KR20190070321A - Fiber reinforced polycarbonate resin composition - Google Patents

Abstract

It is an object of the present invention to provide a glass fiber reinforced polycarbonate resin composition excellent in mechanical strength and rigidity of a glass fiber reinforced polycarbonate resin composition and excellent in releasability and thermal stability and a resin molded product molded from the resin composition . The present invention relates to a resin composition comprising 0.01 to 0.2 parts by weight of a phosphorous ester compound (C) based on 100 parts by weight of a resin composition comprising 40 to 80% by weight of a polycarbonate resin (A) and 20 to 60% And 0.1 to 2 parts by weight of a fatty acid ester (D).

Description

Fiber reinforced polycarbonate resin composition

The present invention relates to a fiber reinforced polycarbonate resin composition excellent in releasability at the time of injection molding and excellent in rigidity of the obtained molded article while maintaining excellent inherent heat resistance and thermal stability of the polycarbonate resin and a resin molded product .

BACKGROUND ART Polycarbonate resins are widely used industrially in fields such as electric and electronic fields and automobiles because they are thermoplastic resins excellent in mechanical strength, heat resistance and thermal stability. The glass fiber-reinforced polycarbonate resin is used in a housing of an electric appliance or an electronic appliance, a housing of a power tool, or the like because of its excellent strength and rigidity. BACKGROUND ART In recent years, portable terminals such as smart phones have been demanded to be light in weight because they carry their products. Housings of these products and internal chassis of electric / electronic parts are injection molded at high temperature in order to achieve further thinning. For this reason, there is a demand for a molding material excellent in not only mechanical strength and rigidity but also releasability and thermal stability of a thin-wall portion.

However, the conventional glass fiber-reinforced polycarbonate resin composition has not sufficiently studied the releasability and thermal stability, and there is a problem that when releasing a molded article having a thin-walled portion, the releasing is difficult or breakable.

In order to improve the mechanical strength and rigidity of the glass fiber-reinforced polycarbonate resin composition, a plurality of methods of containing an inorganic filler in the polycarbonate resin are known. Patent Document 1 proposes a glass fiber-reinforced polycarbonate resin composition comprising polycarbonate resin, glass fiber, trialkyl phosphite and polyethylene wax, which is excellent in impact resistance, rigidity and dimensional stability. However, the releasability and thermal stability of the 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 fiber filler of L / D? 3 is blended with a specific viscosity average molecular weight polycarbonate resin. Patent Document 3 proposes a low anisotropic 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 the patent document 2 nor the patent document 3 discusses releasability and thermal stability.

Japanese Patent Application Laid-Open No. 57-094039 Japanese Patent Application Laid-Open No. 05-287185 Japanese Patent Application Laid-Open No. 04-100830

It is an object of the present invention to provide a glass fiber reinforced polycarbonate resin composition excellent in mechanical strength and rigidity of a glass fiber reinforced polycarbonate resin composition and excellent in releasability and thermal stability and a resin molded product molded from the resin composition .

The inventors of the present invention have conducted intensive studies in order to solve the above problems. As a result, it has been found that the glass fiber-reinforced polycarbonate resin composition has excellent mechanical strength and a high mechanical strength by containing glass fibers, a phosphorous acid ester compound having a specific structure and a fatty acid ester in a polycarbonate resin It is possible to obtain a glass fiber-reinforced polycarbonate resin composition excellent in rigidity and excellent in releasability and thermal stability, thus completing the present invention.

That is, the present invention relates to a resin composition comprising 0.01 to 0.2 wt% of a phosphorous acid ester compound (C) based on 100 parts by weight of a resin composition comprising 40 to 80 wt% of a polycarbonate resin (A) and 20 to 60 wt% And 0.1 to 2 parts by weight of a fatty acid ester (D).

It is preferable that the viscosity average molecular weight of the polycarbonate resin (A) is 16,000 to 30,000.

It is preferable that the glass fiber (B) is treated with an epoxy-based bundling agent or an urethane-based bundling agent and the average cross-sectional diameter of the fiber is 6 to 20 占 퐉.

It is preferable that the glass fiber (B) has a flat cross section in which the average value of the long diameter of the fiber cross section is 10 to 50 占 퐉 and the average value of the long diameter to the short diameter (long diameter / short diameter) is 2 to 8.

It is preferable that the phosphorous ester compound (C) is a compound represented by the following formula (1) or a compound represented by the following formula (2).

In general formula (1)

(Wherein 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 an integer of 0 to 3)

In general formula (2)

(In the general formula (2), R ³ represents an alkyl group of 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.)

Wherein the phosphorous acid ester compound (C) represented by the general formula (1) is at least one selected from the group consisting of 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10- -3,9-diphosphaspiro [5,5] undecane or 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) Oxa-3,9-diphosphaspiro [5,5] undecane.

It is preferable that the phosphite ester compound (C) represented by the general formula (2) is tris (2,4-di-t-butylphenyl) phosphite.

The fatty acid ester (D) is preferably pentaerythritol tetra stearate.

The thermoplastic elastomer (E) is preferably contained in an amount of 0.2 to 20 parts by weight based on 100 parts by weight of the polycarbonate resin (A) and the glass fiber (B).

It is preferable that the thermoplastic elastomer (E) is a hydrogenated styrene-based thermoplastic elastomer or a polyester-based thermoplastic elastomer.

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

The glass fiber-reinforced polycarbonate resin composition of the present invention is excellent in the mechanical strength and rigidity of the glass fiber-reinforced polycarbonate resin composition and is excellent in releasability and thermal stability, so that its industrial utility value is high. For example, it can be used as a substitute for a thin-walled housing used in an electric appliance or an electronic appliance, or as a substitute for a metal product used for an internal chassis, and the weight of the product can be reduced. In addition, when an external force is applied to a molded article obtained from such a resin composition, the occurrence of the problem that the molded article is bent and damages the electronic parts stored in the molded article is suppressed as much as possible.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples and the like, but the present invention is not limited to the following embodiments and examples, and the present invention is not limited to the embodiments and examples, Can be implemented.

The fiber-reinforced polycarbonate resin composition of the present invention is characterized in that the phosphorous ester 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) And 0.1 to 2 parts by weight of a fatty acid ester (D).

The polycarbonate resin (A) used in the present invention is prepared by a phosgene method in which various dihydroxy diaryl compounds are reacted with phosgene or an ester exchange method in which a dihydroxy diaryl compound is reacted with a carbonic ester such as diphenyl carbonate And a typical example thereof is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).

Examples of the dihydroxy diaryl compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2- (4-hydroxy-3-propylphenyl) propane, 2,2-bis (4-hydroxy- (Hydroxyaryl) alkanes such as 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy-3,5-dichlorophenyl) (Hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy- Dihydroxydiaryl ethers such as 3'-dimethyl diphenyl ether, dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydro Dihydroxydialylsulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfone, Dihydroxy-3,3'-dimethyldiphenylsulfone and dihydroxydiarylsulfone such as dihydroxy-3,3'-dimethyldiphenylsulfone.

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

The dihydroxyaryl compound may be mixed with a trivalent or higher phenol compound as shown below. Examples of the phenol having three or more valences include fluoroglucine, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6- - (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -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 19,000 to 26,000 from the viewpoint of molding processability and strength. In preparing such a polycarbonate resin, a molecular weight regulator, a catalyst, and the like can be used as needed.

The blending amount of the polycarbonate resin (A) is preferably 40 to 80% by weight, more preferably 50 to 70% by weight. When it exceeds 80% by weight, the rigidity is poor, and when it is less than 40% by weight, a molded article which is poor in thermal stability occurs.

The glass fiber (B) to be used in the present invention is not particularly limited, and may be a round-section glass fiber whose cross section having an average value of the ratio of the major axis to the minor axis (long diameter / minor diameter) And the average value of the ratio of the short diameter (long diameter / short diameter) is 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 improvement of the mechanical strength is not sufficient, and when the polycarbonate resin exceeding 8 mm is produced, the dispersibility of the glass fiber into the polycarbonate resin is inferior, And the productivity is likely to deteriorate.

In the case where the glass fiber (B) is a circularly-sectioned glass fiber whose cross section having an average value of the ratio of the major axis to the minor axis of the cross section of the fiber (long diameter / short diameter) is 1 to 1.5, the glass fiber preferably has a diameter of 6 to 20 μm Do. When the diameter of the glass fiber is less than 6 占 퐉, the mechanical strength is poor and when it exceeds 20 占 퐉, the appearance tends to deteriorate. The diameter of the glass fiber is more preferably 7 to 18 占 퐉, and still more preferably 8 to 15 占 퐉.

The circular cross-section glass fibers having an average value of the ratio of the major axis to the minor axis (long diameter / short diameter) of the cross section of the fibers available from the market and having a cross section of 1 to 1.5 are 10 μm in diameter or 13 μm in diameter, Is 2 to 6 mm. Examples of the glass fiber available on the market include CS321 and CS311 manufactured by KCC, and CS03MAFT737 manufactured by OWENS CORNING JAPAN.

In the case where the glass fiber (B) is a flat-section glass fiber having an average value of the ratio of the major axis to the minor axis of the cross section of the fiber (long diameter / short diameter) is 2 to 8, the average value of the long diameter is 10 to 50 μm, preferably 15 to 40 μm And preferably 25 to 30 mu m. The average value of the ratio of the long diameter to the short diameter (long diameter / short diameter) is 2 to 8, preferably 2 to 7, and more preferably 2.5 to 5. These are prepared according to any conventionally known method.

When the diameter of the flat glass fiber is less than 10 m, the production is difficult. When the diameter is more than 50 m, the appearance of the surface of the molded product of the polycarbonate resin composition may be deteriorated. When the ratio of the long diameter to the short diameter is less than 2, the dimensional stability is poor, while when the ratio is more than 8, the strength may be poor.

Examples of the flat-section glass fiber having an average value of the ratio of the major axis to the minor axis (long diameter / short diameter) of the cross section of the fiber available on the market are 2 to 8, for example, CSG 3PA-820 or CSG 3PA-830 manufactured by NITTO BOSEKI .

The glass fiber (B) can be surface-treated with a silane coupling agent such as amino silane or epoxy silane for the purpose of improving the adhesion with the polycarbonate resin. When glass fibers are handled, they can be focused by a focusing agent such as urethane or epoxy for the purpose of improving handling properties.

The blending amount of the glass fiber (B) is 20 to 60% by weight in the resin composition. If it exceeds 60% by weight, a molded article with poor appearance is generated. If it is less than 20% by weight, strength and rigidity are poor. A more preferable blending amount is 30 to 50 wt%, and most preferably 40 to 45 wt%.

In the glass fiber reinforced polycarbonate resin composition of the present invention, a phosphorous ester compound (C) is blended. By blending the phosphorous ester compound (C), a glass fiber-reinforced polycarbonate resin composition excellent in thermal stability can be obtained without damaging the inherent properties such as mechanical strength inherent in the polycarbonate resin (A).

As the phosphorous ester compound (C), the compound represented by the above general formula (1) is particularly suitable.

In general formula (1)

(Wherein 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 an integer of 0 to 3)

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

Examples of the phosphorous ester compound (C) include, for example, a compound represented by the general formula (2) in addition to the compound represented by the general formula (1).

In general formula (2)

(Wherein R ³ represents an alkyl group of 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)

In the general formula (2), R ³ is an alkyl group having 1 to 20 carbon atoms, and is preferably an alkyl group having 1 to 10 carbon atoms.

Examples of the compound represented by the general formula (2) include triphenylphosphite, tricresylphosphite, tris (2,4-di-t-butylphenyl) phosphite, trisnonylphenylphosphite, etc. . Of these, tris (2,4-di-t-butylphenyl) phosphite is particularly suitable, and for example Irgafos 168 ("Irgafos", manufactured by BASF) is commercially available as BASF Societas Europeae It is possible.

The amount of the phosphorous ester compound (C) is 0.01 to 0.2 parts by weight based on 100 parts by weight of the resin composition comprising the polycarbonate resin (A) and the glass fiber (B). If the blending amount exceeds 0.2 parts by weight, the thermal stability is deteriorated. If it is less than 0.01 part by weight, the thermal stability is poor. More preferably 0.02 to 0.1 part by weight, and most preferably 0.03 to 0.05 part by weight.

In the glass fiber-reinforced polycarbonate resin composition of the present invention, a fatty acid ester (D) is blended. By blending the fatty acid ester (D), it is possible to obtain a glass fiber-reinforced polycarbonate resin composition excellent in releasability and thermal stability without damaging the inherent properties such as mechanical strength of the polycarbonate resin (A).

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

Examples of the aliphatic carboxylic acid include saturated or unsaturated monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids. The aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Of 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 aliphatic carboxylic acids such as palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, , Tetra triacontanoic acid, montanic acid, glutaric acid, adipic acid, and azelaic acid.

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

Specific examples of the alcohol include, for example, alcohols such as octanol, decanol, dodecanol, tetradecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2- Hydroxy perfluoropropanol, neopentylene glycol, ditrimethylol propane, dipentaerythritol, and the like.

Specific examples of the fatty acid ester (D) include, for example, behenyl behenate, octyldodecyl behenate, stearyl stearate, glycerin monopalmitate, glycerin monostearate, glycerin monooleate, glycerin distearate , Glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate. These may be used singly or in combination of two or more kinds . Among them, pentaerythritol stearate is suitable, and LOXIOL VPG861 manufactured by Cognis, for example, is commercially available.

The blending amount of the fatty acid ester (D) is 0.1 to 2 parts by weight based on 100 parts by weight of the resin composition comprising the polycarbonate resin (A) and the glass fiber (B). If the blending amount exceeds 2 parts by weight, stable production becomes difficult. If it is less than 0.1 part by weight, the releasability is poor. More preferably from 0.3 to 1.5 parts by weight, and most preferably from 0.5 to 1.0 part by weight.

The thermoplastic elastomer (E) is preferably blended in the glass fiber-reinforced polycarbonate resin composition of the present invention. 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 inherently possessed by the polycarbonate resin (A) are not impaired A glass fiber-reinforced polycarbonate resin composition excellent in appearance of a molded article can be obtained.

The thermoplastic elastomer (E) is not particularly limited, and examples thereof include thermoplastic elastomers such as 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 a polyamide thermoplastic elastomer. . Among them, a hydrogenated styrene type thermoplastic elastomer and a polyester type thermoplastic elastomer are preferable.

The hydrogenated styrenic thermoplastic elastomer may be selected from the group consisting of a polystyrene-poly (ethylene / propylene) block copolymer, a polystyrene-poly (ethylene / propylene) block-polystyrene copolymer, a polystyrene- Poly (ethylene-ethylene / propylene) block-polystyrene copolymer. These hydrogenated styrene-based thermoplastic elastomers may also be those modified with maleic anhydride or amine. These may be used alone or in combination of two or more. Of these, polystyrene-poly (ethylene / butylene) block-polystyrene copolymers are suitable, for example, SEPTON 8004, 8007 manufactured by KURARAY Co., Tuftec H1062, H1051 and H1043 manufactured by Asahi Kasei are commercially available .

From the viewpoint of the appearance of a molded article, the content of the styrene unit is preferably 55% by weight or more in the hydrogenated styrene-based thermoplastic elastomer. As the hydrogenated styrene thermoplastic elastomer having a styrene unit content of 55 wt% or more, for example, SEPTON 8104 manufactured by KURARAY, Tuftec H1043 manufactured by Asahi Kasei, and the like are commercially available.

The polyester-based thermoplastic elastomer is a thermoplastic elastomer comprising a multi-block copolymer composed of a hard segment and a soft segment (at least one soft segment selected from the group consisting of an aliphatic polyether, an aliphatic polyester and a polycarbonate to a hard segment made of an aromatic polyester Linked block copolymer). As the hard segment, an aromatic polyester is suitable. Specific examples thereof include polybutylene terephthalate, polybutylene naphthalate and the like. These may be used alone or in combination of two or more.

As the soft segment, aliphatic polyether, aliphatic polyester and polycarbonate are suitable, and specific examples include poly (epsilon -caprolactone), polytetramethylene glycol, polyalkylene carbonate and the like. These may be used alone or in combination of two or more. As such a block copolymer (copolymer), at least one copolymer selected from the group consisting of a polyester-polyester copolymer, a polyester-polyether copolymer, and a polyester-polycarbonate copolymer is preferably used.

Examples of the polyester-based thermoplastic elastomer (E) available on the market include Hytrel manufactured by DU PONT-TORAY, and PELPRENE manufactured by TOYOBO.

As the thermoplastic elastomer, a hydrogenated styrene-based thermoplastic elastomer and a polyester-based thermoplastic elastomer may be used in combination. A glass fiber-reinforced polycarbonate resin composition having improved adhesion between the polycarbonate resin (A) and the glass fiber (B) can be obtained by using both in combination.

The blending amount of the polyester thermoplastic elastomer (E) used in the present invention is 0.2 to 20 parts by weight per 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) 20 parts by weight. If the blending amount exceeds 20 parts by weight, stable production becomes difficult, which is not preferable. When the amount is less than 0.2 part by weight, adhesion between the polycarbonate resin (A) and the glass fiber (B) is poor, which is not preferable. More preferably from 0.3 to 15 parts by weight, and most preferably from 0.4 to 10 parts by weight.

In the glass fiber reinforced polycarbonate resin composition of the present invention, for example, a polycarbonate resin is fed from a first feeder (raw material feed port) into an extruder barrel, the glass fiber is melted to a second feeder (For example, a kneading disk) or the like which is generally available to the screw used for kneading after supplying the kneaded product from the extruder barrel to the extruder barrel through the extruder barrel, Or by appropriately changing the arrangement of the kneaded material. A drawing forming method in which a polycarbonate resin is impregnated into the fiber while pulling the glass fiber can be used.

In addition, the polycarbonate resin composition of the present invention may contain various resins, antioxidants, fluorescent whitening agents, pigments, dyes, carbon black, fillers, release agents, ultraviolet absorbers, antistatic agents, An additive such as a flame retardant, an electrodeposition agent (liquid paraffin, epoxidized soybean oil, etc.), a flame retardant, an organic metal salt, and a polytetrafluoroethylene resin for preventing dropping may be added.

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 These may be used alone or in combination of two or more.

Examples of the antioxidant include phosphorus antioxidants and phenol antioxidants. Among them, a semi-hindered phenol-based antioxidant and a hindered phenol-based antioxidant are suitably used. Examples of the semi-hindered phenol antioxidant include SUMILIZER GA-80 manufactured by Sumitomo Chemical Co., Ltd., and hindered phenol antioxidants include Irganox 1076 manufactured by BASF. .

The resin molded article of the present invention is characterized by being obtained by molding the fiber-reinforced polycarbonate resin composition. As the molding method of the fiber-reinforced resin molded article of the present invention, extrusion molding or injection molding is used. For extrusion molding, molding such as sheet or extrusion molding using an extruder, or injection molding, a mold capable of molding the molded article and an injection molding machine of 100 to 200T class are used. The molding processing temperature is preferably 230 to 260 占 폚. Since the molded body is excellent in appearance, it can be suitably applied to a housing such as a camera or a smart phone.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily changed or changed within a range not departing from the gist of the present invention. Unless specifically stated otherwise, "%" and "part" in the examples indicate "% by weight" and "part by weight" based on weight standards, respectively.

Details of the raw materials used are as follows.

1. Polycarbonate resin (A):

1-1. Polycarbonate resin synthesized with bisphenol A and phosgene

(CALIBER 200-20, Sumika Styron Polycarbonate, viscosity average molecular weight 19000, hereinafter referred to as " PC1 "

1-2. Polycarbonate resin synthesized from bisphenol A and phosgene

(CALIBER 200-13 manufactured by Sumika Styron Polycarbonate, viscosity average molecular weight: 21,000, hereinafter referred to as "PC2"

1-3. Polycarbonate resin synthesized from bisphenol A and phosgene

(CALIBRE 200-3 manufactured by Sumika Styron Polycarbonate, viscosity average molecular weight: 28,000, hereinafter referred to as "PC3" briefly)

2. Glass fiber (B):

2-1. Circular cross-section fiberglass

(CS321 manufactured by KCC, fiber diameter: 10 m, fiber length: 3 mm,

Epoxy-based bundling agent, hereinafter referred to as " GF1 "

2-2. Circular cross-section fiberglass

(CS311 manufactured by KCC, fiber diameter: 10 m, fiber length: 3 mm,

Urethane-based bundling agent, hereinafter referred to simply as " GF2 "

2-3. Flat cross-section glass fiber

(Abbreviated as "GF3", CSG 3PA-830 manufactured by Nitto Boseki, long diameter 28 μm, short diameter 7 μm, fiber length 3 mm, epoxy /

3. Phosphoric ester compound (C):

3-1. (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5 , 5] undecan

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

Irgafos 168 (trade name, manufactured by BASF, hereinafter referred to as " compound C2 "),

3-3. Bis [2,4-bis (?,? - dimethylbenzyl) phenoxy] -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5 ] Undecan

Doverphos S-9228 (trade name, manufactured by Dover Chemical Co., hereinafter abbreviated as " C3 "),

4. Fatty acid ester (D):

Pentaerythritol stearate

LOXIOL VPG861 (trade name, manufactured by Cognis, hereinafter abbreviated as " D1 "),

5. Thermoplastic elastomer (E):

5-1. The hydrogenated styrenic thermoplastic elastomer

5-1-1. Polystyrene-poly (ethylene / butylene) block-polystyrene copolymer

SEPTON 8104 (trade name, manufactured by KURARAY Co., styrene unit content 60 wt%, briefly described as "E1")

5-1-2. Polystyrene-poly (ethylene / butylene) block-polystyrene copolymer

SEPTON 8007L (trade name, manufactured by KURARAY, styrene unit content 30% by weight, referred to briefly as "E2")

5.2. The polyester-based thermoplastic elastomer

5-2-1. Polyester-polyester copolymer

PELPRENE S-3001 (trade name, manufactured by TOYOBO, briefly described as "E3")

Hard segment: Polybutylene terephthalate

Soft segment: poly (epsilon -caprolactone)

5-2-2. Polyester-polyether copolymer

PELPRENE P-150B (trade name, manufactured by TOYOBO, briefly described as "E4")

Hard segment: Polybutylene terephthalate

Soft segment: polytetramethylene glycol

5-2-3. Polyester-polyether copolymer

PELPRENE EN-3000 (trade name, manufactured by TOYOBO, simply referred to as " E5 ")

Hard segment: Polybutylene naphthalate

Soft segment: polytetramethylene glycol

5-2-4. Polyester-polycarbonate copolymer

PELPRENE C-2003 (trade name, manufactured by TOYOBO, briefly described as "E6")

Hard segment: Polybutylene terephthalate

Soft segment: polyalkylene carbonate

Examples 1 to 67 and Comparative Examples 1 to 32 (Production of pellets)

The above various components were kneaded at a melting temperature of 300 占 폚 using a twin-screw extruder (TEM-37SS, manufactured by TOSHIBA MACHINE) at the mixing ratios shown in Tables 1 to 10 to obtain a glass fiber reinforced polycarbonate resin composition. The glass fiber reinforced polycarbonate resin is produced by feeding a polycarbonate resin, a phosphorous ester compound, a fatty acid ester and a thermoplastic elastomer into a extruder barrel from a first feeder (raw material feed port), sufficiently melting the resin composition, (Filler feed port) into an extruder barrel, followed by kneading to obtain a glass fiber-reinforced polycarbonate resin composition pellet.

≪ Bending modulus of molded article >

Each of the pellets of the resin compositions obtained above was dried at 125 DEG C for 4 hours, and then a test specimen having a thickness of 4 mm according to the ISO test method was set at an injection pressure of 100 MPa using an injection molding machine (ROBOSHOT S2000i100B, manufactured by FANUC Corporation) And the bending elastic modulus (rigidity) was measured according to ISO 178 using the obtained test pieces. The bending modulus of elasticity was at least 6000 MPa.

<Thermal Stability>

The pellets and the bending elastic modulus (rigidity) of the various resin compositions obtained above were measured and dissolved in dichloromethane, and the insoluble matter in the solution was filtered using a NO.1 filter paper. The filtrate was dried up, and a predetermined amount (0.25 g) of the obtained polymer was dissolved in 50 ml of dichloromethane. Using a Cannon-Fenske viscometer, the viscosity of the diluted dichloromethane solution was measured at 23 占 폚, and the viscosity average molecular weight of each test piece was determined using the SCHNELL equation.

(Wherein the Schnell) [η] = 1.23 × 10 -4 · M 0.83

[?]: intrinsic viscosity, M: viscosity average molecular weight

The lowering of the molecular weight, which is an index of the thermal stability, made the value (DELTA Mv) obtained by subtracting the viscosity average molecular weight of the test piece from the viscosity average molecular weight of the pellets less than 2000.

<Formality>

The pellets of the various resin compositions obtained above were dried at 125 DEG C for 4 hours, respectively, and then molded using an injection molding machine (ROBOSHOT S2000i100B, manufactured by FANUC Corporation) under the conditions of a cylinder set temperature of 300 DEG C, a mold temperature of 50 DEG C, The releasability was evaluated. The mold was subjected to measurement of the protruding load applied to the protruded fin when the cup-shaped molded product was molded using a cup-shaped mold-resistant mold (shape of the molded product: 70 mm in diameter, 20 mm in height and 4 mm in thickness) As a criterion for evaluation, a mold release resistance value of less than 800N was good.

<Appearance of molded article>

The roughness of the surface of the molded product with the glass fiber was observed with naked eyes for the test piece whose bending elastic modulus (rigidity) was measured, and it was determined that the surface of the molded product was not roughened by the glass fiber.

&Lt; Adhesion property between polycarbonate resin and glass fiber >

The cross section of the test piece on which the flexural modulus (rigidity) was measured was observed at 500-fold using a scanning electron microscope (S-3400N, manufactured by Hitachi), and the glass fiber having the resin- , And the glass fiber was regarded as having good adhesiveness, and is indicated by &quot; &quot; in the table and defective is indicated by &quot; x &quot; Before the observation, the test piece was subjected to gold deposition (gold deposition) using an ion sputter (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 which did not satisfy the constituent requirements of the present invention had the following defects respectively. In Comparative Example 1, the blending amount of the glass fiber (B) was smaller than the specified amount, and the bending elastic modulus was inferior. In Comparative Example 2, the blending amount of the glass fiber (B) was larger than the specified amount, and pellets could not be produced. In Comparative Example 3, the compounding amount of the phosphorous ester compound (C) was smaller than the specified amount, and the thermal stability was inferior. In Comparative Example 4, the compounding amount of the phosphorous ester compound (C) was larger than the specified amount, and the thermal stability was inferior. In Comparative Example 5, the amount of the fatty acid ester (D) was less than the specified amount, and the releasability was inferior. In Comparative Example 6, the blending amount of the fatty acid ester (D) was larger than the specified amount, and pellets could not be produced.

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 which did not satisfy the constituent requirements of the present invention had the following defects respectively. In Comparative Example 7, the blending amount of the glass fiber (B) was smaller than the specified amount, and the bending elastic modulus was inferior. In Comparative Example 8, the blending amount of the glass fiber (B) was larger than the specified amount, and pellets could not be produced. In Comparative Example 9, the compounding amount of the phosphorous acid ester compound (C) was smaller than the specified amount, and the thermal stability was inferior. In Comparative Example 10, the compounding amount of the phosphorous ester compound (C) was larger than the specified amount, and the thermal stability was inferior. In Comparative Example 11, the amount of the fatty acid ester (D) was less than the specified amount, and the releasability was poor. In Comparative Example 12, the blending amount of the fatty acid ester (D) was larger than the specified amount, and pellets could not be produced. In Comparative Example 13, the blending amount of the hydrogenated styrene-type 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 blending amount of the hydrogenated styrene-based thermoplastic elastomer (E) was larger than the specified amount, and the appearance of the molded article 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 which did not satisfy the constituent requirements of the present invention had the following defects respectively. In Comparative Example 15, the blending amount of the glass fiber (B) was smaller than the specified amount, and the bending elastic modulus was inferior. In Comparative Example 16, the blending amount of the glass fiber (B) was larger than the specified amount, and pellets could not be produced. In Comparative Example 17, the amount of the phosphorous ester compound (C) was less than the specified amount, and the thermal stability was inferior. In Comparative Example 18, the blending amount of the phosphorous ester compound (C) was larger than the specified amount, and the thermal stability was inferior. In Comparative Example 19, the amount of the fatty acid ester (D) was less than the specified amount, and the releasability was inferior. In Comparative Example 20, the blending amount of the fatty acid ester (D) was larger than the specified amount, and pellets could not be produced. In Comparative Example 21, the blending amount of the polyester 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 blending amount of the polyester-based thermoplastic elastomer (E) was larger than the specified amount, and the production of the pellets was impossible. In Comparative Example 23, the blending amount of the hydrogenated styrene thermoplastic elastomer (F) was larger than the specified amount, and the appearance of the molded article 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 to 32, those which did not satisfy the constituent requirements of the present invention had the following defects respectively. In Comparative Example 24, the blending amount of the glass fiber (B) was smaller than the specified amount, and the bending elastic modulus was inferior. In Comparative Example 25, the blending amount of the glass fiber (B) was larger than the specified amount, and the production of the pellets was impossible. In Comparative Example 26, the compounding amount of the phosphorous ester compound (C) was less than the specified amount, and the thermal stability was inferior. In Comparative Example 27, the compounding amount of the phosphorous ester compound (C) was larger than the specified amount, and the thermal stability was inferior. 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 blending amount of the fatty acid ester (D) was larger than the specified amount, and pellets could not be produced. In Comparative Example 30, the blending amount of the polyester 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 31, the blending amount of the polyester-based thermoplastic elastomer (E) was larger than the specified amount, and the production of pellets was impossible. In Comparative Example 32, the blending amount of the hydrogenated styrene-type thermoplastic elastomer (F) was larger than the specified amount, and the appearance of the molded article was inferior.

The glass fiber-reinforced polycarbonate resin composition of the present invention is excellent in the mechanical strength and rigidity of the glass fiber-reinforced polycarbonate resin composition and is excellent in releasability and thermal stability, so that its industrial utility value is high. For example, it can be used as a substitute for a thin-walled housing used in an electric appliance or an electronic appliance, or as a substitute for a metal product used for an internal chassis, and the weight of the product can be reduced. In addition, when an external force is applied to a molded article obtained from such a resin composition, the occurrence of a problem that the molded article is bent and damages electronic components stored in the molded article is suppressed as much as possible.

Claims (11)

0.01 to 0.2 parts by weight of a phosphorous acid ester compound (C) and 100 to 50 parts by weight of a fatty acid ester (D), based on 100 parts by weight of a resin composition comprising 40 to 80% by weight of a polycarbonate resin (A) ) Of 0.1 to 2 parts by weight based on 100 parts by weight of the fiber-reinforced polycarbonate resin composition. The method according to claim 1,
Wherein the polycarbonate resin (A) has a viscosity average molecular weight of 16,000 to 30,000. The method according to claim 1 or 2,
Wherein the glass fiber (B) is treated with an epoxy-based bundling agent or an urethane-based bundling agent, and the fiber cross-section has an average diameter of 6 to 20 占 퐉. The method of claim 3,
The fiber-reinforced polycarbonate resin composition according to any one of claims 1 to 3, wherein the glass fiber (B) has a flat cross section with an average value of the long diameter of the fiber cross section of 10 to 50 占 퐉 and an average value of the long diameter / short diameter ratio (long diameter / short diameter) The method according to any one of claims 1 to 4,
Wherein the phosphorous ester compound (C) is a compound represented by the following general formula (1) or a compound represented by the following general formula (2).
In general formula (1)

(Wherein 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 an integer of 0 to 3)
In general formula (2)

(In the general formula (2), R ³ represents an alkyl group of 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 method of claim 5,
Wherein the phosphorous acid ester compound (C) represented by the general formula (1) is at least one selected from the group consisting of 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10- -3,9-diphosphaspiro [5,5] undecane or 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) Oxa-3,9-diphosphaspiro [5,5] undecane. The method of claim 5,
Wherein the phosphite-based compound (C) represented by the general formula (2) is tris (2,4-di-t-butylphenyl) phosphite. The method according to any one of claims 1 to 7,
Wherein the fatty acid ester (D) is pentaerythritol tetra stearate. The method according to any one of claims 1 to 8,
The fiber-reinforced polycarbonate resin composition according to claim 1, wherein the thermoplastic elastomer (E) is contained in an amount of 0.2 to 20 parts by weight based on 100 parts by weight of the polycarbonate resin (A) and the glass fiber (B). The method of claim 9,
Wherein the thermoplastic elastomer (E) is a hydrogenated styrene-based thermoplastic elastomer or a polyester-based thermoplastic elastomer. A resin molded article obtained by molding the fiber-reinforced polycarbonate resin composition according to any one of claims 1 to 10.