JPWO2018074066A1 - Fiber reinforced polycarbonate resin composition - Google Patents

Abstract

The present invention molds a glass fiber reinforced polycarbonate resin composition excellent in releasability and thermal stability and its resin composition without impairing the excellent mechanical strength and rigidity of the glass fiber reinforced polycarbonate resin composition. It aims at providing the resin molded product which becomes. In the present invention, 0.01% of the phosphite compound (C) is added 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). It is related with the fiber reinforced polycarbonate resin composition characterized by containing -0.2 weight part and fatty acid ester (D) 0.1-2 weight part.

Description

  The present invention provides a fiber-reinforced polycarbonate resin composition excellent in mold release properties at the time of injection molding while maintaining the excellent heat resistance and thermal stability inherently possessed by the polycarbonate resin, and the rigidity of the resulting molded product, and its The present invention relates to a resin molded product obtained by molding a resin composition.

  Since the polycarbonate resin is a thermoplastic resin excellent in mechanical strength, heat resistance, thermal stability, etc., it is widely used industrially in the electric and electronic fields and the automobile field. 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 part. There was a problem that it was easy to generate a malfunction such as.

  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. Patent Document 1 proposes a glass fiber reinforced polycarbonate resin composition excellent in 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 composition in which 50 to 240 parts by weight of a fibrous filler having L / D ≧ 3 is blended with a polycarbonate resin having a specific viscosity average molecular weight. Patent Document 3 proposes a low-anisotropy high-rigidity glass fiber reinforced resin molded article made of 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.

JP-A-57-094039 JP 05-287185 A JP 04-1000083

  The present invention molds a glass fiber reinforced polycarbonate resin composition excellent in releasability and thermal stability and its resin composition without impairing the excellent mechanical strength and rigidity of the glass fiber reinforced polycarbonate resin composition. It aims at providing the resin molded product which becomes.

  As a result of intensive studies to solve the above problems, the present inventor has made glass fiber reinforced polycarbonate resin composition by adding glass fiber, phosphite compound having a specific structure and fatty acid ester to polycarbonate resin. The present inventors have found that a glass fiber reinforced polycarbonate resin composition excellent in releasability and thermal stability can be obtained without impairing the excellent mechanical strength and rigidity of the product.

  That is, in the present invention, phosphite compound (C) is added to 100 parts by weight of a resin composition composed of 40 to 80% by weight of polycarbonate resin (A) and 20 to 60% by weight of glass fiber (B). The present invention relates to a fiber reinforced polycarbonate resin composition comprising 0.1 to 0.2 parts by weight and 0.1 to 2 parts by weight of fatty acid ester (D).

  It is preferable that the viscosity average molecular weight of polycarbonate resin (A) is 16000-30000.

  It is preferable that the glass fiber (B) is treated with an epoxy sizing agent or a urethane sizing agent, and the average diameter of the fiber cross section is 6 to 20 μm.

  The glass fiber (B) preferably has a flat cross section having an average value of the major axis of the fiber cross section of 10 to 50 μm and an average ratio of the major axis to the minor axis (major axis / minor axis) of 2 to 8.

（式中、Ｒ^１及びＲ^２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）
一般式（２）

（一般式（２）において、Ｒ^３は炭素数１〜２０のアルキル基、またはアルキル基で置換されてもよいアリール基を、ｃは０〜３の整数を示す。）The phosphite compound (C) is preferably a compound represented by the following general formula (1) or a compound represented by the following general formula (2).
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 Represents an integer of ~ 3)
General formula (2)

(In General Formula (2), R ³ 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- Tetraoxa-3,9-diphosphaspiro [5,5] undecane or 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3, It is preferably 9-diphosphaspiro [5,5] undecane.

  The phosphite compound (C) represented by the general formula (2) is preferably tris (2,4-di-t-butylphenyl) phosphite.

  The fatty acid ester (D) is preferably pentaerythritol tetrastearate.

Furthermore, it is preferable that 0.2-20 weight part of thermoplastic elastomer (E) is included with respect to 100 weight part of polycarbonate resin (A) and glass fiber (B).

The thermoplastic elastomer (E) is preferably a hydrogenated styrene thermoplastic elastomer or a polyester thermoplastic elastomer.

The present invention also relates to a resin molded product obtained by molding the fiber-reinforced polycarbonate resin composition.

  The glass fiber reinforced polycarbonate resin composition of the present invention is excellent in releasability and thermal stability without impairing the excellent mechanical strength and rigidity of the glass fiber reinforced polycarbonate resin composition. Is expensive. For example, it can be used as a substitute for a metal product used for a thin casing or an internal chassis used for an electric device or an electronic device, and the product can be reduced in weight. In addition, when an external force is applied to a molded product obtained from such a resin composition, the molded product may bend and cause problems such as damage to electronic components stored in the molded product. Can be suppressed.

  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 fiber reinforced polycarbonate resin composition of the present invention is a phosphite compound based on 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). It contains 0.01 to 0.2 parts by weight of (C) and 0.1 to 2 parts by weight of fatty acid ester (D).

  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 from 10,000 to 100,000, more preferably from 16,000 to 30,000, and even more preferably from 19000 to 26000, 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 amount of the polycarbonate resin (A) is 40 to 80% by weight, preferably 50 to 70% by weight. If it exceeds 80% by weight, the rigidity is inferior, and if it is less than 40% by weight, a molded product having poor thermal stability is generated.

  The glass fiber (B) used in the present invention is not particularly limited, and a circular cross-section glass fiber having a substantially circular cross section with an average value of the major axis to minor axis ratio (major axis / minor axis) of the fiber cross section of 1 to 1.5. However, it may be a flat cross-section glass fiber having an average value of the major axis / minor axis ratio (major axis / minor axis) of 2 to 8.

  The number average fiber length of the glass fiber (B) is preferably 1 to 8 mm, more preferably 2 to 5 mm. The glass fiber is produced according to any conventionally known method. When the number average fiber length is 1 mm or less, the mechanical strength is not sufficiently improved. When a polycarbonate resin exceeding 8 mm is produced, the glass fiber falls off from the resin because the dispersibility of the glass fiber in the polycarbonate resin is inferior. Productivity tends to decrease.

In the case where the glass fiber (B) is a circular cross-section glass fiber having a substantially circular cross section with an average value of the major axis to minor axis ratio (major axis / minor axis) of 1 to 1.5, the diameter of the glass fiber is 6 It is preferable that it is ˜20 μm. When the diameter of the glass fiber is less than 6 μm, the mechanical strength is inferior, and when it exceeds 20 μm, the appearance tends to deteriorate. The diameter of the glass fiber is more preferably 7 to 18 μm, still more preferably 8 to 15 μm.

  Commercially available fiber cross-section glass fibers having an average ratio of major axis to minor axis (major axis / minor axis) of 1 to 1.5 and having a substantially circular cross section are 10 μm in diameter and 13 μm in diameter. Some of these have a number average length of 2 to 6 mm. Examples of glass fibers available on the market include CS321 and CS311 manufactured by KCC, CS03MAFT737 manufactured by Owens Corning Japan, and the like.

  When the glass fiber (B) is a flat cross-section glass fiber having an average ratio of the major axis to the minor axis (major axis / minor axis) of 2 to 8 in the fiber cross section, the average value of the major axis is 10 to 50 μm, preferably 15 to It is 40 μm, more preferably 25 to 30 μm. Moreover, the average value of the ratio of the major axis to the minor axis (major axis / minor axis) is 2 to 8, preferably 2 to 7, more preferably 2.5 to 5. These are produced according to any conventionally known method.

  If the major axis of the flat cross-section glass fiber is less than 10 μm, the production is difficult, and if it exceeds 50 μm, the appearance of the molded product surface of the polycarbonate resin composition may be impaired. When the ratio of the major axis to the minor axis is less than 2, the dimensional stability is inferior, and when it exceeds 8, the strength may be inferior.

  Examples of the flat cross-section glass fibers having an average ratio of the major axis to the minor axis (major axis / minor axis) of 2 to 8 that are commercially available are CSG 3PA-820 and CSG 3PA- manufactured by Nitto Boseki Co., Ltd. 830 or the like.

  The glass fiber (B) can be surface-treated with a silane coupling agent such as aminosilane or epoxysilane for the purpose of improving the adhesion with the polycarbonate resin. Further, when glass fibers are handled, they can be focused by a bundling material such as urethane or epoxy for the purpose of improving the handleability.

  The compounding quantity of glass fiber (B) is 20 to 60 weight% in a resin composition. When it exceeds 60% by weight, a molded product having poor appearance is generated. If it is less than 20% by weight, it is inferior in strength and rigidity. 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 of 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), the compound represented by the general formula (1) is particularly suitable.
General formula (1)

（式中、Ｒ^１及びＲ^２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 Represents an integer of ~ 3)

  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、Ｒ^３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）

(Wherein R ³ 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 General Formula (2), R ³ 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, Irgaphos 168 manufactured by BASF ("Irgafos" is a registered trademark of BISF Societas Europea) is commercially available. Are available.

  The compounding quantity of a phosphite-type compound (C) is 0.01-0.2 weight part with respect to 100 weight part of resin compositions which consist of polycarbonate resin (A) and glass fiber (B). On the other hand, if the blending amount exceeds 0.2 parts by weight, the thermal stability becomes worse. If it is less than 0.01 parts by weight, 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.

  Fatty acid ester (D) is mix | blended with the glass fiber reinforced polycarbonate resin composition of this invention. 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, Examples include montanic acid, glutaric acid, adipic acid, and azelaic acid.

  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, ditrimethylolpropane. And dipentaerythritol.

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

  The compounding quantity of fatty-acid ester (D) is 0.1-2 weight part with respect to 100 weight part of resin compositions which consist of polycarbonate resin (A) and glass fiber (B). If the amount exceeds 2 parts by weight, stable production becomes difficult. If it is less than 0.1 parts by weight, the releasability is poor. 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 of the present invention preferably contains a thermoplastic elastomer (E). By blending the thermoplastic elastomer (E), the adhesion between the polycarbonate resin (A) and the glass fiber (B) is improved, and the properties such as the mechanical strength inherent to the polycarbonate resin (A) are not impaired. Furthermore, a glass fiber reinforced polycarbonate resin composition having an excellent appearance of a molded product can be obtained.

  The thermoplastic elastomer (E) is not particularly limited, and is an olefin thermoplastic elastomer, a styrene thermoplastic elastomer, a hydrogenated styrene thermoplastic elastomer, a polyester thermoplastic elastomer, an acrylic thermoplastic elastomer, a polyurethane thermoplastic elastomer. And polyamide-based thermoplastic elastomers. Of these, hydrogenated styrene-based thermoplastic elastomers and polyester-based thermoplastic elastomers are preferred.

  Hydrogenated styrene thermoplastic elastomers are polystyrene-poly (ethylene / propylene) block copolymer, polystyrene-poly (ethylene / propylene) block-polystyrene copolymer, polystyrene-poly (ethylene / butylene) block-polystyrene copolymer. And a polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene copolymer. 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, 8007, Asahi Kasei Corporation Tuftec H1062, H1051, H1043, etc. are commercially available. is there.

  The hydrogenated styrene thermoplastic elastomer preferably has a styrene unit content of 55% by weight or more from the viewpoint of the appearance of the molded product. Examples of the hydrogenated styrene-based thermoplastic elastomer having a styrene unit content of 55% by weight or more include commercially available Kuraray Septon 8104, Asahi Kasei Tuftec H1043, and the like.

  The polyester-based thermoplastic elastomer is a multi-block copolymer composed of a hard segment and a soft segment (one or more selected from the group consisting of an aliphatic polyether, an aliphatic polyester, and a polycarbonate in a hard segment composed of an aromatic polyester). Block copolymer having soft segments bonded). The hard segment is preferably an aromatic polyester, and specific examples thereof include polybutylene terephthalate and polybutylene naphthalate. These can be used alone or in combination of two or more.

  As the soft segment, aliphatic polyether, aliphatic polyester, polycarbonate and the like are suitable, and specific examples include poly (ε-caprolactone), polytetramethylene glycol, polyalkylene carbonate and the like. These can be used alone or in combination of two or more. Examples of such a block copolymer (copolymer) include one or more copolymers selected from the group consisting of polyester-polyester copolymers, polyester-polyether copolymers, and polyester-polycarbonate copolymers. Is preferred.

  Examples of the commercially available polyester-based thermoplastic elastomer (E) include Hytrel manufactured by Toray DuPont and Perprene manufactured by Toyobo.

  As the thermoplastic elastomer, a hydrogenated styrene thermoplastic elastomer and a polyester thermoplastic elastomer can be used in combination. By using both together, a glass fiber reinforced polycarbonate resin composition in which the adhesion between the polycarbonate resin (A) and the glass fiber (B) is further improved is obtained.

  The compounding amount of the polyester-based thermoplastic elastomer (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). It is 0.2-20 weight part with respect to it. If the blending amount exceeds 20 parts by weight, it is not preferable because stable production becomes difficult. If it is less than 0.2 parts by weight, the adhesion between the polycarbonate resin (A) and the glass fiber (B) is inferior. More preferably, it is 0.3-15 weight part, Most preferably, it is 0.4-10 weight part.

  In the glass fiber reinforced polycarbonate resin composition of the present invention, for example, the polycarbonate resin is supplied from the first feeder (raw material supply port) into the extruder barrel, and after the resin is sufficiently melted, the glass fiber is supplied to the second feeder (filler). A generally available disk (for example, a kneading disk) or the like is applied to the screw used for kneading after being fed into the extruder barrel from the supply port), and a plurality of such disks can be used as a screw configuration by a known method. It is possible to perform kneading while adjusting the arrangement of the disk as appropriate. 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. Especially, a semi hindered phenolic antioxidant and a hindered phenolic antioxidant are used suitably. Examples of semi-hindered phenolic antioxidants include Sumitomo Chemical's Sumilizer GA-80, and examples of hindered phenolic antioxidants include BASF's Irganox 1076, which are one or more. You may use together.

  The resin molded product of the present invention is obtained by molding the fiber-reinforced polycarbonate resin composition. 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. Since the molded body is excellent in appearance, it can be preferably applied to a housing such as a camera or a smartphone.

  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):
1-1. 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”)
1-2. 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”)
1-3. 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):
2-1. Circular cross-section glass fiber (CS321 manufactured by KCC, fiber diameter 10 μm, fiber length 3 mm,
Epoxy sizing agent (hereinafter abbreviated as “GF1”)
2-2. Circular cross-section glass fiber (CS311 manufactured by KCC, fiber diameter 10 μm, fiber length 3 mm,
Urethane sizing agent (hereinafter abbreviated as “GF2”)
2-3. Flat cross-section glass fiber (CSG 3PA-830 manufactured by Nitto Boseki Co., Ltd., major axis 28 μm, minor axis 7 μm, fiber length 3 mm, epoxy / urethane sizing agent, hereinafter abbreviated as “GF3”)

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”)

3-3. 3,9-bis [2,4-bis (α, α-dimethylbenzyl) phenoxy] -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] represented by the following formula: Undecane)

Ｄｏｖｅｒｐｈｏｓ Ｓ−９２２８（商品名、Ｄｏｖｅｒ Ｃｈｅｍｉｃａｌ社製、以下「Ｃ３」と略記）

Doverphos S-9228 (trade name, manufactured by Dover Chemical, hereinafter abbreviated as “C3”)

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

5. Thermoplastic elastomer (E):
5-1. Hydrogenated styrene thermoplastic elastomer 5-1-1. Polystyrene-poly (ethylene / butylene) block-polystyrene copolymer Septon 8104 (trade name, manufactured by Kuraray Co., Ltd., styrene unit content 60 wt%, abbreviated as “E1”)
5-1-2. Polystyrene-poly (ethylene / butylene) block-polystyrene copolymer Septon 8007L (trade name, manufactured by Kuraray Co., Ltd., styrene unit content 30 wt%, abbreviated as “E2”)
5.2. Polyester thermoplastic elastomer 5-2-1. Polyester-polyester copolymer Perprene S-3001 (trade name, manufactured by Toyobo Co., Ltd., abbreviated as “E3”)
Hard segment: Polybutylene terephthalate Soft segment: Poly (ε-caprolactone)
5-2-2. Polyester-polyether copolymer Perprene P-150B (trade name, manufactured by Toyobo Co., Ltd., abbreviated as “E4”)
Hard segment: polybutylene terephthalate Soft segment: polytetramethylene glycol 5-2-3. Polyester-polyether copolymer Perprene EN-3000 (trade name, manufactured by Toyobo Co., Ltd., abbreviated as “E5”)
Hard segment: polybutylene naphthalate Soft segment: polytetramethylene glycol 5-2-4. Polyester-polycarbonate copolymer Perprene C-2003 (trade name, manufactured by Toyobo Co., Ltd., abbreviated as “E6”)
Hard segment: Polybutylene terephthalate Soft segment: Polyalkylene carbonate

Examples 1 to 67 and Comparative Examples 1 to 32 (Preparation of pellets)
The above-mentioned various blending components are kneaded at a blending ratio shown in Tables 1 to 10 at a melting temperature of 300 ° C. using a twin screw extruder (TEM-37SS manufactured by Toshiba Machine Co., Ltd.), and a glass fiber reinforced polycarbonate resin composition. Got. Glass fiber reinforced polycarbonate resin is made by supplying polycarbonate resin, phosphite compound, fatty acid ester and thermoplastic elastomer from the first feeder (raw material supply port) into the extruder barrel, and sufficiently melting the resin composition. The fibers were fed into the extruder barrel from the second feeder (filler supply port) and then kneaded to obtain glass fiber-reinforced polycarbonate resin composition pellets.

<Bending elastic 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. A bending elastic modulus of 6000 MPa or more was considered good.

<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 It was.

<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 800 N was considered good.

<Appearance of molded product>
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 adhesiveness between the polycarbonate resin and the glass fiber was considered good, and “◯” in the table indicates that the defect is indicated by “X” in the table. Before observation, the cross section of the test piece was vapor-deposited using ion sputtering (Hitachi, E-1010).

  As shown in Examples 1 to 13, those satisfying the constituent requirements of the present invention satisfied the required performance.

  On the other hand, as shown in Comparative Examples 1 to 6, 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 poor. 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.

  As shown in Examples 14 to 29, those satisfying the constituent requirements of the present invention satisfied the required performance.

  On the other hand, as shown in Comparative Examples 7 to 14, those that did not satisfy the constituent requirements of the present invention had the following drawbacks. Comparative Example 7 was a case where the blending amount of the glass fiber (B) was less than the specified amount, and the bending elastic modulus was inferior. Comparative Example 8 was a case where the blending amount of the glass fiber (B) was larger than the specified amount, and it was impossible to produce a pellet. Comparative Example 9 was a case where the blending amount of the phosphite compound (C) was less than the specified amount, and the thermal stability was poor. Comparative Example 10 was a case where the blending amount of the phosphite compound (C) was larger than the specified amount, and the thermal stability was inferior. In Comparative Example 11, the compounding amount of the fatty acid ester (D) was less than the specified amount, and the releasability was inferior. In Comparative Example 12, the amount of the fatty acid ester (D) was larger than the specified amount, and it was impossible to produce pellets. Comparative Example 13 was a case where the blended amount of the hydrogenated styrene thermoplastic elastomer (E) was less than the specified amount, and the adhesion between the polycarbonate resin and the glass fiber was inferior. In Comparative Example 14, the amount of the hydrogenated styrene thermoplastic elastomer (E) was greater than the specified amount, and the appearance of the molded product was inferior.

  As shown in Examples 30 to 48, those satisfying the constituent requirements of the present invention satisfied the required performance.

  On the other hand, as shown in Comparative Examples 15 to 23, those that did not satisfy the constituent requirements of the present invention had the following drawbacks. Comparative Example 15 was a case where the blending amount of the glass fiber (B) was less than the specified amount, and the bending elastic modulus was inferior. In Comparative Example 16, the amount of glass fiber (B) was greater than the specified amount, and it was impossible to produce pellets. Comparative Example 17 was a case where the blending amount of the phosphite compound (C) was less than the specified amount, and the thermal stability was poor. Comparative Example 18 was a case where the blending amount of the phosphite compound (C) was larger than the specified amount, and the thermal stability was poor. The comparative example 19 was a case where the compounding quantity of fatty-acid ester (D) was less than a regulation amount, and the mold release property was inferior. In Comparative Example 20, the amount of the fatty acid ester (D) was larger than the specified amount, and it was impossible to produce pellets. Comparative Example 21 was a case where the blending amount of the polyester-based thermoplastic elastomer (E) was less than the specified amount, and the adhesion between the polycarbonate resin and the glass fiber was inferior. In Comparative Example 22, the amount of the polyester-based thermoplastic elastomer (E) was larger than the specified amount, and it was impossible to produce pellets. In Comparative Example 23, the amount of the hydrogenated styrene-based thermoplastic elastomer (F) was greater than the specified amount, and the appearance of the molded product was inferior.

  As shown in Examples 49 to 67, those satisfying the constituent requirements of the present invention satisfied the required performance.

  On the other hand, as shown in Comparative Examples 24-32, those that do not satisfy the constituent requirements of the present invention have the following drawbacks. In Comparative Example 24, the blending amount of the glass fiber (B) was less than the specified amount, and the flexural modulus was inferior. In Comparative Example 25, the amount of glass fiber (B) was greater than the specified amount, and it was impossible to produce pellets. In Comparative Example 26, the amount of the phosphite compound (C) was less than the specified amount, and the thermal stability was inferior. In Comparative Example 27, the amount of the phosphite compound (C) was greater than the specified amount, and the thermal stability was poor. In Comparative Example 28, the amount of the fatty acid ester (D) was less than the specified amount, and the releasability was inferior. In Comparative Example 29, the amount of the fatty acid ester (D) was larger than the specified amount, and it was impossible to produce pellets. Comparative Example 30 was a case where the blending amount of the polyester-based thermoplastic elastomer (E) was less than the specified amount, and the adhesion between the polycarbonate resin and the glass fiber was inferior. Comparative Example 31 was a case where the blending amount of the polyester-based thermoplastic elastomer (E) was larger than the specified amount, and it was impossible to produce pellets. In Comparative Example 32, the amount of the hydrogenated styrene thermoplastic elastomer (F) was greater than the specified amount, and the appearance of the molded product was inferior.

The glass fiber reinforced polycarbonate resin composition of the present invention is excellent in releasability and thermal stability without impairing the excellent mechanical strength and rigidity of the glass fiber reinforced polycarbonate resin composition. Is expensive. For example, it can be used as a substitute for a metal product used for a thin casing or an internal chassis used for an electric device or an electronic device, and the product can be reduced in weight. In addition, when an external force is applied to a molded product obtained from such a resin composition, the molded product may bend and cause problems such as damage to electronic components stored in the molded product. Can be suppressed.

Claims (11)

  The phosphorous ester compound (C) is added in an amount of 0.01 to 0.2 with respect to 100 parts by weight of the resin composition composed of 40 to 80% by weight of the polycarbonate resin (A) and 20 to 60% by weight of the glass fiber (B). A fiber-reinforced polycarbonate resin composition containing 0.1 to 2 parts by weight of a fatty acid ester (D).   The fiber-reinforced polycarbonate resin composition according to claim 1, wherein the polycarbonate resin (A) has a viscosity average molecular weight of 16,000 to 30,000.   The fiber-reinforced polycarbonate resin composition according to claim 1 or 2, wherein the glass fiber (B) is treated with an epoxy-based sizing agent or a urethane-based sizing agent, and an average diameter of a fiber cross section is 6 to 20 µm.   The glass fiber (B) has a flat cross section having an average value of the major axis of the fiber cross section of 10 to 50 µm and an average ratio of the major axis to the minor axis (major axis / minor axis) of 2 to 8. The fiber reinforced polycarbonate resin composition as described in 2. The phosphite compound (C) is a compound represented by the following general formula (1) or a compound represented by the following general formula (2). Fiber reinforced polycarbonate resin composition.
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 Represents an integer of ~ 3)
General formula (2)

(In General Formula (2), R ³ 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- Tetraoxa-3,9-diphosphaspiro [5,5] undecane or 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3, The fiber-reinforced polycarbonate resin composition according to claim 5, which is 9-diphosphaspiro [5,5] undecane.   The fiber-reinforced polycarbonate resin composition according to claim 5, wherein the phosphite compound (C) represented by the general formula (2) is tris (2,4-di-t-butylphenyl) phosphite.   The fiber-reinforced polycarbonate resin composition according to any one of claims 1 to 7, wherein the fatty acid ester (D) is pentaerythritol tetrastearate. The fiber reinforced polycarbonate according to any one of claims 1 to 8, further comprising 0.2 to 20 parts by weight of the thermoplastic elastomer (E) with respect to 100 parts by weight of the polycarbonate resin (A) and the glass fiber (B). Resin composition. The fiber-reinforced polycarbonate resin composition according to claim 9, wherein the thermoplastic elastomer (E) is a hydrogenated styrene-based thermoplastic elastomer or a polyester-based thermoplastic elastomer. The resin molded product obtained by shape | molding the fiber reinforced polycarbonate resin composition in any one of Claims 1-10.