinforcing fiber layer aligned in one direction opened in advance, the resin film and release paper were stacked on the upper and lower surfaces in this order and set in a heating press. Then, the laminated body such as the reinforcing fiber layer and the resin film is heated for 3 minutes at the following setting conditions of the heating press apparatus, that is, the heating temperature of 240 ° C. and 1 MPa, and then 5 to 10 with a cooling plate set to 20 ° C. A prepreg of 130 to 250 μm was obtained by cooling for a few minutes.

<Making flame retardant evaluation sheet>
The fiber prepreg having a thickness of 130 to 250 μm was cut into a width of 40 mm × length of 150 mm × thickness of 130 to 250 μm to obtain a test piece for a combustion test.

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

As shown in Table 1, the polycarbonate resin compositions of the examples contain 60 to 88% by mass of the polycarbonate resin (A) and 12 to 40% by mass of the phosphorus flame retardant (B), and have a flow value at 240 ° C. It is adjusted to 9 to 120 × 0.01 cc / sec. It was confirmed that all of the polycarbonate resin compositions of these examples were excellent in the impregnation property to the fiber during prepreg production. Furthermore, the prepregs of Examples produced using the polycarbonate resin composition had good flame retardancy and heat resistance.
On the other hand, as shown in Table 2, the content of the phosphorus-based flame retardant (B) in the polycarbonate resin composition is low, and the flow value is 7 × 0.01 cc / sec, which is within the range of the above examples. In Comparative Example 1 lower than the lower limit value, the fiber impregnation property and the prepreg flame retardance were inferior. Further, in Comparative Example 2 in which 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, measurement was not possible. It was confirmed that the heat resistance was poor.
In the prepregs of Examples 1 to 14, the volume content value (Vf value) of the continuous fiber reinforcement (C) was adjusted within the range of 25 to 60%. ) Was lower than the lower limit of the above range, the prepreg of Example 15 showed that the resin dripped from the test piece and showed slightly inferior flame retardancy. And in the prepreg of Example 16 whose volume content value (Vf value) is higher than the upper limit of the said range, the result in which the impregnation property with respect to the fiber of a resin composition was a little inferior compared with the other Example was shown. However, also in these examples, prepregs that can be used without any particular problem were 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 value adjusted as described above, the fiber reinforcement is impregnated. The polycarbonate prepreg and the like excellent in flame retardancy and heat resistance can be realized. Furthermore, it was confirmed that the impregnation property and flame retardancy can be further improved by adjusting the volume content value (Vf value) in the prepreg within a predetermined range.

Claims

A polycarbonate resin composition containing 60 to 88% by mass of a polycarbonate resin (A) and 12 to 40% by mass of a phosphorus-based flame retardant (B), wherein the flow rate at 240 ° C. of the polycarbonate resin composition is 9 to 120. X A polycarbonate resin composition of 0.01 cc / sec.
The polycarbonate resin composition according to claim 1, wherein the phosphorus flame retardant (B) contains at least one of a condensed phosphate ester and a phosphazene flame retardant.
The condensed phosphate ester includes at least one of triphenyl phosphate, bisphenol A tetraphenyl phosphate, resorcinol tetraphenyl phosphate, resorcinol tetra-2,6-xylenol phosphate;
The polycarbonate resin composition according to claim 2, wherein the phosphazene-based flame retardant includes at least one of phenoxyphosphazene, (poly) tolyloxyphosphazene, and (poly) phenoxytolyloxyphosphazene.
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 the continuous fiber reinforcement (C) with the polycarbonate resin composition according to any one of claims 1 to 3, wherein the continuous fiber reinforcement (C) has a volume content (Vf value) of 25. 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 contained in a volume content (Vf value) of 25 to 60%. Polycarbonate prepreg.
A laminate containing the polycarbonate prepreg according to claim 5 or 6.
The molded object which heat-shaped the laminated body of Claim 7.