JP2018141037A - Fiber-reinforced resin molded article - Google Patents

Abstract

SOLUTION: A fiber-reinforced resin molded article contains a polycarbonate resin composition that contains 100 pts.wt. of a main component containing 40-80 wt% polycarbonate resin (A) and 20-60 wt% glass fiber (B), as well as 0.01-0.2 pts.wt. of a phosphorous ester compound (C), 0.1-2 pts.wt. of a fatty acid ester (D), 0.5-10 pts.wt. of polyamide copolymer (E), and up to 10 pts.wt. of hydrogenated styrenic thermoplastic elastomer (F), and is a thin cabinet, housing, casing, cover, or internal chassis used in electric electronic apparatus.EFFECT: A fiber-reinforced resin molding is excellent in mold releasability, thermal stability, appearance in molded article and adhesiveness between a polycarbonate resin and a glass fiber, without impairing excellent mechanical strength or rigidity of a polycarbonate resin composition.SELECTED DRAWING: None

Description

  The present invention improves the adhesiveness between the polycarbonate resin and the glass fiber while maintaining the excellent heat resistance and thermal stability inherent to the polycarbonate resin, and has excellent mold release properties at the time of injection molding. The present invention relates to a fiber reinforced resin molded product for a specific use, which is formed by molding a polycarbonate resin composition having excellent appearance and rigidity.

  Polycarbonate resins are thermoplastic resins with excellent mechanical strength, heat resistance, thermal stability, and the like, and are therefore widely used industrially in the electrical and electronic fields and automobile fields.

  Polycarbonate resins reinforced with glass fibers are excellent in strength and rigidity, and thus are used in casings for electrical and electronic devices, casings for electric tools, and the like. In recent years, portable terminals such as smartphones have been required to be light in weight because they carry the product. The casings of these products and the internal chassis of electrical and electronic parts are injection molded at high temperatures in order to achieve further thinning. Therefore, there is a demand for a molding material that is excellent not only in mechanical strength and rigidity but also in releasability and thermal stability of the thin portion.

  However, the conventional glass fiber reinforced polycarbonate resin composition has not been sufficiently examined for releasability and thermal stability, and it is difficult to release or crack when releasing a molded product having a thin portion. There was a problem that it was easy to generate a malfunction such as. Further, since the adhesion between the polycarbonate resin and the glass fiber is insufficient, there is a problem that the mechanical strength and appearance of the molded product are inferior.

  In order to improve the mechanical strength and rigidity of the glass fiber reinforced polycarbonate resin composition, a plurality of methods for adding an inorganic filler to the polycarbonate resin are known (for example, see Patent Documents 1 to 5).

  For example, Patent Document 1 proposes a glass fiber reinforced polycarbonate resin composition having excellent impact resistance, rigidity, and dimensional stability, which is made of polycarbonate resin, glass fiber, trialkyl phosphite, and polyethylene wax. However, the releasability and thermal stability of this resin composition have not been studied.

  Patent Document 2 proposes a glass fiber reinforced polycarbonate comprising 50 to 240 parts by weight of a fibrous filler with L / D ≧ 3 in a polycarbonate resin having a specific viscosity average molecular weight. Further, Patent Document 3 proposes a low-anisotropic high-rigidity glass fiber reinforced resin molded product comprising a polycarbonate resin and glass fibers having a number average aspect ratio of 4 to 10. However, neither Patent Document 2 nor Patent Document 3 discusses releasability and thermal stability.

  Patent Document 4 proposes a glass fiber reinforced polycarbonate having improved impact resistance and moldability, which is made of polycarbonate resin, glass fiber, and heat-resistant styrene elastomer. However, the thermal stability of this resin composition and the adhesiveness between polycarbonate resin and glass fiber have not been studied. Patent Document 5 proposes a glass fiber reinforced polycarbonate having improved toughness composed of a polycarbonate resin, glass fiber, and a partially hydrogenated block copolymer. However, the thermal stability and releasability of this resin composition, the adhesion between the polycarbonate resin and the glass fiber, and the appearance of the molded product have not been studied.

JP-A-57-094039 JP 05-287185 A JP 04-1000083 JP 03-273052 A Special table 2005-524749

  The present invention provides a polycarbonate resin composition that is excellent in releasability, thermal stability, appearance of a molded product, and adhesion between polycarbonate resin and glass fiber without impairing the excellent mechanical strength and rigidity of the polycarbonate resin composition. An object of the present invention is to provide a fiber-reinforced resin-resin-molded product used in a specific application.

  As a result of earnest research to solve the above-mentioned problems, the present inventor has found that a glass fiber, a phosphite compound having a specific structure, a fatty acid ester, a specific polyamide copolymer and a specific polyamide copolymer are used in a polycarbonate resin. By including the hydrogenated styrene-based thermoplastic elastomer, the excellent mechanical strength and rigidity of the glass fiber reinforced polycarbonate resin composition are not impaired, and the mold release property, thermal stability, appearance of the molded product, and the polycarbonate resin The polycarbonate resin composition excellent in the adhesiveness of glass fiber was obtained, and it discovered that the molded article formed by shape | molding this could be applied suitably for a specific use, and came to complete this invention.

  That is, in the present invention, the phosphite compound (C) is added in an amount of 0.1 to 100 parts by weight of the main component composed of 40 to 80% by weight of the polycarbonate resin (A) and 20 to 60% by weight of the glass fiber (B). 01 to 0.2 parts by weight, 0.1 to 2 parts by weight of fatty acid ester (D), 0.5 to 10 parts by weight of polyamide copolymer (E), and hydrogenated styrene-based thermoplastic elastomer (F) The present invention relates to a fiber reinforced resin molded article characterized by being a thin-walled casing used for electric and electronic equipment, which contains a polycarbonate resin composition containing up to 10 parts by weight.

  The fiber reinforced resin molded product of the present invention is excellent in mold release, thermal stability, appearance of molded product, and adhesion between polycarbonate resin and glass fiber without impairing the excellent mechanical strength and rigidity of the polycarbonate resin composition. Because it is excellent, its industrial utility value is high. In particular, it is useful as a substitute for metal products used for thin casings, housings, casings, covers, or internal chassis used in electrical equipment and electronic equipment, and the weight of the products can be reduced. In addition, when an external force is applied to the fiber-reinforced resin molded product of the present invention, the occurrence of problems such as bending of the molded product and damaging electronic components housed inside the molded product is suppressed as much as possible. .

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples and the like, and is within the scope of the present invention. Any change can be made.

  The use of the fiber-reinforced resin molded product of the present invention is a thin housing for electric and electronic equipment, and means a use including a housing, a casing, a cover, an internal chassis, or the like. In particular, a thin case, a housing and the like of a portable electronic device are preferable examples. More specifically, there are laptop computers, portable information terminals such as smart phones, video cameras, digital cameras, thin-walled cases such as smart meters, housings, casings, and substitutes for metal products used in internal chassis.

  The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. A typical example of the polymer is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.

  These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be used in combination.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  The viscosity average molecular weight of the polycarbonate resin (A) is not particularly limited, but is usually in the range of 10,000 to 100,000, more preferably 16,000 to 30,000, and even more preferably 19000 to 26,000 in terms of moldability and strength. Moreover, when manufacturing this polycarbonate resin, a molecular weight modifier, a catalyst, etc. can be used as needed.

  The compounding quantity of polycarbonate resin (A) is 40 to 80 weight%. If it exceeds 80% by weight, the rigidity is inferior, and if it is less than 40% by weight, a molded product having inferior thermal stability may be generated.

  The glass used for the glass fiber (B) used in the present invention is preferably alkali-free glass (E glass). The diameter of the glass fiber is preferably 6 μm or more, and the optimum range is 6 to 20 μm. Further, the number average fiber length of the glass fibers is preferably 1 to 8 mm. These are produced according to any conventionally known method.

  If the diameter of the glass fiber (B) used by this invention is the range of 6-20 micrometers, since it is excellent in rigidity, it is preferable. In addition, when the number average fiber length is 1 mm or less, the mechanical strength is not improved sufficiently, and when producing a polycarbonate resin exceeding 8 mm, the glass fiber is dropped from the resin because the dispersibility of the glass fiber in the polycarbonate resin is inferior. As a result, productivity tends to decrease.

  Commercially available glass fibers include those having a diameter of 10 μm and those having a diameter of 13 μm, and their number average length is 2 to 6 mm. Examples of commercially available glass fibers include CS321 manufactured by KCC and CS03MAFT737 manufactured by Owens Corning Japan.

  The glass fiber (B) used in the present invention can be subjected to a surface treatment with a silane coupling agent such as aminosilane or epoxysilane for the purpose of improving the adhesion to the polycarbonate resin. Further, when glass fiber is handled, it can be bundled with a bundling agent such as urethane or epoxy for the purpose of improving the handleability.

  The compounding quantity of the glass fiber (B) used by this invention is 20 to 60 weight%. If it exceeds 60% by weight, a molded product with poor appearance may be generated, which is not preferable. On the other hand, if it is less than 20% by weight, the strength and rigidity are inferior. A more preferable blending amount is 30 to 50% by weight, most preferably 40 to 45% by weight.

  The glass fiber reinforced polycarbonate resin composition used in the present invention contains a phosphite compound (C). By blending the phosphite compound (C), the glass fiber reinforced polycarbonate resin composition excellent in thermal stability is obtained without impairing properties such as mechanical strength inherent in the polycarbonate resin (A). can get.

As the phosphite compound (C) used in the present invention, the compound represented by the general formula (1) is particularly suitable.
General formula (1)

（式中、Ｒ１及びＲ２は、それぞれ独立して、炭素数１〜２０のアルキル基又はアルキル基で置換されていてもよいアリール基を示し、ａ及びｂは、それぞれ独立して、０〜３の整数を示す）

(In the formula, R 1 and R 2 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group optionally substituted with an alkyl group, and a and b each independently represent 0 to 3 Indicates an integer)

  As the compound represented by the general formula (1), for example, ADK STAB PEP-36 manufactured by ADEKA (“ADEKA STAB” is a registered trademark) and Doverphos S-9228 manufactured by Dover Chemical are commercially available.

Examples of the phosphite compound (C) include compounds represented by the general formula (2) in addition to the compounds represented by the general formula (1).
General formula (2)

（式中、Ｒ３は、炭素数１〜２０のアルキル基又はアルキル基で置換されていてもよいアリール基を示し、ｃは、０〜３の整数を示す）

(In the formula, R3 represents an alkyl group having 1 to 20 carbon atoms or an aryl group optionally substituted with an alkyl group, and c represents an integer of 0 to 3).

  In the general formula (2), R3 is an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.

  Examples of the compound represented by the general formula (2) include triphenyl phosphite, tricresyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, and trisnonylphenyl phosphite. It is done. Among these, tris (2,4-di-t-butylphenyl) phosphite is particularly suitable. For example, Irgafos 168 manufactured by BASF ("Irgafos" is a registered trademark of BASF Societas Europea) is commercially available. Is available.

  The compounding amount of the phosphite compound (C) used in the present invention is 100 parts by weight of a resin composition comprising 40 to 80% by weight of polycarbonate resin (A) and 20 to 60% by weight of glass fiber (B). The content is 0.01 to 0.2 parts by weight based on the weight. If the blending amount exceeds 0.2 parts by weight, the thermal stability is adversely deteriorated. If it is less than 0.01 part by weight, it is not preferable because the thermal stability is poor. More preferably, it is 0.02-0.1 weight part, Most preferably, it is 0.03-0.05 weight part.

  The glass fiber reinforced polycarbonate resin composition used in the present invention contains a fatty acid ester (D). By blending the fatty acid ester (D), the properties such as mechanical strength inherent in the polycarbonate resin (A) are not impaired, and a glass fiber reinforced polycarbonate resin composition excellent in releasability and thermal stability is obtained. can get.

  As the fatty acid ester (D) used in the present invention, a usual condensation compound of an aliphatic carboxylic acid and an alcohol can be used.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. The aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, monocarboxylic acids and dicarboxylic acids having 6 to 36 carbon atoms are preferable, and saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferable.

  Specific examples of the aliphatic carboxylic acid include, for example, palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellic acid, tetratriacontanoic acid , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.

  Examples of the alcohol include saturated or unsaturated monohydric alcohols and polyhydric alcohols, and these alcohols may have a substituent such as a fluorine atom, a chlorine atom, a bromine atom, or an aryl group. Among these, a saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol and aliphatic saturated polyhydric alcohol having 30 or less carbon atoms are more preferable. Aliphatic alcohols include alicyclic alcohols.

  Specific examples of the alcohol include, for example, octanol, decanol, dodecanol, tetradecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylol. Examples include propane and dipentaerythritol.

  Specific examples of the fatty acid ester (D) used in the present invention include, for example, behenyl behenate, octyldodecyl behenate, stearyl stearate, glycerol monopalmitate, glycerol monostearate, glycerol monooleate, glycerol Distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, etc., these may be used alone or in combination A combination of the above can be used. Among these, pentaerythritol stearate is preferable, and for example, Roxyol VPG861 manufactured by Cognis is commercially available.

  The blending amount of the fatty acid ester (D) used in the present invention is 0 with respect to 100 parts by weight of the resin composition comprising 40 to 80% by weight of the polycarbonate resin (A) and 20 to 60% by weight of the glass fiber (B). .1 to 2 parts by weight. A blending amount exceeding 2 parts by weight is not preferable because stable production becomes difficult. If it is less than 0.1 parts by weight, it is not preferable because it is inferior in mold release. More preferably, it is 0.3-1.5 weight part, Most preferably, it is 0.5-1.0 weight part.

  The glass fiber reinforced polycarbonate resin composition used in the present invention contains a polyamide copolymer (E). By blending the polyamide copolymer (E), the adhesion between the polycarbonate resin (A) and the glass fiber (B) is improved, and the properties such as mechanical strength inherent in the polycarbonate resin (A) may be impaired. In addition, a glass fiber reinforced polycarbonate resin composition excellent in the appearance of the molded product is obtained.

  The polyamide copolymer (E) used in the present invention is a random copolymerized polyamide comprising a plurality of monomers. Monomers include lactams such as ε-caprolactam and lauryl lactam, amino acids such as 11-aminoundecanoic acid, dicarboxylic acids such as adipic acid and isophthalic acid, and diamines such as ethylenediamine and hexamethylenediamine, and two or more types of monomers Is used. For example, PLATMID H106, H2519, etc. manufactured by Arkema are commercially available.

  The polyamide copolymer (E) used in the present invention has a melting point of 90 to 120 ° C. and a plant-derived carbon component of 10 to 10 in order to improve the adhesion between the polycarbonate resin (A) and the glass fiber (B). A 90% polyamide copolymer is preferred. More preferably, it is a polyamide copolymer having a melting point of 100 to 110 ° C. and a plant-derived carbon component of 20 to 80%. As a polyamide copolymer having a melting point of 90 to 120 ° C. and a plant-derived carbon component of 10 to 90%, for example, PLATMID M1276, HX2592 and the like manufactured by Arkema are commercially available.

  The compounding amount of the polyamide copolymer (E) used in the present invention is 100 parts by weight of a resin composition comprising 40 to 80% by weight of the polycarbonate resin (A) and 20 to 60% by weight of the glass fiber (B). 0.5 to 10 parts by weight. If the blending amount exceeds 10 parts by weight, the appearance of the molded product is inferior. If it is less than 0.5 part by weight, the adhesion between the polycarbonate resin and the glass fiber is inferior, which is not preferable. More preferably, it is 1-8 weight part, Most preferably, it is 3-5 weight part.

  The hydrogenated styrene-based thermoplastic elastomer (F) can be blended with the glass fiber reinforced polycarbonate resin composition used in the present invention, if necessary. By blending the hydrogenated styrene thermoplastic elastomer (E), the adhesion between the polycarbonate resin (A) and the glass fiber (B) is further improved, and the properties such as the mechanical strength inherent in the polycarbonate resin (A) are improved. A glass fiber reinforced polycarbonate resin composition which is not damaged and has an excellent appearance of a molded product is obtained.

  The hydrogenated styrenic thermoplastic elastomer (F) used in the present invention comprises a polystyrene-poly (ethylene / propylene) block copolymer, a polystyrene-poly (ethylene / propylene) block-polystyrene copolymer, a polystyrene-poly ( Ethylene / butylene) block-polystyrene copolymer, polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene copolymer, and the like. In addition, as these hydrogenated styrene-based thermoplastic elastomers, those modified with maleic anhydride or amine can also be used. Furthermore, these can be used individually or in combination of 2 or more types. Among these, polystyrene-poly (ethylene / butylene) block-polystyrene copolymers are suitable, and for example, Kuraray Septon 8004 and 8007 are commercially available.

  The hydrogenated styrene thermoplastic elastomer (F) used in the present invention preferably has a styrene unit content of 55% by weight or more from the viewpoint of the appearance of the molded product. As a hydrogenated styrene thermoplastic elastomer having a styrene unit content of 55% by weight or more, for example, Kuraray Septon 8104 is commercially available.

  The blended amount of the hydrogenated styrenic thermoplastic elastomer (F) used in the present invention is 100% by weight of a resin composition comprising 40 to 80% by weight of polycarbonate resin (A) and 20 to 60% by weight of glass fiber (B). Up to 10 parts by weight per part. If the blending amount exceeds 10 parts by weight, the appearance of the molded product is inferior. More preferred is up to 8 parts by weight, most preferred up to 5 parts by weight.

  In the glass fiber reinforced polycarbonate resin composition used in the present invention, for example, the polycarbonate resin is supplied from the first feeder (raw material supply port) into the extruder barrel and the glass fiber is secondly melted after the resin is sufficiently melted. After feeding into the extruder barrel from the feeder (filler supply port), a generally available disk (for example, a kneading disk) or the like is applied to the screw used for kneading, and this disk is configured by a known method. It is possible to use a plurality of the above, or to adjust the arrangement of the disk as appropriate to perform kneading. A pultrusion method in which a polycarbonate resin is impregnated into the fiber while drawing the glass fiber can also be used.

  Furthermore, various resins, antioxidants, fluorescent brighteners, pigments, dyes, carbon black, fillers, mold release agents, ultraviolet absorbers are added to the polycarbonate resin composition of the present invention within the range not impairing the effects of the present invention. , Antistatic agents, rubber, softeners, spreading agents (liquid paraffin, epoxidized soybean oil, etc.), flame retardants, additives such as organic metal salts, polytetrafluoroethylene resin for preventing dripping, etc. .

  Examples of the various resins include high impact polystyrene, ABS, AES, AAS, AS, acrylic resin, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polysulfone, polyphenylene sulfide resin, and the like. It may be used in combination with more than one species.

  Examples of the antioxidant include phosphorus antioxidants and phenolic antioxidants. Of these, hindered phenolic antioxidants are preferably used. For example, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis [ Examples include 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate. Examples of the antioxidant include Irganox 1076 manufactured by Ciba Specialty Chemicals.

  As the method for molding the fiber-reinforced resin molded product of the present invention, extrusion molding or injection molding is used. For extrusion molding, a mold such as a sheet using an extruder or profile extrusion is used. For injection molding, a mold capable of forming the molded product and an injection molding machine of 100 to 200 Т class are used. The molding processing temperature is preferably 230 to 260 ° C.

  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 changed or modified without departing from the spirit of the present invention. Unless otherwise specified, “%” and “parts” in the examples indicate “% by weight” and “parts by weight” based on the weight standard, respectively.

Details of the raw materials used are as follows.
1. Polycarbonate resin (A):
Polycarbonate resin synthesized from bisphenol A and phosgene (manufactured by Sumika Stylon Polycarbonate, Caliber 200-20, viscosity average molecular weight 19000, hereinafter abbreviated as “PC1”)
Polycarbonate resin synthesized from bisphenol A and phosgene (manufactured by Sumika Stylon Polycarbonate Co., Ltd. Caliber 200-13, viscosity average molecular weight 21000, hereinafter abbreviated as “PC2”)
Polycarbonate resin synthesized from bisphenol A and phosgene (manufactured by Sumika Stylon Polycarbonate, Caliber 200-3, viscosity average molecular weight 28000, hereinafter abbreviated as “PC3”)

2. Glass fiber (B):
E glass fiber (CS321 manufactured by KCC, fiber diameter 10 μm, fiber length 3 mm,
Epoxy sizing agent (hereinafter abbreviated as “GF”)

3. Phosphite compound (C):
3-1. 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro represented by the following formula [5,5] Undeka

アデカスタブＰＥＰ−３６（商品名、ＡＤＥＫＡ社製、以下「化合物Ｃ１」という）

ADK STAB PEP-36 (trade name, manufactured by ADEKA, hereinafter referred to as “Compound C1”)

3-2. Tris (2,4-di-t-butylphenyl) phosphite represented by the following formula

イルガフォス１６８（商品名、ＢＡＳＦ社製、以下「化合物Ｃ２」という）

Irgaphos 168 (trade name, manufactured by BASF, hereinafter referred to as “Compound C2”)

4). Fatty acid ester (D):
Pentaerythritol stearate Roxyol VPG861 (trade name, manufactured by Cognis, hereinafter abbreviated as “D1”)

5. Polyamide copolymer (E):
5-1. Polyamide copolymer (melting point 110 ° C, plant-derived carbon component 20%)
PLATAMID M1276 (trade name, manufactured by Arkema Corporation, hereinafter abbreviated as “E1” 5-2. Polyamide copolymer (melting point: 106 ° C., plant-derived carbon component: 80%)
PLATAMID HX2592 (trade name, manufactured by Arkema Inc., hereinafter abbreviated as “E2”)

6). Hydrogenated styrenic thermoplastic elastomer (F):
Polystyrene-poly (ethylene / butylene) block-polystyrene copolymer Septon 8104
(Trade name, manufactured by Kuraray Co., Ltd., styrene unit content 60 wt%, abbreviated as “F1”)

(Pellet creation)
The above-mentioned various blending components are kneaded at a blending ratio shown in Tables 1 and 2 using a twin screw extruder (TEM-37SS manufactured by Toshiba Machine Co., Ltd.) at a melting temperature of 300 ° C., and a glass fiber reinforced polycarbonate resin composition. I got a thing. The glass fiber reinforced polycarbonate resin supplies polycarbonate resin, phosphite ester compound and fatty acid ester into the extruder barrel from the first feeder (raw material supply port), and after the resin composition is sufficiently melted, the glass fiber is secondly added. After feeding into the extruder barrel from the feeder (filler supply port), kneading was performed to obtain glass fiber reinforced polycarbonate resin composition pellets.

(Evaluation of flexural modulus of molded product)
The pellets of the various resin compositions obtained above were each dried at 125 ° C. for 4 hours, and then subjected to an ISO test method using an injection molding machine (manufactured by FANUC, ROBOSHOT S2000i100B) at a set temperature of 300 ° C. and an injection pressure of 100 MPa. A test piece having a thickness of 4 mm was prepared, and the flexural modulus (rigidity) was measured according to ISO 178 using the obtained test piece. When the flexural modulus was good at 6000 MPa or more, it was expressed as “◯” in the table, and when it was less than 6000 MPa, it was regarded as defective and indicated by “X” in the table.

(Evaluation of thermal stability)
The pellets of the various resin compositions obtained above and the test pieces measured for flexural modulus (rigidity) were dissolved in dichloromethane, and NO. The insoluble matter in the solution was filtered using 1 filter paper. The filtrate was dried up, and a certain amount (0.25 g) of the obtained polymer was dissolved in 50 ml of dichloromethane. The viscosity of the dilute dichloromethane solution was measured at 23 ° C. using a Canon-Fenske viscometer, and the viscosity average molecular weight of each test piece was determined using the Schnell equation.
(Schnell equation) [η] = 1.23 × 10 ⁻⁴ · M ^0.83
[Η]: Intrinsic viscosity, M: Viscosity average molecular weight In addition, a decrease in molecular weight, which is an index of thermal stability, indicates that the value obtained by subtracting the viscosity average molecular weight of the test piece from the viscosity average molecular weight of the pellet (ΔMv) is less than 2000 In the table, it is represented by ○, and the case of 2000 or more was regarded as defective and represented by × in the table.

(Evaluation of releasability)
The pellets of the resin compositions obtained above were each dried at 125 ° C. for 4 hours, and then cooled using an injection molding machine (FANUC, ROBOSHOT S2000i100B) at a cylinder set temperature of 300 ° C. and a mold temperature of 50 ° C. The releasability was evaluated under the condition of time 20 seconds. Using a cup-type mold release resistance mold (molded product shape: 70 mm in diameter, 20 mm in height, 4 mm in thickness), the protruding load applied to the protruding pin when molding a cup-shaped molded product is measured. The mold release resistance value was obtained. As a criterion for evaluation, a release resistance value of less than 800N is good, and when it is 800N or more, it is regarded as defective and is indicated by x in the table.

(Evaluation of molded product appearance)
About the test piece which measured the bending elastic modulus (rigidity), the roughness of the molded article surface by glass fiber was observed visually, and the thing by which the molded article surface by glass fiber was not rough was made favorable.

(Adhesiveness between polycarbonate resin and glass fiber)
About the cross section of the test piece whose bending elastic modulus (rigidity) was measured, it was observed at 500 times using a scanning electron microscope (manufactured by Hitachi, S-3400N). The thing made the adhesiveness of polycarbonate resin and glass fiber favorable. Before observation, the cross section of the test piece was vapor-deposited using ion sputtering (Hitachi, E-1010).

  As shown in Examples 1 to 14, those satisfying the constituent requirements of the present invention satisfied the required performance.

On the other hand, as shown in Comparative Examples 1 to 9, those not satisfying the constituent requirements of the present invention had the following defects.
The comparative example 1 was a case where the compounding quantity of glass fiber (B) was less than a regulation amount, and the bending elastic modulus was inferior.
In Comparative Example 2, the amount of glass fiber (B) was greater than the specified amount, and it was impossible to produce pellets.
Comparative Example 3 was a case where the blending amount of the phosphite compound (C) was less than the specified amount, and the thermal stability was inferior.
Comparative Example 4 was a case where the blending amount of the phosphite compound (C) was larger than the specified amount, and the thermal stability was poor.
Comparative Example 5 was a case where the compounding amount of the fatty acid ester (D) was less than the specified amount, and the releasability was inferior.
Comparative Example 6 was a case where the blending amount of the fatty acid ester (D) was larger than the specified amount, and it was impossible to produce pellets.
Comparative Example 7 was a case where the blending amount of the polyamide copolymer (E) was less than the specified amount, and the adhesion between the polycarbonate resin and the glass fiber was inferior.
In Comparative Example 8, it was impossible to produce pellets when the blending amount of the polyamide copolymer (E) was larger than the specified amount.
Comparative Example 9 was a case where the blended amount of the hydrogenated styrene-based thermoplastic elastomer (F) was larger than the specified amount, and the appearance of the molded product was inferior.

  The fiber reinforced resin molded product of the present invention is excellent in mold release, thermal stability, appearance of molded product, and adhesion between polycarbonate resin and glass fiber without impairing the excellent mechanical strength and rigidity of the polycarbonate resin composition. Because it is excellent, its industrial utility value is high. In particular, it is useful as a substitute for metal products used for thin casings, housings, casings, covers, or internal chassis used in electrical equipment and electronic equipment, and the weight of the products can be reduced. In addition, when an external force is applied to the fiber-reinforced resin molded product of the present invention, the occurrence of problems such as bending of the molded product and damaging electronic components housed inside the molded product is suppressed as much as possible. .

Claims (10)

  0.01-0.2 wt.% Of the phosphite compound (C) with respect to 100 wt. Parts of the main component consisting of 40-80 wt.% Of the polycarbonate resin (A) and 20-60 wt.% Of the glass fiber (B). Parts, 0.1-2 parts by weight of fatty acid ester (D), 0.5-10 parts by weight of polyamide copolymer (E), and up to 10 parts by weight of hydrogenated styrene-based thermoplastic elastomer (F). A fiber-reinforced resin molded article comprising a polycarbonate resin composition, which is a thin-walled casing used for electrical and electronic equipment.   The fiber reinforced resin molded article according to claim 1, wherein the polycarbonate resin (A) has a viscosity average molecular weight of 16000 to 30000.   The fiber-reinforced resin molded article according to claim 1, wherein the glass fiber (B) is treated with at least one of an epoxy-based sizing agent and a urethane-based sizing agent, and has an average diameter of 6 to 20 µm. The fiber reinforcement according to claim 1, wherein the phosphite compound (C) is one or more compounds selected from compounds represented by the following general formula (1) or the following general formula (2). Resin molded product.
General formula (1)

(In the formula, R 1 and R 2 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group optionally substituted with an alkyl group, and a and b each independently represent 0 to 3 Indicates an integer)
General formula (2)

(In General Formula (2), R3 represents an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group, and c represents an integer of 0 to 3).   The phosphite compound (C) represented by the general formula (1) is 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10. The polycarbonate resin composition according to claim 4, which is -tetraoxa-3,9-diphosphaspiro [5,5] undecane.   The polycarbonate resin composition according to claim 4, wherein the phosphite compound (C) represented by the general formula (2) is tris (2,4-di-t-butylphenyl) phosphite.   The fiber reinforced resin molded article according to claim 1, wherein the fatty acid ester (D) is pentaerythritol tetrastearate.   The fiber-reinforced resin molded article according to claim 1, wherein the polyamide copolymer (E) is a polyamide copolymer having a melting point of 90 to 120 ° C and a plant-derived carbon component of 10 to 90%.   The fiber-reinforced resin molded article according to claim 1, wherein the hydrogenated styrene thermoplastic elastomer (F) is a polystyrene-poly (ethylene / butylene) block-polystyrene copolymer.   The fiber reinforced resin molding according to claim 1, wherein the hydrogenated styrene-based thermoplastic elastomer (F) is a polystyrene-poly (ethylene / butylene) block-polystyrene copolymer having a styrene unit content of 55% by weight or more. Goods.