JP2016222774A - Fiber-reinforced polypropylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition excellent in rigidity, dimensional stability and chemical resistance.SOLUTION: There is provided a fiber-reinforced polypropylene resin composition which contains: a resin component composed of 50 to 90 pts.wt. of (A) a polypropylene resin (A component) and 50 to 10 pts.wt. of (B) a polycarbonate resin (B component); and 5 to 100 pts.wt. of a carbon fiber (C component) with respect to 100 pts.wt. of the resin component, the carbon fiber (C component) having a surface oxygen concentration (O/C) of 0.15 or more which is a ratio of atom number of oxygen (O) and carbon (C) of a fiber surface measured by an X-ray photoelectron spectroscopy.SELECTED DRAWING: None

Description

  The present invention relates to a fiber reinforced polypropylene resin composition. More specifically, the present invention relates to a fiber-reinforced polypropylene resin composition having excellent rigidity, dimensional stability, and chemical resistance, and suitable for electrical / electronic parts, home appliances, automobile-related parts, infrastructure-related parts, housing-related parts, and the like.

  Polypropylene resins are widely used industrially in electrical and electronic parts, home appliances, housings, packaging materials, automobile parts and the like because they are excellent in moldability and chemical resistance and have a low specific gravity. Furthermore, in recent years, it has been widely used for automobile applications such as bumpers and interior / exterior parts due to the demand for automobile weight reduction. However, compared with so-called engineering plastics, heat resistance and dimensional stability are insufficient.

  On the other hand, polycarbonate resin, among other engineering plastics, is particularly excellent in impact resistance, heat resistance, creep resistance, and dimensional stability, so it can be used in electrical / electronic / OA equipment casings and parts, automotive interior / exterior parts. It is used in a wide range of fields such as furniture, musical instruments, and miscellaneous goods.

  Various attempts have been made to blend polypropylene resin and polycarbonate resin for the purpose of imparting characteristics such as dimensional stability of polycarbonate resin to polypropylene resin. However, the compatibility between the polypropylene resin and the polycarbonate resin is not good, and there is a problem of delamination and significant physical property deterioration.

  Therefore, various resin compositions have been proposed for the purpose of improving the compatibility. For example, a resin composition using an elastomer graft-modified with a hydroxyl group-containing vinyl monomer as a compatibilizer (see Patent Documents 1 and 2), polypropylene modified with a hydroxyl group-containing vinyl monomer as a compatibilizer, ethylene and carbon number A resin composition using an ethylene-α-olefin copolymer composed of 4 or more α-olefins as an impact resistance agent (see Patent Document 3), and a styrene-ethylene-butylene-styrene block copolymer as a compatibilizing agent. Examples thereof include resin compositions (see Patent Documents 4 and 5). As described above, a polypropylene resin composition to which an elastomer component is added as a compatibilizing agent is excellent in impact resistance but has insufficient rigidity and strength. As a matter of course, the addition of the fibrous filler improves the rigidity and strength to some extent. However, in the presence of the elastomer, the effect of improving the rigidity by adding the fibrous filler is not sufficient, and therefore the fiber is more than necessary. There is a problem that a filler needs to be added.

JP-A-7-330972 JP-A-8-134277 JP 2005-132937 A Japanese Patent Laid-Open No. 5-17633 JP 2014-88475 A

  The object of the present invention is a fiber reinforced polypropylene resin composition that is excellent in rigidity, dimensional stability and chemical resistance, and is suitably used for electrical / electronic parts, home appliances, automobile-related parts, infrastructure-related parts, housing-related parts, etc. It is to provide an article and a molded article comprising the article.

  As a result of intensive studies to solve such problems, the present inventors have found that a fiber-reinforced polypropylene resin composition comprising a polypropylene resin, a polycarbonate resin, and a specific carbon fiber causes delamination due to incompatibility and a significant decrease in physical properties. And found surprising effects of excellent rigidity, dimensional stability and chemical resistance. That is, according to the present invention, (C) 100 parts by weight of (A) polypropylene resin (component A) 50 to 90 parts by weight and (B) 50 to 10 parts by weight of polycarbonate resin (component B) (C) ) Carbon fiber (C component) having a surface oxygen concentration (O / C) which is a ratio of the number of atoms of oxygen (O) and carbon (C) on the fiber surface measured by X-ray photoelectron spectroscopy is 0.15 or more ) Is contained in an amount of 5 to 100 parts by weight.

  One of the more preferable embodiments of the present invention is characterized in that (2) the component B is a polycarbonate resin containing 20 to 100 mol% of the carbonate constituent unit represented by the following formula [1] in all carbonate constituent units. It is a fiber reinforced polypropylene resin composition as described in said structure (1).

In the general formula [1], R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 20 carbon atoms. A cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, and the number of carbon atoms It represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. A and b are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2].

(In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a carbon atom. Represents a group selected from the group consisting of an aryl group having 6 to 14 carbon atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 to 14 carbon atoms Aryl group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and carbon R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or 6 to 12 carbon atoms. Or a plurality of them, which may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7, e is a natural number, f Is 0 or a natural number, e + f is a natural number of 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms)

One of the more preferable embodiments of the present invention is the above-mentioned constitution (1), wherein 1 to 20 parts by weight of (D) modified polyolefin resin (D component) is contained per 100 parts by weight of (3) resin component Or it is a fiber reinforced polypropylene resin composition as described in (2).
One of the more preferable embodiments of the present invention is (4) an injection-molded article comprising the fiber-reinforced polypropylene resin composition according to any one of the above-described configurations (1) to (3).

Hereinafter, the present invention will be specifically described.
(A component: polypropylene resin)
The polypropylene resin used as the component A of the present invention is a propylene polymer, but in the present invention, a copolymer with other monomers is also included. Examples of the polypropylene resin of the present invention include a homopolypropylene resin, a block copolymer of propylene, ethylene, and an α-olefin having 4 to 10 carbon atoms (also referred to as “block polypropylene”), propylene, ethylene, and 4 to 4 carbon atoms. 10 random copolymers with α-olefin (also referred to as “random polypropylene”). “Block polypropylene” and “random polypropylene” are also collectively referred to as “polypropylene copolymer”.

In the present invention, one or more of the above-mentioned homopolypropylene resin, block polypropylene, and random polypropylene may be used as the polypropylene resin, and among them, homopolypropylene and block polypropylene are preferable. In addition, the modified polypropylene resin which is D component is not contained in a polypropylene resin.
Examples of the α-olefin having 4 to 10 carbon atoms used for the polypropylene copolymer include 1-butene, 1-pentene, isobutylene, 3-methyl-1-butene, 1-hexene, and 3,4-dimethyl-1. -Butene, 1-heptene, 3-methyl-1-hexene are included.

The content of ethylene in the polypropylene copolymer is preferably 5% by weight or less in all monomers. The content of the α-olefin having 4 to 10 carbon atoms in the polypropylene copolymer is preferably 20% by weight or less in all monomers.
The polypropylene copolymer is preferably a copolymer of propylene and ethylene or a copolymer of propylene and 1-butene, and particularly preferably a copolymer of propylene and ethylene.

  The melt flow rate (230 ° C., 2.16 kg) of the polypropylene resin in the present invention is preferably 0.1 to 5 g / 10 min, more preferably 0.2 to 4 g / 10 min, and 0.3 to 3 g / 10 min is particularly preferable. If the melt flow rate of the polypropylene resin is less than 0.1 g / 10 min, the moldability is inferior due to high viscosity, and if it exceeds 5 g / 10 min, sufficient toughness may not be exhibited. The melt flow rate is also called “MFR”. MFR was measured according to ISO1133.

  Content of A component is 50-90 weight part in 100 weight part of resin components, Preferably it is 60-90 weight part, More preferably, it is 70-90 weight part, Most preferably, it is 80-90 weight part. If the component A is less than 50 parts by weight, the chemical resistance is not sufficient, and if it exceeds 90 parts by weight, the tensile fracture strength and dimensional stability are not sufficient, which is not preferable.

(B component: polycarbonate resin)
The polycarbonate resin used as the component B of the present invention is usually obtained by reacting a dihydroxy compound and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, and a carbonate prepolymer by a solid phase transesterification method. A polymerized product or a product obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method. The dihydroxy component used here may be any one that is usually used as a dihydroxy component of an aromatic polycarbonate, and may be a bisphenol or an aliphatic diol. As the bisphenols, bisphenols represented by the following formula [3] are preferably used.

In the general formula [3], R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 20 carbon atoms. A cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, and the number of carbon atoms It represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. A and b are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [4].

(In the above general formula [4], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a carbon atom. Represents a group selected from the group consisting of an aryl group having 6 to 14 carbon atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 to 14 carbon atoms Aryl group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and carbon R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or 6 to 12 carbon atoms. Or a plurality of them, which may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7, e is a natural number, f Is 0 or a natural number, e + f is a natural number of 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms)

  Specific examples of bisphenols include, for example, 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl). -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3, 3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3′-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3 -T-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydride) Xylphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-) 4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9- Bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4′-dihydroxydiphenyl ether 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 4, , 4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3 , 3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 2,2′-diphenyl-4,4′-sulfonyldiphenol, 4,4′-dihydroxy-3,3 '-Diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4 -Hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydroxyphenyl) cycl Hexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1,3- Adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, and the like.

  Examples of the aliphatic diols include 2,2-bis- (4-hydroxycyclohexyl) -propane, 1,14-tetradecanediol, octaethylene glycol, 1,16-hexadecanediol, 4,4′-bis (2- Hydroxyethoxy) biphenyl, bis {(2-hydroxyethoxy) phenyl} methane, 1,1-bis {(2-hydroxyethoxy) phenyl} ethane, 1,1-bis {(2-hydroxyethoxy) phenyl} -1- Phenylethane, 2,2-bis {(2-hydroxyethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-methylphenyl} propane, 1,1-bis {(2-hydroxyethoxy) ) Phenyl} -3,3,5-trimethylcyclohexane, 2,2-bis {4- (2-hydroxy) Ethoxy) -3,3′-biphenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-isopropylphenyl} propane, 2,2-bis {3-tert-butyl-4- (2-hydroxy) Ethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) phenyl} butane, 2,2-bis {(2-hydroxyethoxy) phenyl} -4-methylpentane, 2,2-bis {(2 -Hydroxyethoxy) phenyl} octane, 1,1-bis {(2-hydroxyethoxy) phenyl} decane, 2,2-bis {3-bromo-4- (2-hydroxyethoxy) phenyl} propane, 2,2- Bis {3,5-dimethyl-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {3-cyclohexyl-4- (2-hydroxyethyl) Xyl) phenyl} propane, 1,1-bis {3-cyclohexyl-4- (2-hydroxyethoxy) phenyl} cyclohexane, bis {(2-hydroxyethoxy) phenyl} diphenylmethane, 9,9-bis {(2-hydroxy) Ethoxy) phenyl} fluorene, 9,9-bis {4- (2-hydroxyethoxy) -3-methylphenyl} fluorene, 1,1-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,1-bis { (2-hydroxyethoxy) phenyl} cyclopentane, 4,4′-bis (2-hydroxyethoxy) diphenyl ether, 4,4′-bis (2-hydroxyethoxy) -3,3′-dimethyldiphenyl ether Ter, 1,3-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1 , 4-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1,4-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,3-bis {(2-hydroxyethoxy) phenyl} Cyclohexane, 4,8-bis {(2-hydroxyethoxy) phenyl} tricyclo [5.2.1.02,6] decane, 1,3-bis {(2-hydroxyethoxy) phenyl} -5,7-dimethyl Adamantane, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 1,4: 3,6-dianhydro-D-sorbitol (Isosorbide), 1,4: 3,6-dianhydro-D-mannitol (isomannide), 1,4: 3,6-dianhydro-L-iditol Isoidide), and the like.

  Among these, aromatic bisphenols are preferable, and among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4 -Hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-sulfonyl Diphenol, 2,2′-dimethyl-4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) Propyl} benzene and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, particularly 2,2-bis 4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-sulfonyl diphenol, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

  The polycarbonate resin used as the component B of the present invention may be a branched polycarbonate resin by using a branching agent in combination with the dihydroxy compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

  These polycarbonate resins are produced by a reaction means known per se for producing ordinary aromatic polycarbonate resins, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. The basic means of the manufacturing method will be briefly described.

  In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours. The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating with an inert gas atmosphere to distill the generated alcohol or phenols. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for transesterification can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

  In the present invention, a terminal terminator is used in the polymerization reaction. The end terminator is used for molecular weight control, and the obtained polycarbonate resin is excellent in thermal stability as compared with the other one because the end is blocked. Examples of the terminal terminator include monofunctional phenols represented by the following general formulas [5] to [7].

[In the formula, A is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkylphenyl group (the alkyl portion has 1 to 9 carbon atoms), a phenyl group, or a phenylalkyl group (the alkyl portion having 1 to 9 carbon atoms). And r is an integer from 1 to 5, preferably from 1 to 3].

[Wherein Y is —R—O—, —R—CO—O— or —R—O—CO—, wherein R is a single bond or a carbon number of 1 to 10, preferably 1 to 5; A valent aliphatic hydrocarbon group, and n represents an integer of 10 to 50. ]

  Specific examples of the monofunctional phenols represented by the general formula [5] include, for example, phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenyl. Phenol, isooctylphenol, etc. are mentioned. The monofunctional phenols represented by the general formulas [6] to [7] are phenols having a long-chain alkyl group or an aliphatic ester group as a substituent, and using these, the terminal of the polycarbonate resin is used. These not only function as a terminal terminator or molecular weight regulator, but also improve the melt fluidity of the resin and facilitate molding, as well as reducing the water absorption rate of the resin. used. The substituted phenols represented by the general formula [6] preferably have n of 10 to 30, particularly 10 to 26. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, Examples include eicosylphenol, docosylphenol, and triacontylphenol. Further, as the substituted phenols represented by the general formula [7], compounds in which X is —R—CO—O— and R is a single bond are suitable, and n is 10 to 30, particularly 10 to 26. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Among these monofunctional phenols, monofunctional phenols represented by the above general formula [5] are preferable, more preferably alkyl-substituted or phenylalkyl-substituted phenols, and particularly preferably p-tert-butylphenol, p -Cumylphenol or 2-phenylphenol. It is desirable that these monofunctional phenolic terminal terminators be introduced at least 5 mol%, preferably at least 10 mol%, based on the total terminals of the obtained polycarbonate resin. Or a mixture of two or more thereof.

  The polycarbonate resin used as the component B of the present invention may be a polyester carbonate obtained by copolymerizing an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof within a range that does not impair the spirit of the present invention. Good.

The viscosity average molecular weight of the polycarbonate resin used as the component B of the present invention is preferably in the range of 13,000 to 25,000, more preferably 13,000 to 21,000, and further in the range of 16,000 to 21,000. More preferably, the range of 16,000 to 20,000 is most preferable. If the molecular weight exceeds 25,000, the melt viscosity becomes too high and the moldability may be inferior, and if the molecular weight is less than 13,000, there may be a problem in mechanical strength. In addition, the viscosity average molecular weight as used in the field of this invention was calculated | required and calculated | required first using the Ostwald viscometer from the solution which melt | dissolved the polycarbonate resin 0.7g in 20 ml of methylene chloride in the specific viscosity computed by following Formula. The viscosity average molecular weight M is determined by inserting the specific viscosity by the following formula.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The polycarbonate resin used as the component B of the present invention preferably has a total Cl (chlorine) content in the resin of 0 to 200 ppm, more preferably 0 to 150 ppm. If the total Cl content in the polycarbonate resin exceeds 200 ppm, the hue and thermal stability may deteriorate, which is not preferable.

(C component: carbon fiber)
Examples of the carbon fiber used as the C component of the present invention include carbon fiber, carbon milled fiber, and carbon nanotube. Among these, carbon fiber is preferable in that it has excellent mechanical strength and can impart good electrical conductivity. As the carbon fiber, any of cellulose, polyacrylonitrile, pitch and the like can be used. Also obtained by a method in which a raw material composition composed of a polymer and a solvent with aromatic methylene bonds of aromatic sulfonic acids or their salts and a solvent is spun or molded and then carbonized without passing through an infusibilization step represented by a method such as carbonization. It is also possible to use those that have been used. Furthermore, any of general-purpose type, medium elastic modulus type, and high elastic modulus type can be used. Among these, polyacrylonitrile-based high elastic modulus type is particularly preferable. Moreover, although the average fiber diameter of carbon fiber is not specifically limited, 3-15 micrometers is preferable, More preferably, it is 5-13 micrometers. A carbon fiber having an average fiber diameter in such a range can exhibit good mechanical strength and fatigue characteristics without impairing the appearance of the molded product. Moreover, 60-500 micrometers is preferable as a number average fiber length in a resin composition, as for the preferable fiber length of a carbon fiber, More preferably, it is 80-400 micrometers, Especially preferably, it is 100-300 micrometers. The number average fiber length is a value calculated by an image analyzer from an optical microscope observation from the carbon fiber residue collected by high temperature ashing of the molded product, dissolution with a solvent, and decomposition with a chemical. is there. Further, when calculating such a value, a value having a length equal to or shorter than the fiber length is a value obtained by a method not counting. Furthermore, the surface of the carbon fiber is preferably oxidized for the purpose of enhancing the compatibility with the matrix resin and improving the dispersibility of the polypropylene resin and the polycarbonate resin. The mechanism of the present invention is not yet clear, but by oxidizing the surface of the carbon fiber, the polarity of the surface is improved, and the adhesion between the non-polar propylene resin and the carbon fiber is further reduced. As a result, it is considered that dispersibility with a polycarbonate resin having relatively low polarity is improved. The degree of oxidation treatment can be quantified by the surface oxygen concentration (O / C) on the carbon fiber. The carbon fiber used as the C component of the present invention has a surface oxygen concentration (O / C) which is a ratio of the number of atoms of oxygen (O) and carbon (C) on the fiber surface measured by X-ray photoelectron spectroscopy. It is 0.15 or more, preferably 0.18 or more, and more preferably 0.2 or more. When the surface oxygen concentration is less than 0.15, the compatibility between the polypropylene resin and the polycarbonate resin becomes insufficient, which is not preferable. The upper limit of the surface oxygen concentration is not particularly limited, but it is generally preferably 0.5 or less from the balance between the handleability and productivity of carbon fibers. Although the oxidation treatment method is not particularly limited, for example, (1) a method of treating carbon fiber with an acid or alkali or a salt thereof, or an oxidizing gas, and (2) a fiber or a fibrous carbon filler capable of being carbonized. Preferred examples include a method of firing at a temperature of 700 ° C. or higher in the presence of an inert gas containing an oxygen-containing compound, and (3) a method of heat-treating in the presence of an inert gas after oxidizing the carbon fiber. Is done.

The carbon fibers used as the component C of the present invention are preferably those subjected to a bundling treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like. In particular, carbon fibers treated with an olefin resin, a urethane resin, or an epoxy resin are suitable in the present invention because they are excellent in mechanical strength.
Content of C component is 5-100 weight part with respect to 100 weight part of resin components, Preferably it is 5-70 weight part, More preferably, it is 10-70 weight part. If the content of the C component is less than 5 parts by weight, the compatibility between the A component and the B component is insufficient, and the rigidity and tensile fracture strength are not sufficiently exhibited. If the content exceeds 100 parts by weight, the strand breaks during kneading extrusion. There arises a problem that surging occurs and the productivity is lowered.

(D component: modified polyolefin resin)
A modified polyolefin resin can be further added as a D component to the fiber-reinforced polypropylene resin composition of the present invention. The modified polyolefin resin improves the interfacial adhesion between the polypropylene resin and the carbon fiber, and improves the strength (flexural modulus, bending strength) of the carbon fiber reinforced polypropylene resin composition.

The modified polyolefin resin is preferably an acid-modified polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof. Examples of modified polyolefin resins include polyethylene resins and polypropylene resins, with polypropylene resins being preferred. The modified polypropylene resin includes a propylene homopolymer, a propylene random copolymer, a propylene block copolymer, and the like. For modification of the polyolefin resin, methods such as graft modification and copolymerization can be used. Examples of the unsaturated carboxylic acid used to modify the polyolefin resin include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, and angelic acid. Is mentioned. The unsaturated carboxylic acid derivatives include acid anhydrides, esters, amides, imides, metal salts, etc., for example, maleic anhydride, itaconic anhydride, citraconic anhydride, nadic anhydride, methyl acrylate, Examples include methyl methacrylate, ethyl acrylate, butyl acrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, maleimide, N-butylmaleimide, sodium acrylate, and sodium methacrylate. Among these, unsaturated dicarboxylic acids and derivatives thereof are preferable, and maleic anhydride or phthalic anhydride is particularly preferable. The crystallization temperature (Tc) of the modified polypropylene resin is usually 90 to 125 ° C, preferably 110 to 120 ° C. The intrinsic viscosity is usually 0.1 to 2.4 dl / g, preferably 0.2 to 1.6 dl / g. The crystallization temperature (Tc) of the modified polyolefin resin can be measured by a differential scanning calorimeter (DSC). The intrinsic viscosity of the modified polyolefin resin can be measured at 135 ° C. in tetralin. A suitable carboxylic acid addition amount of the modified polyolefin resin is preferably in the range of 0.1 to 14% by weight, and more preferably in the range of 0.8 to 8% by weight. Acid addition amount is determined by measuring the IR spectra of the acid-modified polyolefin ^resin, it can be calculated from the area of the peak of 1670cm ^-1 ~1810cm -1.

  The content of component D is preferably 1 to 20 parts by weight, more preferably 5 to 20 parts by weight, and still more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the resin component. If the content of component D is less than 1 part by weight, the strength may be insufficient. If it exceeds 20 parts by weight, the cost increases industrially.

(Other ingredients)
Various additives can be blended in the fiber-reinforced polypropylene resin composition of the present invention as long as the effects of the present invention are not impaired. Examples of such additives include phosphorus heat stabilizers, phenol heat stabilizers, sulfur-containing antioxidants, mold release agents, ultraviolet absorbers, hindered amine light stabilizers, flame retardants, and dyes and pigments.

(Phosphorus heat stabilizer)
As the phosphorus stabilizer used in the present invention, any of phosphite compounds, phosphonite compounds, and phosphate compounds can be used.
Various phosphite compounds can be used. Specific examples include phosphite compounds represented by the following general formula [8], phosphite compounds represented by the following general formula [9], and phosphite compounds represented by the following general formula [10].

[Wherein R ³¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group or alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a halo or alkylthio thereof (an alkyl group) Represents 1 to 30 carbon atoms) or a hydroxy substituent, and three R ³¹ can be selected from the same or different from each other, and a cyclic structure can be selected by being derived from dihydric phenols. ]

[Wherein R ³² and R ³³ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkylaryl group, an aralkyl group having 7 to 30 carbon atoms, and an alkyl group having 4 to 20 carbon atoms. A cycloalkyl group, a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms is shown. The cycloalkyl group and the aryl group can be selected from those not substituted with an alkyl group or those substituted with an alkyl group. ]

[Wherein R ³⁴ and R ³⁵ are alkyl groups having 12 to 15 carbon atoms. Note that R ³⁴ and R ³⁵ can be selected in any case that are the same or different from each other. ]

  Examples of the phosphonite compound include a phosphonite compound represented by the following general formula [11] and a phosphonite compound represented by the following general formula [12].

[In the ^formula, Ar 1, Ar ² represents a 2- (4-oxyphenyl) propyl-substituted aryl group of the aryl group or alkyl aryl group having 6 to 20 carbon atoms, or 15-25 carbon atoms, the four Ar ¹ Either the same or different from each other can be selected. Alternatively, ^two Ar ² can be selected to be the same or different from each other. ]

  Preferable specific examples of the phosphite compound represented by the above general formula [8] include diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenylmono (Tridecyl) phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite are mentioned.

  Preferred specific examples of the phosphite compound represented by the above general formula [9] include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, etc., preferably distearyl pentaerythritol diphosphite, Examples thereof include bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. Such phosphite compounds can be used alone or in combination of two or more.

  Preferable specific examples of the phosphite compound represented by the general formula [10] include 4,4'-isopropylidenediphenol tetratridecyl phosphite.

  Preferable specific examples of the phosphonite compound represented by the general formula [11] include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di -N-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert) -Butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propyl) Phenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) -4,4′-bifu Nylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylenedi Examples thereof include phosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite is preferred, and tetrakis ( 2,4-di-tert-butylphenyl) -biphenylenediphosphonite is more preferred. The tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferably a mixture of two or more, specifically tetrakis (2,4-di-tert-butylphenyl) -4,4. '-Biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -3,3' -It is possible to use one or two or more of biphenylene diphosphonites in combination, but a mixture of these three is preferable.

  Preferable specific examples of the phosphonite compound represented by the general formula [12] include bis (2,4-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-n -Butylphenyl) -3-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3 -Phenyl-phenylphosphonite bis (2,6-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, Bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butyl) Benzyl) -3-phenyl-phenylphosphonite and the like, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, bis (2,4-di-tert-butylphenyl) -phenyl-phenyl Phosphonite is more preferred. The bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl) -4- One or two of phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite can be used in combination. It is a mixture. In the case of two kinds of mixtures, the mixing ratio is preferably in the range of 5: 1 to 4 by weight, and more preferably in the range of 5: 2 to 3.

On the other hand, as phosphate compounds, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl Examples thereof include phosphate and diisopropyl phosphate, and trimethyl phosphate is preferable.
Among the phosphorus-containing heat stabilizers, more preferred compounds include compounds represented by the following general formulas [13] and [14].

[In the formula [13], R ³⁶ and R ³⁷ each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. ]

(In the formula [14], R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group. A group or an aralkyl group, R ⁴⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴⁶ represents a hydrogen atom or a methyl group.)

In the formula [13], R ³⁶ and R ³⁷ are preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. Specific examples of the compound represented by the formula [13] include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butyl). Phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) Examples thereof include phosphite, and tris (2,6-di-tert-butylphenyl) phosphite is particularly preferable.

  Specifically, the compound represented by the formula [14] is a phosphite derived from 2,2′-methylenebis (4,6-di-tert-butylphenol) and 2,6-di-tert-butylphenol, 2 2,2'-methylenebis (4,6-di-tert-butylphenol) and phosphites derived from phenol, especially from 2,2'-methylenebis (4,6-di-tert-butylphenol) and phenol. Derived phosphites are preferred.

  The content of the phosphorus heat stabilizer is preferably 0.001 to 3.0 parts by weight, more preferably 0.01 to 2.0 parts by weight, and still more preferably 0.05 to 100 parts by weight with respect to 100 parts by weight of the resin component. 1.0 part by weight. If the content of the phosphorous heat stabilizer is less than 0.001 part by weight, the mechanical properties may not be sufficiently exhibited, and if it exceeds 3.0 parts by weight, the mechanical properties may not be sufficiently exhibited.

(Phenolic heat stabilizer)
The phenolic stabilizer used in the present invention generally includes hindered phenols, semi-hindered phenols, and less hindered phenol compounds, but particularly in terms of applying a heat-stable formulation to polypropylene resins. A hindered phenol compound is more preferably used. Specific examples of such hindered phenol compounds include vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate, 2-tert-butyl-6. -(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert) -Butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methyl Bis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′-ethylidene-bis (4,6-di-tert- Butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3 -(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [ 2-tert-butyl-4-methyl 6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] Phthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4,8,10- Tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2 ′ -Thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-di-thiobis (2,6-di-tert- Butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ', 5'-di tert-butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6 Dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3 ′, 5 '-Di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like can be mentioned and can be preferably used.

  More preferably, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl) -2'-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane Further, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate is preferable.

(Sulfur-containing antioxidant)
In the fiber-reinforced polypropylene resin composition of the present invention, a sulfur-containing antioxidant can also be used as an antioxidant. It is particularly suitable when the resin composition is used for rotational molding or compression molding. Specific examples of such sulfur-containing antioxidants include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate. , Distearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetra (β-laurylthiopropionate) ester, bis [2-methyl-4 -(3-laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. be able to. More preferably, a pentaerythritol tetra ((beta) -lauryl thiopropionate) ester can be mentioned.

  The phosphorus stabilizers, phenol stabilizers, and sulfur-containing antioxidants listed above can be used alone or in combination of two or more. The content of the phenol-based stabilizer and the sulfur-containing antioxidant is preferably 0.0001 to 1 part by weight with respect to 100 parts by weight of the resin component. More preferably, it is 0.0005-0.5 weight part, More preferably, it is 0.001-0.2 weight part.

(Release agent)
The fiber-reinforced polypropylene resin composition of the present invention preferably further contains a release agent for the purpose of improving productivity during molding and reducing distortion of the molded product. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound ( And fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like. Among these, fatty acid esters are preferable as a release agent. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, as carbon number of this alcohol, it is the range of 3-32, More preferably, it is the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, a polyhydric alcohol is more preferable.

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetreic acid . Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred.

  The above aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats such as beef tallow and lard and vegetable oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Accordingly, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid are preferably used.

The fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). However, partial esters are more preferably full esters because they usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures. The acid value in the fatty acid ester of the present invention is preferably 20 or less, more preferably 4 to 20 and even more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially zero. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially zero. These characteristics can be obtained by a method defined in JIS K 0070.
The content of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and still more preferably 0.05 to 0.5 parts by weight with respect to 100 parts by weight of the resin component. It is. In such a range, the fiber-reinforced polypropylene resin composition of the present invention has good release properties and roll release properties.

(UV absorber)
The fiber-reinforced polypropylene resin composition of the present invention can contain an ultraviolet absorber. In the benzophenone series, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy- 5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) ) Methane, 2-hydroxy Examples include -4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

  In the benzotriazole series, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-Dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3 , 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2- Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 Di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- ( 2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4 -One), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacryloxy) Copolymerization of ethylphenyl) -2H-benzotriazole with vinyl monomer copolymerizable with the monomer And 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a copolymer of vinyl monomer copolymerizable with the monomer, 2-hydroxyphenyl-2H-benzotriazole skeleton A polymer having

  In the hydroxyphenyl triazine series, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) -1,3,5-triazin-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol Illustrated. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

In the cyclic imino ester system, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazine) -4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one), and the like.
In the case of cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenylacryloyl) oxy ] Methyl) propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene and the like.

  Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby the ultraviolet-absorbing monomer and / or the light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate. A polymer type ultraviolet absorber obtained by copolymerization with a monomer such as may be used. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate. The

Of these, benzotriazoles and hydroxyphenyltriazines are preferred in terms of ultraviolet absorption, and cyclic iminoesters and cyanoacrylates are preferred in terms of heat resistance and hue (transparency). You may use the said ultraviolet absorber individually or in mixture of 2 or more types.
The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, further preferably 0.03 to 1 part by weight, based on 100 parts by weight of the resin component. Preferably it is 0.05-0.5 weight part.

(Hindered amine light stabilizer)
The fiber-reinforced polypropylene resin composition of the present invention can contain a hindered amine light stabilizer. The hindered amine light stabilizer is generally called HALS (Hindered Amine Light Stabilizer) and is a compound having a 2,2,6,6-tetramethylpiperidine skeleton in the structure. For example, 4-acetoxy-2,2,6 , 6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2, 2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2, 2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6- Tramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarbamoyloxy) -2,2,6 , 6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, bis (2 , 2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6,6-tetramethyl-4-) Piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl) 4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) carbonate, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) oxalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, bis (1,2,2,6,6-pentamethyl-4) -Piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) terephthalate, N, N'- Bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, 1,2-bis (2,2,6,6-tetramethyl-4-piperi Ruoxy) ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyltolylene) -2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl-4 -Piperidyl) -benzene-1,3,5-tricarboxylate, N, N ', N ", N'''-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2) , 6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N ′ -Bis (2,2,6,6-tetramethyl-4-pi Polycondensate of peridyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{6- (1,1,3,3-tetra Methylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6- Tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2, 6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4 Tricarboxylate 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionyloxy] 2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, and a condensate with β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.

  The hindered amine light stabilizers are roughly classified according to the binding partner of the nitrogen atom in the piperidine skeleton, the NH type (hydrogen is bonded to the nitrogen atom), the NR type (the alkyl group (R) is bonded to the nitrogen atom), There are three types of N-OR type (an alkoxy group (OR) is bonded to a nitrogen atom), but when applied to a polycarbonate resin, N-R is a low basicity from the viewpoint of the basicity of the hindered amine light stabilizer. More preferably, the N-OR type is used. The said hindered amine light stabilizer can be used individually or in combination of 2 or more types.

  The content of the hindered amine light stabilizer is preferably 0 to 1 part by weight, more preferably 0.05 to 1 part by weight, still more preferably 0.08 to 0.7 part per 100 parts by weight of the resin component. Part by weight, particularly preferably 0.1 to 0.5 part by weight. When the content of the hindered amine light stabilizer is more than 1 part by weight, it is not preferable because an appearance defect due to gas generation and a decrease in physical properties due to decomposition of the polycarbonate resin may occur. Further, if it is less than 0.05 parts by weight, sufficient light resistance may not be exhibited.

(Flame retardants)
The fiber reinforced polypropylene resin composition of the present invention can be provided with flame retardancy by blending a flame retardant. As such a flame retardant, conventionally, various compounds known as a flame retardant for thermoplastic resins, particularly polycarbonate resins, can be applied. More preferably, (i) halogen flame retardants (for example, brominated polycarbonate compounds) (Ii) Phosphorous flame retardants (eg, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, and phosphazene compounds), (iii) metal salt flame retardants (eg, organic sulfonic acid) Alkali (earth) metal salts, borate metal salt flame retardants, stannate metal salt flame retardants, etc.), and (iv) silicone flame retardants comprising silicone compounds. The compounding of the compound used as a flame retardant not only improves the flame retardancy but also provides, for example, an improvement in antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.

  The content of the flame retardant is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 28 parts by weight, and still more preferably 0.08 to 25 parts by weight with respect to 100 parts by weight of the resin component. . When the content of the flame retardant is less than 0.01 parts by weight, sufficient flame retardancy may not be obtained, and when it exceeds 30 parts by weight, the impact strength and chemical resistance may be greatly reduced.

(Dye and pigment)
The fiber-reinforced polypropylene resin composition of the present invention can further provide a molded product containing various dyes and pigments and exhibiting various design properties. By blending a fluorescent brightening agent or other fluorescent dye that emits light, a better design effect that makes use of the luminescent color can be imparted. In addition, a fiber-reinforced polypropylene resin composition having coloring with a very small amount of dye and pigment and vivid coloring can also be provided.

  Examples of the fluorescent dye (including a fluorescent brightening agent) used in the present invention include a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin.

Examples of dyes other than the above bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone And dyes such as dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of this invention can mix | blend a metallic pigment, and can also obtain a better metallic color. As the metallic pigment, those having a metal film or a metal oxide film on various plate-like fillers are suitable.
The content of the dye / pigment is preferably 0.00001 to 1 part by weight and more preferably 0.00005 to 0.5 part by weight with respect to 100 parts by weight of the resin component.

(Other resins)
In the resin composition of the present invention, other resins may be used in a small proportion within a range where the effects of the present invention are exhibited.
Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, and polyethylene. Examples of the resin include polyolefin resin, polymethacrylate resin, phenol resin, and epoxy resin.

(Other fillers)
In the resin composition of the present invention, other fillers can be used in a small proportion within a range in which the effects of the present invention are exhibited.
Such other fillers include fibrous fillers such as potassium titanate whisker, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone koji fiber, metal fiber, wollastonite, sericite, kaolin, Metallic compounds such as silicates such as mica, clay, bentonite, asbestos, talc and alumina silicate, swellable layered silicates such as montmorillonite and synthetic mica, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide and iron oxide Non-fibrous fillers such as carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and silica Can be mentioned.

(Other additives)
In addition, in the resin composition of the present invention, additives known per se can be blended in a small proportion for imparting various functions to the molded article and improving the characteristics. These additives are used in usual amounts as long as the object of the present invention is not impaired. Such additives include sliding agents (eg, PTFE particles), fluorescent dyes, inorganic phosphors (eg, phosphors having aluminate as a mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents , Photocatalytic antifouling agents (for example, fine particle titanium oxide, fine particle zinc oxide), radical generators, infrared absorbers (heat ray absorbers), and photochromic agents.

(Method for producing fiber-reinforced polypropylene resin composition)
There is no restriction | limiting in particular in the method of manufacturing the fiber reinforced polypropylene resin composition of this invention, A well-known method can be used. For example, a method of mixing each component in a solution state and evaporating the solvent or precipitating in the solvent can be mentioned. From an industrial point of view, a method of kneading each component in a molten state is preferable. For melt kneading, generally used kneading apparatuses such as a single or twin screw extruder and various kneaders can be used. A biaxial high kneader is particularly preferable. In melt kneading, the cylinder set temperature of the kneading apparatus is preferably in the range of 200 to 360 ° C, more preferably in the range of 200 ° C to 300 ° C, and further preferably in the range of 230 to 280 ° C. At the time of kneading, each component may be mixed uniformly in advance with a device such as a tumbler or a Henschel mixer, or if necessary, a method of omitting the mixing and separately supplying each of the components separately to the kneading device is also used. be able to.

(Molding method of molded product made of fiber reinforced polypropylene resin composition)
Molded articles made of the fiber reinforced polypropylene resin composition of the present invention are molded by injection molding, extrusion molding, and other various molding methods, but do not go through a kneading process in advance and are dry blended during injection molding or extrusion molding. The resin composition of the present invention can be kneaded during the melt processing operation to directly obtain a molded product.

  The fiber-reinforced polypropylene resin composition of the present invention is excellent in rigidity, dimensional stability, chemical resistance, and is useful for electrical / electronic parts, home appliances, automobile-related parts, infrastructure-related parts, housing-related parts, etc. Its industrial effect is exceptional.

  The form for carrying out the present invention is a summary of the preferred ranges of the above-mentioned requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
The following items were evaluated.

1. Evaluation of polycarbonate resin (component B) (i) Viscosity average molecular weight (Mv)
Using a Ostwald viscometer, a specific viscosity (η _SP ) calculated by the following formula was determined from a solution of polycarbonate resin in 100 ml of methylene chloride at 20 ° C.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight Mv was calculated from the obtained specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7

(Ii) Polydiorganosiloxane Component Content Using JNM-AL400 manufactured by JEOL Ltd., the ¹ H-NMR spectrum of the polycarbonate-polydiorganosiloxane copolymer resin was measured, and the integration of the peak derived from the dihydric phenol (I) was performed. The ratio was calculated by comparing the integral ratio of the peak derived from the dihydroxyaryl-terminated polydiorganosiloxane (II).
Polydiorganosiloxane component content (wt%) = [A / (A + B)] × 100
A: [Integral ratio of ¹ H peak of dihydroxyaryl-terminated polydiorganosiloxane (II)] × [Molecular weight of polydiorganosiloxane moiety]
B: [Integral ratio of ¹ H peak of dihydric phenol (I)] × [Molecular weight of dihydric phenol]

2. Evaluation of carbon fiber (C component) (i) Surface oxygen concentration (O / C)
The carbon fiber from which the dirt adhering to the surface was removed with superheated steam was cut to about 20 mm and spread on a copper sample support. Next, the sample support was set in the sample chamber, and the inside of the sample chamber was kept at 1 × 10 ⁻⁸ Torr. Subsequently, AlKα ₁ and ₂ were used as the X-ray source, and the measurement was performed by changing the photoelectron escape angle between 10 ° and 90 °. In addition, the binding energy value of the C _1s main peak (peak top) was adjusted to 284.6 eV as a correction value for the peak accompanying charging during measurement. The C _1s peak area was determined by drawing a straight base line in the range of 282 to 296 eV. The O _1s peak area was determined by drawing a straight base line in the range of 528 to 540 eV. Here, the surface oxygen concentration is calculated as an atomic ratio by using a sensitivity correction value unique to the apparatus from the ratio of the O _1s peak area to the C _1s peak area. As an X-ray photoelectron spectroscopy apparatus, ESCA-1600 (sensitivity correction value: 2.33) manufactured by ULVAC-PHI Co., Ltd. was used.

3. Evaluation of fiber reinforced polypropylene resin composition (i) Tensile properties (tensile fracture strength)
Measurement was performed at a test speed of 50 mm / min according to ISO 527. The test piece was a dumbbell-type test piece, and the parallel part shape was length 80 mm × width 10 mm × thickness 4 mm.

(Ii) Rigidity (flexural modulus)
Using a test piece of length 80 mm × width 10 mm × thickness 4 mm, measurement was performed at a test speed of 2 mm / min according to ISO178.

(Iii) Chemical resistance A test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm is immersed in a solvent (acetone) at 23 ° C. for 12 hours, then taken out from the solvent, and the solvent adhering to the test piece is soaked in the waste cloth. Let The surface of the immersed test specimen was visually observed, and “O” indicates that no abnormality was observed in the appearance, and “X” indicates abnormality in the appearance.

(Iv) Dimensional stability (mold shrinkage)
After forming a flat plate with a short side of 50 mm, a long side of 100 mm, and a thickness of 4 mm having a film gate with a thickness of 1.5 mm on one short side, and adjusting the state at 23 ° C., 50% RH for 24 hours, the flow of the flat plate The direction dimension was measured using a three-dimensional measuring machine (MICROPAK 550 manufactured by Mitoyo Seisakusho Co., Ltd.) to determine the molding shrinkage in the flow direction.

(V) Dimensional stability (box warpage)
Form a box-shaped molded product (thickness 2mm) 180mm long x 150mm wide x 30mm high with a gate (one point) on the bottom and adjust the condition at 23 ° C, 50% RH for 24 hours. Then, the looseness of the box-shaped molded product was evaluated by placing it on a smooth surface and pressing the corner of the bottom of the box. A sample in which no rattling was observed was marked with ◯, and a symbol with rattling was marked with ×.

(Vi) Compatibility (Peelability of molded product)
A flat plate having a length of 50 mm, a width of 45 mm, and a thickness of 2 mm was formed, and 100 grids of 1 mm square were cut into a flat plate shape with a cutter. Subsequently, cellophane tape was applied on the grid and evaluated by the presence or absence of peeling of the sample surface. The case where peeling was not observed was marked with ◯, and the case where peeling was seen was marked with X.

[Examples 1-16, Comparative Examples 1-5]
The resin composition which consists of a mixture ratio of Table 1 and Table 2 was created in the following ways. The description will be made according to the symbols in the following table. Each component of the ratio of the table | surface was measured, it mixed uniformly using the tumbler, this mixture was thrown into the extruder, and preparation of the resin composition was performed. As the extruder, a vent type twin screw extruder (Kobe Steel Works KTX-30) having a diameter of 30 mmφ was used. The screw configuration is the first stage kneading zone (consisting of 2 feed kneading discs, 1 feed rotor, 1 return rotor and 1 return kneading disc) before the vent position. Thereafter, a second-stage kneading zone (consisting of a feed rotor × 1 and a return rotor × 1) was provided. The strand was extruded under the conditions of a cylinder temperature and a die temperature of 250 ° C. and a vent suction of 3000 Pa, cooled in a water bath, then cut into a strand with a pelletizer and pelletized. However, in Comparative Example 5, the strand breakage and surging were severe, and a pellet that could be evaluated for molding could not be obtained. After the pellets obtained in Examples 1 to 16 and Comparative Examples 1 to 4 were dried at 100 ° C. for 5 hours with a hot air circulation dryer, test pieces for evaluation were molded using an injection molding machine. The molding conditions were a cylinder temperature of 250 ° C. and a mold temperature of 50 ° C. The evaluation results are shown in Tables 1 and 2.

In addition, each component of symbol description in Table 1 and Table 2 is as follows.
(A component: polypropylene resin)
A-1: Homopolypropylene resin (Prime Polypro E-200GP (product name) MFR = 2.0 g / 10 min manufactured by Prime Polymer Co., Ltd.)
A-2: Homopolypropylene resin (Prime Polypro E-105GM (product name) MFR = 0.5 g / 10 min manufactured by Prime Polymer Co., Ltd.)
A-3: Polypropylene resin (block polymer) (Prime Polypro E-702G (product name) manufactured by Prime Polymer Co., Ltd. MFR = 0.9 g / 10 min)
A-4: Homopolypropylene resin (Prime Polymer Pro Prime Poly E-106G (product name) MFR = 15 g / 10 min)
A-5: Homopolypropylene resin (manufactured by Sun Allomer, Sun Allomer PL400A (product name) MFR = 2.0 g / 10 min)
A-6: Homopolypropylene resin (manufactured by Sun Allomer, Sun Allomer VS200A (product name) MFR = 0.5 g / 10 min)

(B component: polycarbonate resin)
B-1: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 22,400 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WP (product name) manufactured by Teijin Limited)
B-2: Polycarbonate-polydiorganosiloxane copolymer resin powder having a viscosity average molecular weight of 19,400 obtained by the following production method: Thermometer, stirrer, reactor equipped with a reflux condenser, 21951 parts of ion-exchanged water, 48.5% water An aqueous solution of sodium oxide (3674 parts) was added, and 3880 parts of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 7.6 parts of hydrosulfite were dissolved, and then 14565 parts of methylene chloride (dihydroxy compound (I)) 14 moles per mole), and 1900 parts of phosgene was blown in for 60 minutes at 22-30 ° C. with stirring. Next, a solution obtained by dissolving 1131 parts of 48.5% aqueous sodium hydroxide and 108 parts of p-tert-butylphenol in 800 parts of methylene chloride was added, and 430 parts of a polydiorganosiloxane compound represented by the following formula [15] was chlorinated. The solution dissolved in 1600 parts of methylene was emulsified by adding dihydroxyaryl-terminated polydiorganosiloxane (II) at a rate of 0.0008 mol / min per 1 mol of dihydric phenol (I), and then vigorously again. Stir. Under such stirring, 4.3 parts of triethylamine was added while the reaction solution was at 26 ° C., and stirring was continued for 45 minutes at a temperature of 26 to 31 ° C. to complete the reaction. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and poured into a kneader filled with warm water when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water. Then, methylene chloride was evaporated while stirring to obtain a polycarbonate-polydiorganosiloxane copolymer resin powder. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation dryer to obtain a polycarbonate-polydiorganosiloxane copolymer resin powder. (Polydiorganosiloxane component content 8.2%, viscosity average molecular weight 19,400)

B-3: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 25,100 made from bisphenol A and phosgene by a conventional method, Panlite L-1250WQ (product name) manufactured by Teijin Ltd.)
B-4: Modified polycarbonate resin having a viscosity average molecular weight of 19,800 obtained by the following production method A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 3844 parts of a 48% aqueous sodium hydroxide solution and ion-exchanged water 22, 380 parts were charged to this, 1,992 parts 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) 1, After dissolving 773 parts and 7.53 parts hydrosulfite (manufactured by Wako Pure Chemical Industries, Ltd.), 13,210 parts of methylene chloride was added and 2,000 parts of phosgene was added at 15-25 ° C. over about 60 minutes with stirring. Infused. After completion of the phosgene blowing, 640 parts of a 48% aqueous sodium hydroxide solution and 93.2 parts of p-tert-butylphenol were added and stirring was resumed. After emulsification, 3.24 parts of triethylamine was added and further stirred at 28 to 33 ° C. for 1 hour. The reaction was terminated. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and further washed with water until the conductivity of the aqueous phase becomes substantially the same as that of ion-exchanged water. Obtained. Next, this solution is passed through a filter having an aperture of 0.3 μm, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing, and the polycarbonate resin is flaked while distilling off methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder. (Viscosity average molecular weight 19,800)

(C component: carbon fiber)
C-1: carbon fiber having a surface oxygen concentration of 0.20 C-2: carbon fiber having a surface oxygen concentration of 0.25 C-3: carbon fiber having a surface oxygen concentration of 0.10 (D component: modified) Polyolefin resin)
D-1: Maleic acid-modified polyolefin ("Modic P-908" (trade name) manufactured by Mitsubishi Chemical)

Claims (4)

  It is measured by (C) X-ray photoelectron spectroscopy with respect to 100 parts by weight of a resin component comprising (A) 50 to 90 parts by weight of a polypropylene resin (component A) and (B) 50 to 10 parts by weight of a polycarbonate resin (component B). 5 to 100 parts by weight of carbon fiber (component C) having a surface oxygen concentration (O / C) of 0.15 or more, which is the ratio of the number of atoms of oxygen (O) and carbon (C) on the fiber surface. Fiber reinforced polypropylene resin composition. The fiber-reinforced polypropylene resin composition according to claim 1, wherein the component B is a polycarbonate resin containing 20 to 100 mol% of a carbonate constituent unit represented by the following formula [1] in all carbonate constituent units.

In the general formula [1], R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 20 carbon atoms. A cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, and the number of carbon atoms It represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. A and b are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2].

(In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a carbon atom. Represents a group selected from the group consisting of an aryl group having 6 to 14 carbon atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 to 14 carbon atoms Aryl group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and carbon R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or 6 to 12 carbon atoms. Or a plurality of them, which may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7, e is a natural number, f Is 0 or a natural number, e + f is a natural number of 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms)   The fiber-reinforced polypropylene resin composition according to claim 1 or 2, comprising 1 to 20 parts by weight of (D) a modified polyolefin resin (D component) with respect to 100 parts by weight of the resin component.   An injection-molded article comprising the fiber-reinforced polypropylene resin composition according to any one of claims 1 to 3.