JP5134593B2 - Carbon fiber reinforced propylene-based composite material and molded article thereof - Google Patents

Description

  The present invention relates to a carbon fiber reinforced propylene-based composite material and a molded body thereof, and particularly relates to a carbon fiber reinforced propylene-based composite material having improved bending strength and tensile strength and a molded body thereof.

  Since carbon fibers are lightweight and have high strength, carbon fiber composite materials based on thermosetting resins have been used in the aerospace field. Although development of automobile structural members using this carbon fiber composite material is expected as a material for reducing the weight of automobile bodies, there is a problem in moldability (rapid moldability).

  In order to improve the moldability, a method using a thermoplastic resin as a base material can be used. For example, polypropylene resin is suitable for composite materials because of its low specific gravity, high rigidity, and good moldability. However, it is difficult to interact with carbon fibers, and its bending strength and elastic modulus are low. It is a problem.

By the way, the carbon fiber is subjected to a surface treatment in order to improve the adhesiveness with the resin, and the carbon fiber bundle is wound around a bobbin after being treated with a sizing agent called a sizing agent.
Therefore, a carbon fiber reinforced propylene composite material composed of carbon fiber and polypropylene resin is produced by kneading or impregnating sized carbon fiber and polypropylene resin in a molten state. The mechanical strength of the carbon fiber reinforced propylene-based composite material is considered to be greatly affected by the interaction between the carbon fiber and the polypropylene resin and the dispersibility of the carbon fiber in the polypropylene resin matrix (carbon fiber opening property). Therefore, for the purpose of enhancing the interaction between the carbon fiber and the polypropylene resin, from a specific sizing agent for carbon fiber (Patent Document 1), a sizing-treated carbon fiber and a propylene resin modified with maleic anhydride Although the composite material (patent document 2) etc. which become are disclosed, especially the bending strength and bending elastic modulus of a carbon fiber reinforced propylene-type composite material have room for improvement.

JP 2002-13069 A JP 2003-277525 A

  The present invention provides a carbon fiber reinforced propylene composite material having improved bending strength while maintaining a good flexural modulus by using a modified propylene polymer having a low crystallinity or a reduced amount of low molecular weight component, and It is an object to provide the molded body.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that when the modified propylene polymer contains a low crystallinity or low molecular weight component, the adhesive strength between the carbon fiber and the polypropylene resin is low. The carbon fiber reinforced propylene composite material formed from the propylene polymer, the specific modified propylene resin, and the surface-treated carbon fiber has improved bending strength and flexural modulus. As a result, the present invention has been completed.

That is, the present invention includes the following matters.
[1] Graft modification of propylene polymer (A) produced in the presence of Ziegler-Natta catalyst and propylene polymer (F) produced in the presence of metallocene catalyst with monomers containing ethylenically unsaturated bonds A carbon fiber reinforced propylene composite material formed from the modified propylene polymer (B) obtained by the above and the surface-treated carbon fiber (C), the carbon fiber reinforced propylene composite material, A carbon fiber reinforced propylene based composite material satisfying the following requirements (i) to (iv), and the modified propylene polymer (B) satisfying the following requirements (b-1) to (b-4).
(I) The amount of the carbon fiber (C) used is 1 to 80% by weight in a total of 100% by weight of the propylene polymer (A), the modified propylene polymer (B) and the carbon fiber (C). .
(Ii) The melting point (Tm) is 150 ° C. or higher.
(Iii) The amount of the modified propylene polymer (B) used is 0.5 to 40% by weight in a total of 100% by weight of the propylene polymer (A) and the modified propylene polymer (B).
(Iv) The graft amount in the modified propylene polymer (B) is 0.2 to 2% by weight in a total of 100% by weight of the propylene polymer (A) and the modified propylene polymer (B).
(B-1) The melting point (Tm) is 135 ° C. or higher.
(B-2) The graft amount is 1 to 5% by weight.
(B-3) Intrinsic viscosity [η] is 0.2 to 4 dl / g.
(B-4) The amount of components soluble in 70 ° C. o-dichlorobenzene is 3% by weight or less.

[2] The carbon fiber-reinforced propylene composite material according to [1], wherein the modified propylene polymer (B) has a carboxyl group, an acid anhydride group, or a derivative thereof.
[3] The carbon fiber-reinforced propylene composite material according to [1] or [2], wherein the surface treatment is a sizing treatment using an epoxy polymer, a nylon polymer, or a urethane polymer.
[4] The carbon fiber reinforced propylene-based composite material according to any one of [1] to [3], wherein the carbon fiber (C) is a carbon fiber base fabric.
[5] A molded product obtained by molding the carbon fiber-reinforced propylene-based composite material according to any one of [1] to [4].

  According to the present invention, the use of a specific modified propylene-based polymer obtained from a propylene-based polymer produced in the presence of a metallocene catalyst can reduce the amount of low crystallinity or low molecular weight components and thereby strengthen carbon fibers. A propylene-based composite material is obtained, and a carbon fiber-reinforced propylene-based composite material with improved bending strength and a molded body thereof are obtained while maintaining a good flexural modulus. Moreover, the carbon fiber reinforced propylene-based composite material is excellent in the balance of mechanical strength.

  In the present invention, by using a propylene polymer produced in the presence of a metallocene catalyst as a component of the modified propylene polymer, the bending strength of the carbon fiber reinforced propylene composite material can be increased even if the graft amount is relatively small. Can be improved.

  For this reason, the carbon fiber reinforced propylene-based composite material of the present invention is suitable for automobile structural members that require formability in addition to lightness.

Hereinafter, the carbon fiber reinforced propylene-based composite material of the present invention and the molded body thereof will be described.
[Propylene polymer (A)]
The propylene polymer (A) used in the present invention is a polymer produced in the presence of a Ziegler-Natta catalyst. Examples of the propylene polymer (A) include a propylene homopolymer, a random copolymer or a block copolymer of propylene and another small amount of monomer. Other minor monomers include ethylene and α-olefins having 4 to 20 carbon atoms. Specific examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2- Ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene , Dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-nonene Sen, 1-undecene and 1-dodecene and the like, preferably 1-butene, 1-pentene, 1-hexene and 1-octene.

The amount of units derived from propylene in the copolymer of propylene and other small amount of monomers is usually 95 mol% or more, preferably 98 mol% or more.
The melting point (Tm) of the propylene polymer (A) is usually 150 to 170 ° C, preferably 155 to 170 ° C. When the melting point (Tm) of the propylene polymer (A) is less than 150 ° C., the bending strength and the bending elastic modulus of the obtained carbon fiber reinforced propylene composite material may be lowered.

  The melt flow rate (MFR: ASTM D1238, 230 ° C., load 2.16 kg) of the propylene polymer (A) is usually 0.1 to 500 g / 10 min, preferably 0.5 to 350 g / 10 min, more preferably 1. 0.0 to 250 g / 10 min. When the MFR of the propylene-based polymer (A) is less than 0.1 g / 10 min, the openability of the carbon fiber (C) deteriorates, and the bending strength of the obtained carbon fiber-reinforced propylene-based composite material decreases, The appearance of the molded body may deteriorate. On the other hand, if the MFR of the propylene-based polymer (A) is higher than 500 g / 10 min, the toughness of the propylene-based polymer (A) is lowered, so that the bending strength and bending elastic modulus of the obtained carbon fiber reinforced propylene-based composite material are reduced. May decrease.

<Production method of propylene polymer (A)>
The propylene polymer (A) is produced using a Ziegler-Natta catalyst having high stereoregularity. Examples of the Ziegler-Natta catalyst having high stereoregularity include various known catalysts. For example, (a ′) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor, and (b ′ A catalyst comprising: an organometallic compound catalyst component; and (c ′) an organosilicon compound catalyst component having at least one group selected from the group consisting of a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, and derivatives thereof. Is mentioned.

  The solid titanium catalyst component (a ′) can be prepared by contacting the magnesium compound (a′-1), the titanium compound (a′-2) and the electron donor (a′-3).

  Examples of the magnesium compound (a′-1) include a magnesium compound having a reducing ability such as a compound having a magnesium-carbon bond or a magnesium-hydrogen bond, and a magnesium halide, an alkoxymagnesium halide, an aryloxymagnesium halide, an alkoxymagnesium, Examples thereof include magnesium compounds having no reducing ability such as aryloxymagnesium and magnesium carboxylates.

Examples of the titanium compound (a′-2) include tetravalent titanium represented by the general formula Ti (OR) _g X _4-g (R is a hydrocarbon group; X is a halogen atom; 0 ≦ g ≦ 4). Compounds. Specific examples of the titanium compound (a′-2) include titanium tetrahalides such as TiCl ₄ , TiBr ₄ and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (O _{-n-C 4 H 9) Cl} 3, Ti (OC 2 H 5) Br 3 and _{Ti (OCH 2 CH (CH 3} ) 2) trihalide, alkoxy titanium such as _{Br 3; Ti (OCH 3)} 2 Cl 2 _{, Ti (OC 2 H 5)} 2 Cl 2, Ti (O-n-C 4 H 9) 2 Cl 2 and Ti (OC ₂ H _{5) 2} dihalogenated dialkoxy titanium, such as Br _2; Ti (OCH _{3) 3 Cl, Ti (OC 2 H} 5) 3 Cl, Ti (O-n-C 4 H 9) 3 Cl and Ti (OC ₂ H _{5) 3} monohalogenated trialkoxy titanium such as Br; and Ti (OCH _{3 ) 4, Ti (OC 2 H} 5) 4, Ti (O-n-C 4 H 9) 4, Ti (OCH 2 CH (CH 3) 2) 4 and _{i (O- (CH 2) 4} CHCH 3 (C 2 H 5)) 4 and the like tetraalkoxytitanium such.

  Examples of the electron donor (a′-3) include alcohols such as phenol, ethers, ketones, aldehydes, organic acid esters, inorganic acid esters, organic acid halides, amides, acid anhydrides, amines such as ammonia, nitriles, Examples include isocyanates, nitrogen-containing cyclic compounds, and oxygen-containing cyclic compounds.

  In order to prepare the solid titanium catalyst component (a ′), when contacting the magnesium compound (a′-1), the titanium compound (a′-2) and the electron donor (a′-3), silicon In addition, other reaction reagents including phosphorus and aluminum may coexist, or a support may be used using a support.

As a method for preparing the solid titanium catalyst component (a ′), a known method can be used without particular limitation, but a few examples will be briefly described below.
(1) Contacting a hydrocarbon solution of a magnesium compound (a′-1) containing an electron donor (liquefaction agent) (a′-3) with an organometallic compound to precipitate a solid, or depositing And a contact reaction with the titanium compound (a′-2).
(2) A method in which a complex composed of a magnesium compound (a′-1) and an electron donor (a′-3) is contacted and reacted with an organometallic compound, and then a titanium compound (a′-2) is contacted and reacted.
(3) A method in which a titanium compound (a′-2) and an electron donor (a′-3) are contact-reacted with a contact product between an inorganic carrier and an organic magnesium compound (a′-1). At this time, the contact product may be previously contacted with the halogen-containing compound and / or the organometallic compound.
(4) Loading of magnesium compound (a′-1) from a mixture of a liquefying agent and optionally a magnesium compound (a′-1) solution containing a hydrocarbon solvent, an electron donor (a′-3) and a carrier A method of contacting a titanium compound (a′-2) after obtaining the prepared carrier.
(5) A method of contacting a carrier with a solution containing a magnesium compound (a′-1), a titanium compound (a′-2), an electron donor (a′-3), and optionally a hydrocarbon solvent.

(6) A method of bringing the liquid organomagnesium compound (a′-1) into contact with the halogen-containing titanium compound (a′-2). At this time, the electron donor (a′-3) is used at least once.
(7) A method in which a liquid organomagnesium compound (a′-1) and a halogen-containing compound are contacted, and then a titanium compound (a′-2) is contacted. In this process, the electron donor (a′-3) is used at least once.
(8) A method of bringing the alkoxy group-containing magnesium compound (a′-1) into contact with the halogen-containing titanium compound (a′-2). At this time, the electron donor (a′-3) is used at least once.
(9) A method of contacting a complex comprising an alkoxy group-containing magnesium compound (a′-1) and an electron donor (a′-3) with a titanium compound (a′-2).
(10) A complex composed of an alkoxy group-containing magnesium compound (a′-1) and an electron donor (a′-3) is contacted with an organometallic compound and then contacted with a titanium compound (a′-2). Method.

(11) A method in which a magnesium compound (a′-1), a titanium compound (a′-2), and an electron donor (a′-3) are contacted and reacted in an arbitrary order. Prior to this reaction, each component may be pretreated with a reaction aid such as an electron donor (a′-3), an organometallic compound, or a halogen-containing silicon compound.
(12) A liquid magnesium compound (a′-1) having no reducing ability and a liquid titanium compound (a′-2) are reacted in the presence of an electron donor (a′-3) to form a solid Of depositing a magnesium-titanium complex.
(13) A method of further reacting the titanium compound (a′-2) with the reaction product obtained in (12) above.
(14) A method in which the reaction product obtained in (11) or (12) is further reacted with an electron donor (a′-3) and a titanium compound (a′-2).
(15) A solid substance obtained by pulverizing a magnesium compound (a′-1), a titanium compound (a′-2), and an electron donor (a′-3) is used as a halogen, a halogen compound or A method of treating with any of aromatic hydrocarbons. In this method, only the magnesium compound (a′-1), a complex compound composed of the magnesium compound (a′-1) and the electron donor (a′-3), or the magnesium compound (a′-1) is used. ) And the titanium compound (a′-2) may be pulverized. Further, after pulverization, pretreatment with a reaction aid may be performed, and then treatment with halogen or the like may be performed. As the reaction aid, an organometallic compound or a halogen-containing silicon compound is used.

(16) A method of contacting the titanium compound (a′-2) after pulverizing the magnesium compound (a′-1). When the magnesium compound (a′-1) is pulverized and / or contacted, the electron donor (a′-3) is used together with a reaction aid as necessary.
(17) A method of treating the compound obtained in the above (11) to (16) with a halogen, a halogen compound or an aromatic hydrocarbon.
(18) A contact reaction product of a metal oxide, organomagnesium (a′-1) and a halogen-containing compound is brought into contact with an electron donor (a′-3) and more preferably a titanium compound (a′-2). Method.
(19) Magnesium compounds (a′-1) such as magnesium salts of organic acids, alkoxymagnesium and aryloxymagnesium, titanium compounds (a′-2), electron donors (a′-3), and as necessary Depending on the method, contact with a halogen-containing hydrocarbon.
(20) A method of bringing a hydrocarbon solution containing a magnesium compound (a′-1) and alkoxytitanium into contact with an electron donor (a′-3) and, if necessary, a titanium compound (a′-2). In this case, it is preferable that a halogen-containing compound such as a halogen-containing silicon compound coexists.
(21) A liquid magnesium compound (a′-1) having no reducing ability and an organometallic compound are reacted to precipitate a solid magnesium / metal (aluminum) complex, and then an electron donor (a′− 3) A method of reacting the titanium compound (a′-2).

  Examples of the organometallic compound catalyst component (b ′) include those containing a metal selected from Group I to Group III of the periodic table. Specifically, an organoaluminum compound represented by the following formula (1) ( b-1), a complex alkyl compound (b-2) of a Group I metal and aluminum represented by Formula (2), and a Group II or Group III organometallic compound represented by Formula (3) (B-3) and the like.

R ¹ _m Al (OR ² ) _n H _p X _q (1)
In the formula (1), R ¹ and R ² are hydrocarbon groups usually containing 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and these may be the same or different. X represents a halogen atom, and is a number of 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ p <3, 0 ≦ q <3, and m + n + p + q = 3.

R ¹ _m Al (OR ² ) _3-m (R ¹ and R ² are as defined above, and m is preferably a number of 1.5 ≦ m ≦ 3), preferably as formula (1). R ¹ _m AlX _3-m (R ¹ is as defined above, X is a halogen, m is preferably 0 <m <3), R ¹ _m AlH _3-m (R ¹ is as defined above) And m is preferably 2 ≦ m <3) and R ¹ _m Al (OR ² ) _n X _q (where R ¹ and R ² are the same as above, X is halogen, 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).
M ¹ AlR ¹ ₄ (2)
In formula (2), M ¹ is Li, Na or K, and R ¹ is the same as above.
R ¹ R ² M ² (3)
In formula (3), R ¹ and R ² are the same as above, and M ² is Mg, Zn or Cd.

Specific examples of the organosilicon compound catalyst component (c ′) include an organosilicon compound represented by the following formula (4).
SiR ¹ R ² _n (OR ³ ) _3-n (4)
In the formula (4), n is 0, 1 or 2, R ¹ is a group selected from the group consisting of a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group and derivatives thereof, and R ² and R ³ are hydrocarbon groups. Indicates.

Specific examples of R ¹ include cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 3-propylcyclopentyl group, 3-isopropylcyclopentyl group, 3-butylcyclopentyl group, 3-t -Butylcyclopentyl group, 2,2-dimethylcyclopentyl group, 2,3-dimethylcyclopentyl group, 2,5-dimethylcyclopentyl group, 2,2,5-trimethylcyclopentyl group, 2,3,4,5-tetramethylcyclopentyl Cyclopentyl groups such as 2,2,5,5-tetramethylcyclopentyl group, 1-cyclopentylpropyl group and 1-methyl-1-cyclopentylethyl group and derivatives thereof; cyclopentenyl group, 2-cyclopentenyl group, 3- Cyclopentenyl group, 2-methyl-1-cycl Lopentenyl group, 2-methyl-3-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 2-ethyl-3-cyclopentenyl group, 2,2-dimethyl-3-cyclopentenyl group, 2,5-dimethyl Cyclopentenyl groups such as -3-cyclopentenyl group, 2,3,4,5-tetramethyl-3-cyclopentenyl group and 2,2,5,5-tetramethyl-3-cyclopentenyl group and derivatives thereof; and 1,3-cyclopentadienyl group, 2,4-cyclopentadienyl group, 1,4-cyclopentadienyl group, 2-methyl-1,3-cyclopentadienyl group, 2-methyl-2, 4-cyclopentadienyl group, 3-methyl-2,4-cyclopentadienyl group, 2-ethyl-2,4-cyclopentadienyl group, 2,2-dimethyl-2,4-cyclopentadienyl Base 2,3-dimethyl-2,4-cyclopentadienyl group, 2,5-dimethyl-2,4-cyclopentadienyl group and 2,3,4,5-tetramethyl-2,4-cyclopentadiene And cyclopentadienyl groups such as an enyl group and derivatives thereof. Further, as derivatives of cyclopentyl group, cyclopentenyl group or cyclopentadienyl group, indenyl group, 2-methylindenyl group, 2-ethylindenyl group, 2-indenyl group, 1-methyl-2-indenyl group, 1,3-dimethyl-2-indenyl group, indanyl group, 2-methylindanyl group, 2-indanyl group, 1,3-dimethyl-2-indanyl group, 4,5,6,7-tetrahydroindenyl group, 4,5,6,7-tetrahydro-2-indenyl group, 4,5,6,7-tetrahydro-1-methyl-2-indenyl group, 4,5,6,7-tetrahydro-1,3-dimethyl- A 2-indenyl group, a fluorenyl group, etc. are mentioned.

Specific examples of R ² and R ³ include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups. When ^two or more R ² or R ³ are present, R ² or R ³ may be the same or different, and R ² and R ³ may be the same or different. R ² may be cross-linked with R ¹ and an alkylene group.

As the organosilicon compound catalyst component (c ′) represented by the formula (4), R ¹ is a cyclopentyl group, R ² is an alkyl group or a cyclopentyl group, and R ³ is an alkyl group, particularly a methyl group or an ethyl group. An organosilicon compound as a group is preferred.

  Specific examples of the organosilicon compound represented by the formula (4) include cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, 2,5-dimethylcyclopentyltrimethoxysilane, Trialkoxysilanes such as cyclopentyltriethoxysilane, cyclopentenyltrimethoxysilane, 3-cyclopentenyltrimethoxysilane, 2,4-cyclopentadienyltrimethoxysilane, indenyltrimethoxysilane and fluorenyltrimethoxysilane; Dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (3-tert-butylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysila Bis (2,5-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane, dicyclopentenyldimethoxysilane, di (3-cyclopentenyl) dimethoxysilane, bis (2,5-dimethyl-3-cyclopentenyl) dimethoxysilane , Di-2,4-cyclopentadienyldimethoxysilane, bis (2,5-dimethyl-2,4-cyclopentadienyl) dimethoxysilane, bis (1-methyl-1-cyclopentylethyl) dimethoxysilane, cyclopentylcyclo Pentenyldimethoxysilane, cyclopentylcyclopentadienyldimethoxysilane, diindenyldimethoxysilane, bis (1,3-dimethyl-2-indenyl) dimethoxysilane, cyclopentadienylindenyldimethoxysilane, difluorenyldimethyl Dialkoxysilanes such as toxisilane, cyclopentylfluorenyldimethoxysilane and indenylfluorenyldimethoxysilane; tricyclopentylmethoxysilane, tricyclopentenylmethoxysilane, tricyclopentadienylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethyl Methoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane, bis (2,5-dimethylcyclopentyl) cyclopentylmethoxysilane, dicyclopentylcyclopentenylmethoxysilane, Dicyclopentylcyclopentadienylmethoxysilane And monoalkoxysilanes such as diindenylcyclopentylmethoxysilane; and ethylenebiscyclopentyldimethoxysilane.

  Propylene-based polymer (A) is produced using a catalyst comprising the solid titanium catalyst component (a ′), organometallic compound catalyst component (b ′), and organosilicon compound catalyst component (c ′) as described above. In this case, preliminary polymerization can be performed in advance. In the prepolymerization, the olefin is polymerized in the presence of the solid titanium catalyst component (a ′), the organometallic compound catalyst component (b ′), and, if necessary, the organosilicon compound catalyst component (c ′).

  As the prepolymerized olefin, an α-olefin having 2 to 8 carbon atoms is used. Specifically, linear olefins such as ethylene, propylene, 1-butene and 1-octene, and 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, etc. An olefin having a branched structure is used. Two or more of these may be used for copolymerization.

  The prepolymerization is desirably performed so that about 0.1 to 1000 g, preferably about 0.3 to 500 g of a polymer is formed per 1 g of the solid titanium catalyst component (a ′). If the amount of prepolymerization is too large, the production efficiency of the (co) polymer in the main polymerization may decrease. In the prepolymerization, the catalyst is used at a considerably higher concentration than the catalyst concentration in the system in the main polymerization.

  When propylene is continuously multistage polymerized using the catalyst as described above, propylene and the above-mentioned other monomers are copolymerized in any stage or in all stages as long as the object of the present invention is not impaired. You may let them.

  In the case of continuous multistage polymerization, propylene is homopolymerized in each stage, or propylene-based polymer (A) is produced by copolymerizing propylene and a small amount of other monomers. In this polymerization, the solid titanium catalyst component (a ′) (or the prepolymerized catalyst) is usually about 0.0001 to 50 mmol, preferably about 0.001 to 50 mol in terms of titanium atom per 1 L of the polymerization volume. Used in an amount of 10 mmol. The organometallic compound catalyst component (b ') is usually used in an amount of about 1 to 2000 mol, preferably about 2 to 500 mol, in terms of the amount of metal atoms relative to 1 mol of titanium atoms in the polymerization system. The organosilicon compound catalyst component (c ′) is usually used in an amount of about 0.001 to 50 moles, preferably about 0.01 to 20 moles per mole of metal atoms of the organometallic compound catalyst component (b ′). It is done.

  The polymerization may be performed by a gas phase polymerization method or a liquid phase polymerization method such as a solution polymerization method or a suspension polymerization method, and each stage may be performed by a separate method. Moreover, you may carry out by any system of a continuous type and a semi-continuous type, and you may divide each stage into several polymerizers, for example, 2-10 polymerizers. Industrially, it is most preferable to polymerize by a continuous method, and in this case, it is preferable to carry out the polymerization in the second and subsequent stages separately into two or more polymerization vessels, thereby suppressing the generation of gel. .

As the polymerization medium, inert hydrocarbons are usually used, but liquid propylene may be used.
The polymerization conditions for each stage include a polymerization temperature in the range of about −50 to 200 ° C., preferably about 20 to 100 ° C., and a polymerization pressure of normal pressure to 10 MPa (gauge pressure), preferably about 0.2 to 5 MPa (gauge). Pressure).

  After completion of the polymerization, the propylene polymer (A) is obtained as a powder by performing post-treatment steps such as a known catalyst deactivation treatment step, a catalyst residue removal step, and a drying step as necessary.

  The amount of the propylene polymer (A) used is usually 1 to 98.5% by weight in a total of 100% by weight of the propylene polymer (A), the modified propylene polymer (B) and the carbon fiber (C), Preferably it is 10 to 94 weight%, More preferably, it is 30 to 89 weight%.

[Modified propylene polymer (B)]
The modified propylene polymer (B) used in the present invention has at least one functional group capable of reacting with the reactive functional group of the surface-treated carbon fiber (C), and in the presence of a metallocene catalyst. Obtained by graft-modifying the propylene-based polymer (F) produced in step 1 with an ethylenically unsaturated bond-containing monomer. Here, the functional group capable of reacting with the reactive functional group of the surface-treated carbon fiber (C) includes a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, an amino group, a halogen atom, an amide group, and an imide. Groups, ester groups, alkoxysilane groups, acid halide groups, aromatic rings, nitrile groups, and the like, preferably carboxyl groups, acid anhydride groups, and derivatives thereof. Since the propylene polymer (F) produced in the presence of the metallocene catalyst has low crystallinity and low molecular weight components, the modified propylene polymer (B) comprising the propylene polymer (F) as a constituent component is used. If used, it is possible to obtain a carbon fiber reinforced propylene-based composite material with improved bending strength while maintaining a good bending elastic modulus.

The modified propylene polymer (B) satisfies the following requirements (b-1) to (b-4).
(B-1) Melting | fusing point (Tm) is 135 degreeC or more, Preferably it is 140 degreeC or more, More preferably, it is 145 degreeC or more.

When the melting point (Tm) is less than 135 ° C., the flexural modulus of the modified propylene resin is lowered, and the flexural modulus of the carbon fiber reinforced propylene composite material is lowered.
In addition, melting | fusing point (Tm) is an endothermic peak at the time of the 2nd temperature rise measured with the differential scanning calorimeter (DSC).

(B-2) The graft amount in the modified propylene polymer (B) is 1 to 5% by weight, preferably 1.3 to 5% by weight, more preferably 1.8 to 5% by weight.
If the modified propylene polymer (B) having a graft amount in the above range is used, a carbon fiber reinforced propylene composite material with improved bending strength can be obtained while maintaining good bending elastic modulus. When the graft amount is less than 1% by weight, the effect of improving the adhesion between the propylene-based polymer (A) and the carbon fiber (C) by the modified propylene-based polymer (B) tends to decrease, and the resulting carbon fiber The bending strength of the reinforced propylene-based composite material may decrease. On the other hand, when the graft amount exceeds 5% by weight, the dispersibility of the modified propylene polymer (B) in the propylene polymer (A) tends to decrease. Therefore, the effect of improving the adhesion between the propylene polymer (A) and the carbon fiber (C) by the modified propylene polymer (B) is lowered, and the bending strength of the obtained carbon fiber reinforced propylene composite material is lowered. There is a case.

The amount of grafting is about 2 g of the modified propylene polymer (B) completely heated and dissolved in 500 ml of boiling p-xylene. After cooling, it is poured into 1200 ml of acetone, and the precipitate is filtered and dried. to prepare a pressed film obtained by calculating the peak intensity ratio of FT-IR of 1790 cm ^-1 and 974 cm ^-1.

(B-3) The intrinsic viscosity [η] in decalin at 135 ° C. is 0.2-4 dl / g, preferably 0.4-3 dl / g, more preferably 0.6-2 dl / g.
When the intrinsic viscosity [η] is less than 0.2 dl / g, the strength of the modified propylene-based polymer (B) decreases, and the bending strength of the obtained carbon fiber reinforced propylene-based composite material may decrease. On the other hand, when the intrinsic viscosity [η] is higher than 4 dl / g, the dispersibility of the modified propylene polymer (B) in the propylene polymer (A) tends to decrease. Therefore, the effect of improving the adhesion between the propylene polymer (A) and the carbon fiber (C) by the modified propylene polymer (B) is lowered, and the strength of the obtained carbon fiber reinforced propylene composite material may be lowered. .

(B-4) The amount of components soluble in o-dichlorobenzene at 70 ° C. is 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less.
The component soluble in o-dichlorobenzene at 70 ° C. is derived from a low crystalline or low molecular weight component contained in the propylene polymer (F), and when the amount is more than 3% by weight, carbon obtained is obtained. The flexural modulus of the fiber reinforced propylene-based composite material may decrease.

  In addition, the amount of components soluble in 70 ° C. o-dichlorobenzene is measured using a temperature rising elution fractionation (TREF) section for performing crystallinity fractionation in a cross fractionation chromatograph (CFC) measurement device.

  The modified propylene polymer (B) is obtained by graft-modifying the propylene polymer (F) with an ethylenically unsaturated bond-containing monomer having the functional group using an organic peroxide. Hereinafter, the propylene polymer (F), the ethylenically unsaturated bond-containing monomer, and the organic peroxide produced in the presence of the metallocene catalyst will be described in detail.

<Propylene polymer (F)>
The propylene polymer (F) used in the present invention is produced in the presence of a metallocene catalyst. Examples of the propylene-based polymer (F) include a propylene homopolymer, a random copolymer or a block copolymer of propylene and another small amount of monomer, and preferably a propylene homopolymer and propylene. Examples include random copolymers with other small amounts of monomers. Other small amounts of monomers include ethylene and α-olefins having 4 to 20 carbon atoms.

  The melting point (Tm) of the propylene polymer (F) is usually from 145 to 170 ° C, preferably from 150 to 170 ° C, more preferably from 155 to 170 ° C. When the melting point (Tm) of the propylene polymer (F) is less than 145 ° C., the melting point (Tm) of the resulting modified propylene polymer (B) is less than 140 ° C., and the rigidity of the carbon fiber reinforced propylene composite material. And the strength may decrease.

The intrinsic viscosity [η] of the propylene polymer (F) in decalin at 135 ° C. is usually 0.5 to 15 dl / g, preferably 1.0 to 10 dl / g.
The melt flow rate (MFR; 230 ° C., 2.16 kgf) of the propylene polymer (F) is usually 0.001 to 1500 g / 10 min, preferably 0.005 to 100 g / 10 min.

  The molecular weight distribution (Mw / Mn) of the propylene-based polymer (F) is usually 1.5 to 4.0, preferably 1.5 to 3.5, more preferably 1.5 to 3.0. is there. A large molecular weight distribution (Mw / Mn) means that there are many low molecular weight components contained in the propylene polymer (F). When the molecular weight distribution (Mw / Mn) of the propylene polymer (F) is larger than 4.0, the low molecular weight component is further reduced by decomposition or the like when the modified propylene polymer (B) is produced. As a result, the strength of the resulting carbon fiber reinforced propylene-based composite material may be reduced.

  The amount of residual chlorine contained in the raw material of the propylene polymer (F) is usually 3 ppm by weight or less, preferably 1 ppm by weight or less. When the amount of residual chlorine exceeds 3 ppm by weight, free chlorine may be generated during the production of the modified propylene polymer (B), and the low molecular weight modified propylene polymer (B) may be by-produced. . Moreover, the amount of residual chlorine in the modified propylene polymer (B) increases, and the fatigue strength of the resulting carbon fiber reinforced propylene composite material may decrease.

  Further, if the propylene polymer (F) contains even a small amount of a double bond structure, the ethylenically unsaturated bond-containing monomer reacts with the double bond structure during the production of the modified propylene polymer (B). The graft amount in the modified propylene polymer (B) tends to increase.

The sum of the content of the heterogeneous bonds based on the 2,1-insertion and 1,3-insertion of the propylene monomer in the propylene-based polymer (F) is usually 0.1 in a total of 100 mol% of all the bonds derived from propylene. It is 1 mol% or less, preferably 0.05 mol% or less. When the sum of the content of heterogeneous bonds based on 2,1-insertion and 1,3-insertion of propylene monomer is in the above range, the melting point (Tm) of the modified propylene polymer (B) is increased, and the resulting carbon The strength of the fiber-reinforced propylene-based composite material is increased.
In addition, the content of the heterogeneous bond based on 2,1-insertion or 1,3-insertion of the propylene monomer in the propylene-based polymer (F) can be determined from a ¹³ C-NMR spectrum.

Production method of propylene polymer (F) The propylene polymer (F) used in the present invention is propylene in the presence of a polymerization catalyst containing a metallocene compound having a ligand such as a cyclopentadienyl skeleton in the molecule. Is produced by homopolymerization of propylene and copolymerization of propylene and other small amount of monomers.

  The metallocene compound having a ligand having a cyclopentadienyl skeleton in the molecule is represented by the metallocene compound (D1) represented by the following general formula [I] and the following general formula [II] because of its chemical structure. The bridged metallocene compound (D2) is preferable, and the bridged metallocene compound (D2) is preferable.

上記一般式［Ｉ］および［ＩＩ］において、Ｍは第４族遷移金属、好ましくはチタン原子、ジルコニウム原子またはハフニウム原子を示し、Ｑはハロゲン原子、炭化水素基、アニオン配位子、および孤立電子対で配位可能な中性配位子から選ばれる基であり、jは1〜4の整数であり、Ｃｐ¹およびＣｐ²は、Ｍを挟んだサンドイッチ構造を形成するシクロペンタジエニル基または置換シクロペンタジエニル基であり、互いに同一でも異なっていてもよい。置換シクロペンタジエニル基としては、インデニル基、フルオレニル基、アズレニル基、およびこれらの基に１個以上の炭化水素基が置換した基が挙げられ、置換シクロペンタジエニル基がインデニル基、フルオレニル基およびアズレニル基である場合、シクペンタジエニル基に縮合する不飽和環の二重結合の一部は水添されていてもよい。

In the above general formulas [I] and [II], M represents a Group 4 transition metal, preferably a titanium atom, a zirconium atom or a hafnium atom, and Q represents a halogen atom, a hydrocarbon group, an anionic ligand, and a lone electron. A group selected from a neutral ligand capable of coordinating in a pair, j is an integer of 1 to 4, and Cp ¹ and Cp ² are a cyclopentadienyl group forming a sandwich structure sandwiching M or A substituted cyclopentadienyl group, which may be the same or different; Examples of the substituted cyclopentadienyl group include an indenyl group, a fluorenyl group, an azulenyl group, and a group in which one or more hydrocarbon groups are substituted for these groups. The substituted cyclopentadienyl group is an indenyl group or a fluorenyl group. And in the case of an azulenyl group, a part of the double bond of the unsaturated ring condensed to the cycladienyl group may be hydrogenated.

In the general formula [II], Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, -Ge- Divalent germanium-containing group, -Sn-, divalent tin-containing group, ether bond (-O-), carbonyl group (-CO-), sulfide (-S-), sulfoxide (-SO-), sulfone (-SO ₂ -), amino group ^{(-NR a -), - P} (R a) -, - P (O) (R a) -, - BR a - or -AlR ^a - is shown (wherein, R ^a is ^a bond of one or two hydrogen atoms, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms An amino group).

  The polymerization catalyst used in the present invention is represented by the general formula [III] described in the pamphlet of International Publication No. 2001/27124 already filed by the present applicant among the catalysts represented by the general formula [II]. A metallocene catalyst, an organometallic compound, an organoaluminum oxy compound, one or more compounds selected from compounds capable of reacting with the metallocene compound to form ion pairs (cocatalysts), and, if necessary, a particulate carrier It is a metallocene polymerization catalyst.

上記一般式［ＩＩＩ］において、Ｒ¹〜Ｒ¹⁴は水素原子、炭化水素基およびケイ素含有基から選ばれる基を示し、それぞれ同一でも異なっていてもよい。

In the general formula [III], R ^{1 to} R ¹⁴ represent groups selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group, and may be the same or different.

  Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl group. And linear hydrocarbon groups such as n-decanyl group; isopropyl group, t-butyl group, 2,3-dimethylbutyl group, amyl group, 2-methylpentyl group, 3-methylpentyl group, 2-ethylpentyl group Branched hydrocarbon groups such as 4-methylheptyl, 4-propylheptyl and 2,3,4-trimethylpentyl; cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl and adamantyl Cyclic unsaturated hydrocarbon groups such as phenyl group, tolyl group, naphthyl group, biphenyl group, phenanthryl group and anthracenyl group; benzyl group, cumyl group, 1,1-diph Saturated hydrocarbon groups substituted by cyclic unsaturated hydrocarbon groups such as nylethyl group and triphenylmethyl group; methoxy group, ethoxy group, phenoxy group, furyl group, N-methylamino group, N, N'-dimethylamino group , Heteroatom-containing hydrocarbon groups such as N-phenylamino group, pyryl group and thienyl group.

R ^{1 to} R ⁴ are more preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ² and R ⁴ are more preferably a hydrocarbon group having 1 to 20 carbon atoms. It is particularly preferable that ¹ and R ³ are hydrogen atoms, and R ² and R ⁴ are linear or branched alkyl groups having 1 to 5 carbon atoms.

R ^{5 to} R ¹² are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The adjacent substituents of R ^{5 to} R ¹² may be bonded to each other to form a ring. Specifically, benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyl An octahydrodibenzofluorenyl group and an octamethyltetrahydrodicyclopentafluorenyl group may be formed. Among these, it is particularly preferable that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ simultaneously form a fluorene ring that is not a hydrogen atom.

Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group.
Y is a group 14 element, preferably a carbon atom, a silicon atom and a germanium atom, more preferably a carbon atom.

R ¹³ and R ¹⁴ are each a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms and an aryl group having 6 to 20 carbon atoms, more preferably a methyl group, An ethyl group, a phenyl group and a tolyl group; R ¹³ and R ¹⁴ may be the same or different and may be bonded to each other to form a ring, or may be bonded to an adjacent group of R ^{5 to} R ¹² or an adjacent group of R ^{1 to} R ^4. To form a ring.

M is a Group 4 transition metal, preferably a titanium atom, a zirconium atom or a hafnium atom.
Q is a group selected from a halogen atom, a hydrocarbon group, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair, and at least one is preferably a halogen atom or an alkyl group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group are the same as those described above. Anionic ligands include alkoxy groups such as methoxy, t-butoxy and phenoxy groups; carboxylate groups such as acetate and benzoate; and sulfonate groups such as mesylate and tosylate. Neutral ligands that can be coordinated by lone pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine; tetrahydrofuran, diethyl ether, dioxane and 1,2-dimethoxyethane. And ethers.

j is an integer of 1 to 4, and when j is 2 or more, Q may be the same or different.
Specific examples of the metallocene catalyst represented by the general formula [III] include dimethylmethylene (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride, 1-phenylethylidene (4-t-butyl-2-methylcyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and [3- (1 ', 1', 4 ', 4', 7 ' , 7 ', 10', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5-t-butyl-1,2,3,3a-tetrahydropentalene)] Examples include zirconium dichloride.

  One or more compounds selected from organometallic compounds, organoaluminum oxy compounds used together with the metallocene catalyst represented by the above general formula [III], compounds capable of reacting with the metallocene catalyst to form ion pairs, and necessary As the particulate carrier used in accordance with the above, the compounds disclosed in the above-mentioned International Publication No. 2001/27124 pamphlet and JP-A-11-315109 can be used without limitation.

<Ethylenically unsaturated bond-containing monomer>
The ethylenically unsaturated bond-containing monomer used in the present invention is a compound having both an ethylenically unsaturated bond capable of radical polymerization and one or more polar groups in one molecule. Examples of polar groups include halogen atoms, carboxyl groups, acid anhydride groups, epoxy groups, hydroxyl groups, amino groups, amide groups, imide groups, ester groups, alkoxysilane groups, acid halides, aromatic rings, and nitrile groups.

  Specific examples of the ethylenically unsaturated bond-containing monomer include unsaturated carboxylic acids and derivatives thereof (acid anhydrides, acid amides, esters, acid halides and metal salts), imides, hydroxyl group-containing ethylenically unsaturated compounds, and epoxy groups. -Containing ethylenically unsaturated compounds, styrenic monomers, acrylonitrile, vinyl acetate and vinyl chloride, etc., preferably unsaturated carboxylic acids and derivatives thereof, hydroxyl group-containing ethylenically unsaturated compounds and epoxy group-containing ethylenically unsaturated compounds. Can be mentioned.

  Examples of unsaturated carboxylic acids and derivatives thereof include (meth) acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, citraconic acid, crotonic acid, isocrotonic acid, endocis- Bicyclo [2.2.1] hept-2,3-dicarboxylic acid (Nadic acid ™), Nadic anhydride and methyl-endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic And unsaturated carboxylic acids such as methyl nadic acid (trademark) and their anhydrides; and unsaturated carboxylic acid esters such as methyl methacrylate, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, and imides. Is malonyl chloride, maleimide, maleic anhydride, citraconic anhydride, nadi anhydride Examples include succinic acid, acrylic acid, nadic acid, maleic acid, monomethyl maleate, dimethyl maleate and methyl methacrylate, and more preferably acrylic acid, maleic acid, nadic acid, maleic anhydride, nadic anhydride and methacrylic acid. And methyl. Unsaturated carboxylic acid and its derivative may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the hydroxyl group-containing ethylenically unsaturated compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth). Acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono (Meth) acrylate, polyethylene glycol mono (meth) acrylate and 2- (6-hydroxyhexanoyloxy) ethyl acrylate, 10-undecen-1-ol, 1-octene- -Ol, 2-methylol norbornene, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylol acrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, allyloxyethanol and 2-butene -1,4-diol, glycerin monoalcohol and the like, preferably 10-undecen-1-ol, 1-octen-3-ol, 2-methanol norbornene, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylol acrylamide, 2- (meth) Examples include acryloyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol and glycerin monoalcohol, more preferably 2-hydroxyethyl (meth) acrylate and 2 -Hydroxypropyl (meth) acrylate is mentioned. A hydroxyl-containing ethylenically unsaturated compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of the epoxy group-containing ethylenically unsaturated compound include unsaturated glycidyl esters represented by the following formula (IV), unsaturated glycidyl ethers represented by the following formula (V), and formula (VI) And epoxy alkenes represented by:

式（ＩＶ）中、Ｒは重合可能なエチレン性不飽和結合を有する炭化水素基を示す。

In the formula (IV), R represents a hydrocarbon group having a polymerizable ethylenically unsaturated bond.

式（Ｖ）中、Ｒは重合可能なエチレン性不飽和結合を有する炭化水素基を示し、Ｘは−ＣＨ₂−Ｏ−または−Ｃ₆Ｈ₄−Ｏ−で表される２価の基を示す。

In the formula (V), R represents a hydrocarbon group having a polymerizable ethylenically unsaturated bond, and X represents a divalent group represented by —CH ₂ —O— or —C ₆ H ₄ —O—. Show.

式（ＶＩ）中、Ｒ¹は重合可能なエチレン性不飽和結合を有する炭化水素基を示し、Ｒ²は水素原子またはメチル基を示す。

In the formula (VI), R ¹ represents a hydrocarbon group having a polymerizable ethylenically unsaturated bond, and R ² represents a hydrogen atom or a methyl group.

  Specific examples of the epoxy group-containing ethylenically unsaturated compound include glycidyl (meth) acrylate, mono- or diglycidyl ester of itaconic acid, mono-, di- or triglycidyl ester of butenetricarboxylic acid, mono- or diglycidyl ester of tetraconic acid, Mono- or diglycidyl ester of endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ™), endo-cis-bicyclo [2.2.1] hept -5-ene-2,3-dimethyl-2,3-dicarboxylic acid (methyl nadic acid, trademark) mono- or diglycidyl ester, allyl succinic acid mono- or diglycidyl ester, p-styrene carboxylic acid glycidyl ester, allyl Glycidyl ether, 2-methylallyl glycidyl ether Styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3- Examples thereof include methyl-1-pentene, 5,5-epoxy-1-hexene, and vinylcyclohexene monoxide, and preferred are glycidyl acrylate and glycidyl methacrylate. The epoxy group-containing ethylenically unsaturated compound may be used alone or in combination of two or more.

Note that “(meth) acryl” means “acryl” and / or “methacryl”.
Of the above ethylenically unsaturated bond-containing monomers, more preferred are unsaturated carboxylic acids and derivatives thereof, particularly preferred are unsaturated carboxylic acid anhydrides, and most preferred are maleic anhydride.

<Organic peroxide>
Examples of the organic peroxide used in the present invention include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2- Peroxyketals such as bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) valerate and 2,2-bis (t-butylperoxy) butane; di-t-butyl peroxide , Dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane and 2,5- Dialkyl peroxides such as dimethyl-2,5-bis (t-butylperoxy) hexyne-3; Diacyl peroxides such as xoxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,5-dichlorobenzoyl peroxide and m-trioyl peroxide; t -Butyloxyacetate, t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurylate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5- Dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropylcarbonate, cumylperoxyoct Peroxyesters such as tate; peroxydicarbonates such as di (2-ethylhexyl) peroxydicarbonate and di (3-methyl-3-methoxybutyl) peroxydicarbonate; and t-butyl hydroperoxide, cumene hydroperoxide, diisopropyl And hydroperoxides such as benzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide, etc., preferably t-butylperoxybenzoate, Examples include 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylperoxy-2-ethylhexanoate, and dicumyl peroxide.

<Method for Producing Modified Propylene Polymer (B)>
The modified propylene polymer (B) used in the present invention is obtained by subjecting a propylene polymer (F) and an ethylenically unsaturated bond-containing monomer to a modification reaction in the presence of an organic peroxide under heating conditions. Manufactured.

The denaturation temperature is usually 50 to 250 ° C, preferably 60 to 200 ° C.
The time required for denaturation is usually 15 minutes to 20 hours, preferably 0.5 to 10 hours.
The denaturation reaction can be carried out under normal pressure or pressurized conditions.

Denaturation can be carried out in the presence of a solvent or in the absence of a solvent.
When carried out in the presence of a solvent, the solvent includes aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, tetradecane and kerosene; alicyclic rings such as methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane and cyclododecane. Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, ethyltoluene, trimethylbenzene, cymene and diisopropylbenzene; and chlorobenzene, bromobenzene, o-dichlorobenzene, carbon tetrachloride, trichloroethane, trichloroethylene, And halogenated hydrocarbons such as tetrachloroethane and tetrachloroethylene. When carried out in the presence of a solvent, the amount of the ethylenically unsaturated bond-containing monomer relative to 100 parts by weight of the propylene polymer (F) is usually 0.2 to 100 parts by weight, preferably 0.5 to 50 parts by weight, The amount of the organic peroxide is usually 0.001 to 20 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.

  When carried out in the absence of a solvent, it is particularly preferred to carry out the modification reaction by kneading in a molten state. Specifically, a known method for mixing resins or a resin and a solid or liquid additive is used. As a method of mixing, a method of kneading a mixture of each component with a Henschel mixer, a ribbon blender, a blender, etc., and adding several components to a Henschel mixer, a ribbon blender, a blender, etc., respectively, and mixing to make a uniform mixture And a method of kneading the mixture. For kneading, for example, a Banbury mixer, a plast mill, a Brabender plastograph, and a single or twin screw extruder are used.

  Particularly preferably as a modification method of the propylene polymer (F), a propylene polymer (F), an ethylenically unsaturated bond-containing monomer and an organic peroxide, which are sufficiently premixed in advance using a single or twin screw extruder, are used. This is a method of carrying out kneading by supplying from the supply port of the extruder. This is because continuous production is possible with this method, and productivity is improved by using the above method.

  The temperature of the kneading part of the kneader (for example, cylinder temperature in the case of an extruder) is usually 100 to 300 ° C, preferably 160 to 250 ° C. If the temperature is lower than 100 ° C, the graft amount in the modified propylene polymer (B) may not be sufficiently obtained. If the temperature is higher than 250 ° C, the modified propylene polymer (B) is decomposed. There is a case.

  The kneading time is 0.1 to 30 minutes, particularly preferably 0.5 to 5 minutes. If the kneading time is less than 0.1 minutes, a sufficient graft amount may not be obtained, and if the kneading time exceeds 5 minutes, the modified propylene polymer (B) may be decomposed.

  In the production method of the modified propylene polymer (B), when it is produced by melt-kneading, the amount of each component is, for example, 100 parts by weight of the propylene polymer (F) containing ethylenically unsaturated bonds. The monomer is usually 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, and the organic peroxide is usually 0.001 to 10 parts by weight, preferably 0. 0.01 to 5 parts by weight, more preferably 0.1 to 4 parts by weight.

  The modified propylene polymer (B) obtained as described above preferably has a carboxyl group, an acid anhydride group or a derivative thereof, more preferably a carboxyl group, an acid anhydride group, an amide group or an ester. Group, acid halide group and the like.

  The amount of the modified propylene polymer (B) used is 0.5 to 40% by weight, preferably 1 to 30% by weight in a total of 100% by weight of the propylene polymer (A) and the modified propylene polymer (B). %, More preferably 2 to 20% by weight. When the amount of the modified propylene polymer (B) used is less than 0.5% by weight, the interaction between the carbon fiber (C) and the modified propylene polymer (B) is lowered, and the carbon fiber reinforced propylene composite The strength of the material may decrease. On the other hand, when the amount of the modified propylene polymer (B) used is larger than 40% by weight, the strength of the carbon fiber reinforced propylene composite material is lowered due to the strength of the modified propylene polymer (B) itself. There is.

[Surface-treated carbon fiber (C)]
The surface-treated carbon fiber (C) used in the present invention is also simply referred to as “carbon fiber (C)”. "Is a surface treatment of carbon fiber.

  Conventionally known carbon fibers are used as the carbon fibers, and examples thereof include PAN-based carbon fibers made from polyacrylonitrile and pitch-based carbon fibers made from pitch. Moreover, what is called a chopped carbon fiber etc. which cut | judged the fiber raw yarn to desired length is also used. As chopped carbon fiber, for example, in the case of PAN-based carbon fiber, trading card chop (trade name; manufactured by Toray Industries, Inc.), pyrofil (chop) (trade name; manufactured by Mitsubishi Rayon Co., Ltd.) and tenax (chop) (trade name) ; Toho Tenax Co., Ltd.), and pitch-based carbon fiber, Dyalead (trade name; manufactured by Mitsubishi Chemical Corporation), Donakabo (chop) (trade name; manufactured by Osaka Gas Chemical Co., Ltd.) ) And Kureka chop (trade name; manufactured by Kureha Chemical Co., Ltd.). The epoxy polymer, nylon polymer and urethane polymer include Tenax (HTA-C6-SR (epoxy resin sizing); HTA-C6-N (nylon resin sizing); HTA-C6- US (urethane resin sizing)).

  As a method for surface treatment of carbon fiber, a well-known method that is generally used may be used. For example, carbon fiber is subjected to electrolytic surface treatment with an acid or alkaline aqueous solution to impart a functional group to the surface of carbon fiber. And a method of treating with a sizing agent. Among these, sizing treatment using an epoxy polymer, a nylon polymer, a urethane polymer, or the like is preferable.

  The carbon fiber (C) used in the present invention has a fiber diameter of usually larger than 2 μm and 15 μm or less, preferably 3 to 12 μm, more preferably 4 to 10 μm. If the fiber diameter is 2 μm or less, the rigidity of the fiber may be significantly reduced. If the fiber diameter exceeds 15 μm, the aspect ratio of the fiber (L / D: L is length and D is thickness) is reduced. In some cases, sufficient reinforcement efficiency such as heat resistance cannot be obtained. Here, the fiber diameter is obtained by cutting the fiber perpendicularly to the fiber direction, observing the cross section with a microscope, measuring the diameter, and obtaining an average value of the diameters of 100 or more fibers.

  When carbon fiber (C) is used as chopped carbon fiber, the fiber length of carbon fiber (C) is usually 0.01 to 20 mm, preferably 0.5 to 15 mm, more preferably 1 to 10 mm. When the fiber length is less than 0.01 mm, the aspect ratio is small and sufficient reinforcement efficiency cannot be obtained. When the fiber length exceeds 20 mm, the workability and appearance may be significantly deteriorated.

  The carbon fiber reinforced propylene-based composite material of the present invention may be in the form of pellets formed by impregnating a sizing-treated carbon fiber (C) with a propylene-based polymer (A) and a modified propylene-based polymer (B). . In the above-mentioned pellet, it is desirable that carbon long fibers having a length of 4 to 50 mm are arranged in parallel with the same length in the length direction of the pellet.

The fiber length is measured using a caliper or the like, and an average value of fiber lengths of 100 or more fibers is obtained.
The carbon fiber (C) may be a carbon fiber base fabric.

  The carbon fiber (C) is compounded together with other components constituting the carbon fiber reinforced propylene-based composite material of the present invention by using a melt kneading apparatus such as an extruder. It is desirable to select a compounding method that prevents excessive breakage of component (C). In order to achieve this, for example, in melt kneading with an extruder, components other than the carbon fiber (C) component are sufficiently melt kneaded, and then the carbon fiber (C) component is mixed with the resin component by a side feed method or the like. Feeding from a position downstream from the complete melting position is performed to disperse the convergent fibers while minimizing fiber breakage.

  The amount of the carbon fiber (C) used is 1 to 80% by weight, preferably 2 to 60% in the total 100% by weight of the propylene polymer (A), the modified propylene polymer (B) and the carbon fiber (C). % By weight, more preferably 5 to 40% by weight.

[Other ingredients]
If necessary, other components may be added to the carbon fiber reinforced propylene-based composite material of the present invention. Examples of other components include heat stabilizers, weather stabilizers, antistatic agents, lubricants, slip materials, hydrochloric acid absorbents, dispersants, nucleating agents, and flame retardants.

The amount of other components added is usually 0.01 to 10 parts by weight with respect to 100 parts by weight in total of the propylene polymer (A), the modified propylene polymer (B) and the carbon fiber (C).
In addition to the above other components, an elastomer may be added for the purpose of improving the impact resistance of the carbon fiber reinforced propylene-based composite material. The elastomer is not particularly limited, and is a propylene / α-olefin block copolymer, ethylene / α-olefin random copolymer, ethylene / α-olefin / non-conjugated polyene random copolymer, hydrogenated propylene / α-olefin. Examples thereof include block copolymers and other elastic polymers, and mixtures thereof. As the α-olefin, those similar to those already described as the α-olefin constituting the propylene polymer (A) or the modified propylene polymer (B) are used. These α-olefins may be used alone or in combination of two or more.

  Examples of the method for adding the elastomer include a physical blending method such as a melt blending method. The melt blending method refers to a method of mechanically kneading while heating and plasticizing using a mixing roll, a Banbury mixer or a single or twin screw extruder.

When the elastomer is a propylene / α-olefin block copolymer or ethylene / α-olefin random copolymer, the elastomer is added by a method for producing a propylene / α-olefin block copolymer in addition to the physical blending method described above. May be. That is, the production of the propylene / α-olefin block copolymer is carried out by continuously performing the following two steps (step 1 and step 2).
[Step 1] Propylene or propylene and ethylene and / or an α-olefin having 4 or more carbon atoms are (co) polymerized in the presence of a metallocene catalyst to produce a propylene homopolymer or propylene / α-olefin copolymer The process of manufacturing a coalescence.
[Step 2] Propylene and ethylene and / or an α-olefin having 4 or more carbon atoms are copolymerized in the presence of a metallocene catalyst to produce a propylene-containing more ethylene and / or α-olefin than in Step 1. A step of producing an α-olefin copolymer.

  The addition amount of the elastomer is usually 0.5 to 50 parts by weight, preferably 1 to 100 parts by weight with respect to 100 parts by weight in total of the propylene polymer (A), the modified propylene polymer (B) and the carbon fiber (C). 40 parts by weight, more preferably 5 to 30 parts by weight.

[Carbon fiber reinforced propylene composite]
The carbon fiber reinforced propylene composite material of the present invention melts the propylene polymer (A), modified propylene polymer (B), carbon fiber (C), and other optional components obtained as described above. Manufactured by kneading.

The carbon fiber reinforced propylene-based composite material satisfies the following requirements (i) to (iv).
(I) The amount of carbon fiber (C) used is 1 to 80% by weight, preferably 100% by weight in total of propylene polymer (A), modified propylene polymer (B) and carbon fiber (C), preferably It is 2 to 60% by weight, more preferably 5 to 40% by weight. When the content of the carbon fiber (C) is less than 1% by weight, the effect of reinforcing the resin by the carbon fiber (C) does not appear, and when it exceeds 80% by weight, the toughness of the carbon fiber-reinforced propylene composite material is lost. There is a case.
(Ii) The melting point (Tm) is 150 ° C. or higher, preferably 153 ° C. or higher, more preferably 156 ° C. or higher. When the melting point (Tm) is lower than 150 ° C. or more, the heat resistance of the carbon fiber reinforced propylene-based composite material is lowered and may not be suitable for applications requiring heat resistance.
(Iii) The amount of the modified propylene polymer (B) used is 0.5 to 40% by weight, preferably 1 to 30% by weight in the total of the propylene polymer (A) and the modified propylene polymer (B). %, More preferably 2 to 20% by weight. When the amount of the modified propylene polymer (B) used is less than 0.5% by weight, the interaction between the carbon fiber (C) and the modified propylene polymer (B) is lowered, and the carbon fiber reinforced propylene composite The strength of the material may decrease. On the other hand, when the amount of the modified propylene polymer (B) used is larger than 40% by weight, the strength of the carbon fiber reinforced propylene composite material is lowered due to the strength of the modified propylene polymer (B) itself. There is.

(Iv) The weight fraction of the amount of the ethylenically unsaturated bond-containing monomer graft derived from the modified propylene polymer (B) is 100% by weight of the total amount of the propylene polymer (A) and the modified propylene polymer (B). Is 0.2 to 2% by weight, preferably 0.2 to 1.5% by weight, and more preferably 0.2 to 1.0% by weight. The weight fraction of the amount of the ethylenically unsaturated bond-containing monomer graft in the modified propylene polymer (B) with respect to the total amount of 100% by weight of the propylene polymer (A) and the modified propylene polymer (B) is in the above range. In this case, a carbon fiber reinforced propylene-based composite material having improved bending strength while maintaining a good bending elastic modulus can be obtained. Further, in the present invention, instead of the propylene polymer (F) produced in the presence of the metallocene catalyst, for example, a modified propylene polymer using a propylene polymer produced in the presence of a Ziegler-Natta catalyst is used. When (B) is manufactured, the balance between the bending strength and the flexural modulus of the carbon fiber reinforced propylene composite material tends to deteriorate. Compared with the propylene polymer (F), the propylene polymer produced in the presence of a Ziegler-Natta catalyst has many low crystallinity and low molecular weight components, and the resulting modified propylene polymer is also the above modified propylene polymer. This is presumably because the amount of low crystallinity and low molecular weight components increases compared to the polymer (B). If the amount of the ethylenically unsaturated bond-containing monomer graft derived from the modified propylene polymer (B) is less than 0.2% by weight, the interaction between the carbon fiber (C) and the modified propylene polymer (B) decreases. However, the strength of the carbon fiber reinforced propylene-based composite material may be reduced. On the other hand, when the amount of the ethylenically unsaturated bond-containing monomer graft derived from the modified propylene polymer (B) is more than 2% by weight, the compatibility between the propylene polymer (A) and the modified propylene polymer (B) is improved. May deteriorate, or the strength of the carbon fiber reinforced propylene composite material may decrease due to the strength of the modified propylene polymer (B) itself.

[Molded body]
The molded body of the present invention is obtained from the carbon fiber reinforced propylene-based composite material.
Since the carbon fiber reinforced propylene-based composite material exhibits good mechanical strength (in terms of bending strength and tensile strength), examples of suitable uses of the molded body of the present invention include automobile parts (front end, fan sheroud, Cooling fan, engine under cover, engine cover, radiator box, side door, back door inner, back door outer, outer plate, roof rail, door handle, luggage box, wheel cover, handle, cooling module, air cleaner, spoiler, fuel tank , Platforms and side members), motorcycle and bicycle parts (luggage boxes, handles and wheels), housing-related parts (hot water toilet seat parts, bathroom parts, chair legs, valves and meter boxes), and others Used for parts (power tool parts, mower handles, hose joints, resin bolts and concrete formwork), especially automotive parts that require rigidity and durability (front end modules (including fan shrouds, fans and cooling modules)), Air cleaner and door parts), valves, medical equipment, robot forks and frames, and IC trays.

EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.
The analysis methods used in Examples and Comparative Examples of the present invention are as follows.

[M1] Melting point (Tm)
The melting point (Tm) of the propylene polymer (A) and the modified propylene polymer (B) was measured using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer), and the endothermic peak at the third step was determined as the melting point (Tm ).

(Sample preparation conditions)
Molding method: Press mold: Thickness 0.2mm (sample is sandwiched between aluminum foil, press mold using mold)
Molding temperature: 240 ° C. (heating temperature 240 ° C., preheating time: 7 min)
Press pressure: 300 kg / cm ²
Press time: 1 minute After press molding, the mold is cooled to near room temperature with ice water, the sheet is taken out, and about 0.4 g of sheet is enclosed in the following measurement container. Measurement container: Aluminum PAN (DSC PANS 10 μl BO-14- 3015)
Aluminum COVER (DSC COVER BO14-3003)
(Measurement condition)
First step: The temperature is raised to 240 ° C. at 30 ° C./min and held for 10 minutes.
Second step: The temperature is lowered to 30 ° C. at 10 ° C./min.
Third step: The temperature is raised to 240 ° C. at 10 ° C./min.

[M2] Graft amount About 2 g of the modified propylene polymer (B) was sampled and completely dissolved in 500 ml of boiling p-xylene by heating. The p-xylene solution in which the modified propylene polymer (B) was dissolved was transferred to a 2 L beaker and allowed to cool at 23 ° C. for about 1 hour. Thereafter, 1200 ml of acetone was added to precipitate the polymer while stirring. The precipitate was filtered and dried to obtain a purified product of the modified propylene polymer (B) from which the ungrafted content was removed. FT-IR of a press film produced from this purified product was measured, and the amount of maleic anhydride grafted in the modified propylene polymer (B) was calculated in terms of weight% based on the peak intensity ratio of 1790 cm ^-1 and 974 cm ^-1. Asked.

[M3] Amount of components soluble in o-dichlorobenzene at 70 ° C. The amount of components soluble in o-dichlorobenzene at 70 ° C. was measured by cross fraction chromatography (CFC).

The cross fractionation chromatograph (CFC) apparatus is provided with a temperature rising elution fractionation (TREF) part that performs crystallizing fractionation and a GPC part that performs molecular weight fractionation. Using this apparatus, measurement was performed under the following conditions, and the amount at each temperature was calculated.
Measuring device: CFC T-150A type, manufactured by Mitsubishi Yuka Co., Ltd.
Column: Shodex AT-806MS (× 3)
Eluent: o-Dichlorobenzene Flow rate: 1.0 ml / min
Sample concentration: 0.3 wt% / vol% (with 0.1% BHT)
Injection volume: 0.5 ml
Solubility: Complete dissolution Detector: Infrared absorption detection method, 3.42μ (2924 cm ^-1 ), NaCl plate Elution temperature: 0 to 135 ° C, 28 fractions
0, 10, 20, 30, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 94, 97, 100, 103, 1
06, 109, 112, 115, 118, 121, 124, 127, 135 (℃)

The sample was dissolved at 145 ° C. for 2 hours, held at 135 ° C., then cooled to 0 ° C. at 10 ° C./hr and held at 0 ° C. for an additional 60 minutes to coat the sample. The temperature rising elution column capacity is 0.83 ml, and the pipe capacity is 0.07 ml. An infrared spectrometer MIRAN 1A CVF type (CaF ₂ cell) manufactured by FOXBORO was used as a detector, and infrared light of 3.42 μm (2924 cm ⁻¹ ) was detected in an absorbance mode setting with a response time of 10 seconds. The elution temperature was divided into 28 fractions from 0 to 135 ° C. All temperature indications are integers. For example, the elution fraction at 94 ° C. indicates a component eluted at 91 to 94 ° C. The molecular weight of the components not coated even at 0 ° C. and the molecular weight of the fraction eluted at each temperature were measured, and the molecular weight in terms of standard polypropylene was determined using a general-purpose calibration curve. The SEC temperature was 135 ° C, the internal standard injection volume was 0.5 ml, the injection position was 3.0 ml, and the data sampling time was 0.50 seconds. Data processing was performed using an analysis program “CFC data processing (version 1.50)” attached to the apparatus.

[M4] Intrinsic viscosity [η]
Measurement was performed at 135 ° C. using a decalin solvent. About 20 mg of a sample was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After diluting the decalin solution with 5 ml of decalin solvent, the specific viscosity ηsp was measured in the same manner. This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was defined as the intrinsic viscosity.
[Η] = lim (ηsp / C) (C → 0)

[M5] Chlorine amount After combusting 0.8 g of propylene polymer (F) at 400-900 ° C. in an argon / oxygen stream using a burner manufactured by Mitsubishi Kasei, the combustion gas is collected with ultrapure water and concentrated. The subsequent sample solution was measured using an anion column AS4A-SC (manufactured by Dioness) with Nippon Dioneck Co., Ltd. DIONEX-DX300 type ion chromatograph.

[M6] Double Bond Structure in Propylene Polymer (F) The double bond structure shown in FIG. 1 is obtained by H-NMR according to the method described in Polymer, 45, 2883-2888 (2004). Analysis was performed as the number per 1000 carbon atoms (1000 C).

[M7] Measurement of 2,1-insertion and 1,3-insertion content of propylene in propylene-based polymer (F) According to the method described in JP-A-7-145212, carbon nuclear magnetic resonance analysis ( ¹³ C-NMR), the content of 2,1-insertion and 1,3-insertion of propylene was measured.

[M8] Content of skeleton derived from ethylene in propylene-based polymer (F) In order to measure the content of skeleton derived from ethylene in propylene-based polymer (F), samples 20 to 30 mg were Carbon nuclear magnetic resonance analysis ( ¹³ C-NMR) was performed by dissolving in 0.6 ml of 2,4-trichlorobenzene / deuterated benzene (2: 1) solution. Propylene, ethylene and α-olefin were quantitatively determined from the dyad chain distribution. For example, in the case of a propylene / ethylene copolymer, PP = Sαα, EP = Sαγ + Sαβ, EE = 1/2 (Sβδ + Sδδ) + 1 / 4Sγδ are used, and the following equations (Eq-1) and (Eq-2) ).
Propylene (mol%) = (PP + 1 / 2EP) x 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE) (Eq-1)
Ethylene (mol%) = (1 / 2EP + EE) x 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE) (Eq-2)

In this example, the _units of ethylene amount and α-olefin amount in D _insol are expressed in terms of% by weight.

[M9] Molecular weight distribution (Mw / Mn)
The molecular weight distribution of standard polystyrene (Mw / Mn; Mw is the weight average molecular weight, Mn is the number average molecular weight) was measured using GPC-150C Plus manufactured by Waters. This will be described below.

The separation columns are TSKgel GMH6-HT and TSK gel GMH6-HTL, the column size is 7.5 mm in inner diameter and 600 mm in length, the column temperature is 140 ° C., the flow rate is 1.0 ml / min, and the mobile phase is o-Dichlorobenzene (Wako Pure Chemical Industries), 0.025% by weight of BHT (Wako Pure Chemical Industries) as an antioxidant, 0.1% by weight of sample concentration, 500μL of sample injection volume, and a differential refractometer as a detector Using. Standard polystyrene uses a Tosoh product for those with molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and a general calibration method using a pressure chemical product for those with a molecular weight of 1000 ≦ Mw ≦ 4 × 10 ^6. Converted into PP. The Mark-Houwink coefficients of PS and PP are the values described in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970) and Makromol. Chem., 177, 213 (1976)), respectively. Was used.

[M10] Melt flow rate (MFR)
Measured according to ASTM D1238 (230 ° C., load 2.16 kg).

[M11] Metal analysis The sample was precisely weighed in a clean container and treated with ultrapure nitric acid by the microwave decomposition method. Ti and Zr in this decomposition solution were quantified using an ICP-MS apparatus (Agilent Technology Co., Ltd. HP-4500).

[M12] Bending test
Flexural strength and flexural modulus were measured according to JIS K7171.
<Measurement conditions>
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Bending speed: 2 mm / min
Bending span: 64mm

[Production Example 1]
(1) Production of Solid Catalyst Support 300 g of SiO ₂ was sampled in a 1 L branch flask, and 800 mL of toluene was put into a slurry. Next, the solution was transferred to a 5 L four-necked flask, and 260 mL of toluene was added. 2830 mL of methylaluminoxane (MAO) -toluene solution (10 wt% solution) was introduced and stirred at room temperature for 30 minutes. The temperature was raised to 110 ° C. over 1 hour, and the reaction was carried out for 4 hours. After completion of the reaction, it was cooled to room temperature. After cooling, the supernatant toluene was extracted and replaced with fresh toluene until the substitution rate reached 95%.

(2) Production of solid catalyst (support of metal catalyst component on carrier)
In a glove box, 2.0 g of isopropyl (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride was weighed in a 5 L four-necked flask. I took it. The flask was taken out, 0.46 liters of toluene and 1.4 liters of the MAO / SiO ₂ / toluene slurry prepared in the above (1) were added under nitrogen and stirred for 30 minutes to carry. The resulting isopropyl (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99% in n-heptane. The final slurry volume was 4.5 liters. This operation was performed at room temperature.

(3) Production of prepolymerization catalyst 404 g of the solid catalyst component prepared in (2) above, 218 mL of triethylaluminum, and 100 L of heptane were charged into an autoclave equipped with a stirrer with an internal volume of 200 L, maintained at an internal temperature of 15 to 20 ° C., and ethylene 1212 g was charged and reacted with stirring for 180 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 6 g / L. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization 35 kg / hour of propylene and 2.5 NL / hour of hydrogen in a jacketed circulation type tubular polymerizer having an internal volume of 58 L, 42 g / hour of the catalyst slurry produced in (3) as a solid catalyst component, triethylaluminum 8.0 ml / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 30 ° C., and the pressure was 3.1 MPa / G. The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. Propylene was supplied to the polymerization vessel at 65 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.05 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.05 mol%. The polymerization temperature was 68 ° C., and the pressure was 2.9 MPa / G. The resulting propylene homopolymer (F-1) was vacuum dried at 80 ° C.
Table 1 shows the physical properties of the propylene homopolymer (F-1).

[Production Example 2]
(1) Production of solid catalyst carrier To a reaction vessel with a stirrer having an internal volume of 30 L, 17 L of toluene and 650 g of SiO ₂ (Sunsphere H122 manufactured by AGC S-Tech) were put into a slurry. Next, the temperature in the tank was kept at 45 ° C., 64 g of triisobutylaluminum toluene solution was charged in the amount of triisobutylaluminum, and the mixture was stirred for 15 minutes. While maintaining the temperature in the tank at 50 ° C., 2.2 L of MAO-toluene solution (20 wt% solution) was introduced over about 30 minutes and stirred for 30 minutes. The temperature was raised to 95 ° C. over 1 hour, and the reaction was carried out for 4 hours. After completion of the reaction, it was cooled to 60 ° C. After cooling, the supernatant toluene was extracted and replaced with fresh toluene until the substitution rate reached 95%.

(2) Production of solid catalyst (support of metal catalyst component on carrier)
7.9 L of MAO / SiO ₂ / toluene slurry prepared in (1) (1030 g as a solid component) was placed in a reaction tank equipped with a stirrer with an internal volume of 14 L, and the temperature was maintained at 30 to 35 ° C. while stirring. In the glove box, place the [3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) ( 15.5 g of 1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride was weighed. The flask was taken out, diluted with 0.5 liter of toluene, added to the reaction tank, and toluene was added until the liquid volume in the reaction tank reached 10 L. The mixture was stirred for 60 minutes. The resulting [3- (1 ′, 1 ′, 4 ′, 4 ′, 7 ′, 7 ′, 10 ′, 10′-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3- Trimethyl-5-t-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride / MAO / SiO ₂ / toluene slurry was cooled to room temperature and then 92% substituted with n-heptane, The final slurry volume was 10L.

(3) Production of prepolymerization catalyst 1045 g of the solid catalyst component prepared in (2) above was transferred to an autoclave with a stirrer having an internal volume of 200 L in which 18 L of n-heptane had been put in advance, and the internal temperature was adjusted to 15 to 20 ° C. Then, 557 g of triisobutylaluminum was added, and the liquid volume was adjusted to 62 L with n-heptane. While stirring, the temperature was kept at 30 to 35 ° C., 3135 g of ethylene was charged at 630 g / h, and the reaction was allowed to stir for 300 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 8 g / L. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization Propylene was supplied to a vessel polymerization vessel with an internal volume of 100 L with a stirrer so that 124 kg / hour of propylene and hydrogen were 0.20 mol% in the gas phase. The catalyst slurry prepared in (3) was continuously supplied as a solid catalyst component at 8.0 g / hour and triethylaluminum 8.7 ml / hour. The polymerization temperature was 62 ° C. and the pressure was 2.5 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at 17 kg / hour, hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.20 mol%, and ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%. Polymerization was performed at a polymerization temperature of 60 ° C. and a pressure of 2.4 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 6 kg / hour, hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.20 mol%, and ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%. Polymerization was performed at a polymerization temperature of 59 ° C. and a pressure of 2.4 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 6 kg / hour, hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.20 mol%, and ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%. Polymerization was performed at a polymerization temperature of 58 ° C. and a pressure of 2.3 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 6 kg / hour, hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.20 mol%, and ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%. Polymerization was performed at a polymerization temperature of 57 ° C. and a pressure of 2.3 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene copolymer (F-2). The propylene copolymer (F-2) was obtained at 70 kg / h. The propylene copolymer (F-2) was vacuum dried at 80 ° C.
Table 1 shows the physical properties of the propylene copolymer (F-2).

[Production Example 3]
(1) Production of Prepolymerization Catalyst Purified heptane 14L and diethylaluminum chloride 490 g were added to a vessel polymerization vessel with an internal volume of 20 L with a stirrer, and 70 g of a commercially available Solvay type titanium trichloride catalyst (manufactured by Tosoh Finechem) was added. The internal temperature was kept at 20 ° C., and propylene was continuously charged and reacted for 80 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 10 g / L. This prepolymerized catalyst contained 3 g of polypropylene per 1 g of the solid catalyst component.

(2) Main polymerization Purified heptane (120 L) and diethylaluminum chloride (210 g) were added to a vessel polymerization vessel with a stirrer having an internal volume of 275 L, and 30 g was charged as the solid catalyst component prepared in (1). While maintaining the polymerization temperature at 60 ° C. and the polymerization pressure at 0.68 MPa / G, propylene was continuously fed for 4 hours. Hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.07 mol%.

The entire amount of the obtained polypropylene slurry was transferred to an autoclave equipped with a stirrer having an internal volume of 500 L, and 201 g of methanol was charged to deactivate the catalyst. This slurry was transferred to a filter dryer equipped with a stirrer, filtered, and then vacuum dried at 85 ° C. for 6 hours to obtain a propylene homopolymer (F′-1).
Table 1 shows the physical properties of the propylene homopolymer (F′-1).

［製造例４］
製造例１で製造したプロピレン単独重合体（Ｆ−１）１００重量部に対して、エチレン性不飽和結合含有モノマーとして無水マレイン酸（試薬特級、和光純薬（株）製）２．０重量部、有機過酸化物としてｔ−ブチルペルオキシベンゾエート（パーブチルＺ、日油（株）商標）２．０重量部、熱安定剤IRGANOX1010（チバガイギー（株）商標）０．１重量部および熱安定剤ヨシノックスＢＨＴ（吉富ファインケミカル（株）商標）０．１重量部を配合し、ヘンシェルミキサーで３分間ブレンドした。このブレンド物を二軸押出機にて下記の条件で溶融混練して、グラフト反応を行った。反応終了後、造粒して変性プロピレン系重合体（Ｂ−１）を得た。
変性プロピレン系重合体（Ｂ−１）の物性、グラフト量および７０℃のｏ−ジクロロベンゼンに可溶な成分量を表２に示す。

[Production Example 4]
Maleic anhydride (reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.) 2.0 parts by weight as an ethylenically unsaturated bond-containing monomer with respect to 100 parts by weight of the propylene homopolymer (F-1) produced in Production Example 1 , 2.0 parts by weight of t-butylperoxybenzoate (Perbutyl Z, NOF Corporation), 0.1 parts by weight of thermal stabilizer IRGANOX 1010 (trademark of Ciba Geigy) and organic stabilizer Yoshinox BHT (Yoshitomi Fine Chemical Co., Ltd.) 0.1 part by weight was blended and blended for 3 minutes with a Henschel mixer. This blend was melt-kneaded with a twin screw extruder under the following conditions to carry out a graft reaction. After completion of the reaction, granulation was carried out to obtain a modified propylene polymer (B-1).
Table 2 shows the physical properties of the modified propylene polymer (B-1), the amount of grafting, and the amount of components soluble in o-dichlorobenzene at 70 ° C.

<Melting and kneading conditions>
Same-direction biaxial kneader: Product number KZW31-30HG, Technobel Kneading temperature: 210 ° C
Screw rotation speed: 200rpm
Feeder rotation speed: 80 rpm

[Production Example 5]
Production Example 4 was carried out in the same manner as in Production Example 4 except that maleic anhydride was changed to 3.0 parts by weight and t-butylperoxybenzoate was changed to 3.0 parts by weight.
Table 2 shows the physical properties of the modified propylene polymer (B-2), the amount of grafting, and the amount of components soluble in o-dichlorobenzene at 70 ° C.

[Production Example 6]
Production Example 4 was carried out in the same manner as in Production Example 4 except that maleic anhydride was changed to 0.5 parts by weight and t-butylperoxybenzoate was changed to 0.5 parts by weight.
Table 2 shows the physical properties, graft amount, and component amount soluble in o-dichlorobenzene at 70 ° C. of the modified propylene polymer (B-3).

[Production Example 7]
Production Example 4 was carried out in the same manner as Production Example 4 except that the propylene homopolymer (F-1) was changed to the propylene-ethylene copolymer (F-2) obtained in Production Example 2.
Table 2 shows the physical properties of the modified propylene polymer (B-4), the amount of grafting, and the amount of components soluble in o-dichlorobenzene at 70 ° C.

[Production Example 8]
Production Example 4 was carried out in the same manner as Production Example 4 except that the propylene homopolymer (F-1) was changed to the propylene homopolymer (F′-1) obtained in Production Example 3.
Table 2 shows the physical properties of the modified propylene polymer (B′-1), the amount of grafting, and the amount of components soluble in o-dichlorobenzene at 70 ° C.

［実施例１］
チーグラー・ナッタ触媒存在下で製造されたプロピレン単独重合体（Ａ−１）（プライムポリプロＪ１０７Ｇ（商標）（Ｔｍ＝１６０℃、ＭＦＲ＝３０ｇ／分）、（株）プライムポリマー製）７０重量部、製造例４で得られた無水マレイン酸変性プロピレン樹脂（Ｂ−１）１０重量部、チョップドファイバー炭素繊維（Ｃ−１）（エポキシ樹脂サイジング）（ＨＴＡ−Ｃ６−ＳＲ（商標）、東邦テナックス（株）製）２０重量部、熱安定剤IRGANOX1010（商標、チバガイギー（株））０．１重量部、熱安定剤IRGAFOS168（商標、チバガイギー（株））０．１重量部およびステアリン酸カルシウム０．１重量部をタンブラーにて混合後、単軸押出機にて下記条件で溶融混練してペレット状の炭素繊維強化プロピレン系複合材料を調製した。

[Example 1]
70 parts by weight of a propylene homopolymer (A-1) produced in the presence of a Ziegler-Natta catalyst (Prime Polypro J107G (trademark) (Tm = 160 ° C., MFR = 30 g / min), manufactured by Prime Polymer Co., Ltd.) 10 parts by weight of maleic anhydride-modified propylene resin (B-1) obtained in Production Example 4, chopped fiber carbon fiber (C-1) (epoxy resin sizing) (HTA-C6-SR (trademark), Toho Tenax Co., Ltd. )) 20 parts by weight, heat stabilizer IRGANOX 1010 (trademark, Ciba Geigy) 0.1 part by weight, heat stabilizer IRGAFOS168 (trademark, Ciba Geigy) 0.1 part by weight and calcium stearate 0.1 part by weight After mixing with a tumbler, the mixture was melt-kneaded with a single screw extruder under the following conditions to prepare a pellet-like carbon fiber reinforced propylene-based composite material.

The obtained carbon fiber reinforced propylene-based composite material was molded using an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.] under the following conditions.
Table 3 shows the physical properties of the molded product.

<Melting and kneading conditions>
Single-shaft kneader: Part No. Laboplast Mill 10M100, manufactured by Toyo Seiki Co., Ltd. Kneading temperature: 220 ° C
Screw rotation speed: 60rpm
Pellet length: about 5mm <Injection molding conditions>
Injection molding machine: Part number EC40, Toshiba Machine Co., Ltd. cylinder temperature: 210 ° C
Mold temperature: 40 ℃

[Example 2]
In Example 1, it carried out like Example 1 except having changed propylene homopolymer (A-1) into 65 weight part and maleic anhydride modified propylene resin (B-1) at 15 weight part.
Table 3 shows the physical properties of the molded product.

[Example 3]
In Example 1, it carried out similarly to Example 1 except having changed the propylene homopolymer (A-1) to 60 weight part and the maleic anhydride modified propylene resin (B-1) to 20 weight part.
Table 3 shows the physical properties of the molded product.

[Comparative Example 1]
In Example 1, it carried out similarly to Example 1 except having changed the propylene homopolymer (A-1) to 75 weight part and the maleic anhydride modified propylene resin (B-1) to 5 weight part.
Table 3 shows the physical properties of the molded product.

[Comparative Example 2]
70 parts by weight of propylene homopolymer (A-1) (Prime Polypro J107G (trademark) (Tm = 160 ° C., MFR = 30 g / min), manufactured by Prime Polymer Co., Ltd.), maleic anhydride obtained in Production Example 8 Modified propylene resin (B′-1) 10 parts by weight, chopped fiber carbon fiber (C-1) (epoxy resin sizing) (HTA-C6-SR (trademark), manufactured by Toho Tenax Co., Ltd.), heat stable IRGANOX1010 (trademark, Ciba Geigy Co., Ltd.) 0.1 parts by weight, heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Co., Ltd.) 0.1 parts by weight and calcium stearate 0.1 parts by weight were mixed in a tumbler, A pellet-shaped composite material was prepared by melt-kneading in an extruder under the following conditions. The obtained composite material was molded using an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.] under the following conditions.
Table 3 shows the physical properties of the molded product.

<Melting and kneading conditions>
Single-shaft kneader: Part No. Laboplast Mill 10M100, manufactured by Toyo Seiki Co., Ltd. Kneading temperature: 220 ° C
Screw rotation speed: 60rpm
Pellet length: about 5mm <Injection molding conditions>
Injection molding machine: Part number EC40, Toshiba Machine Co., Ltd. cylinder temperature: 210 ° C
Mold temperature: 40 ℃

[Comparative Example 3]
Comparative Example 2 was carried out in the same manner as Comparative Example 2 except that the propylene homopolymer (A-1) was changed to 65 parts by weight and the maleic anhydride-modified propylene resin (B′-1) was changed to 15 parts by weight.
Table 3 shows the physical properties of the molded product.

[Comparative Example 4]
Comparative Example 2 was carried out in the same manner as Comparative Example 2 except that the propylene homopolymer (A-1) was changed to 60 parts by weight and the maleic anhydride-modified propylene resin (B′-1) was changed to 20 parts by weight.
Table 3 shows the physical properties of the molded product.

[Comparative Example 5]
Comparative Example 2 was carried out in the same manner as Comparative Example 2 except that the propylene homopolymer (A-1) was changed to 75 parts by weight and the maleic anhydride-modified propylene resin (B′-1) was changed to 5 parts by weight.
Table 3 shows the physical properties of the molded product.

［実施例４］
チーグラー・ナッタ触媒存在下で製造されたプロピレン単独重合体（Ａ−２）（プライムポリプロＪ１３Ｂ（商標）（Ｔｍ＝１６１℃、ＭＦＲ＝２００ｇ／分）、（株）プライムポリマー製）８０重量部、製造例４で製造された無水マレイン酸変性プロピレン系重合体（Ｂ−１）１０重量部、チョップドファイバー炭素繊維（Ｃ−１）（エポキシ樹脂サイジング）（ＨＴＡ−Ｃ６−ＳＲ（商標）、東邦テナックス（株）製）１０重量部、熱安定剤IRGANOX1010（商標、チバガイギー（株））０．１重量部、熱安定剤IRGAFOS168（商標、チバガイギー（株））０．１重量部およびステアリン酸カルシウム０．１重量部をタンブラーにて混合後、単軸押出機にて下記条件で溶融混練してペレット状の炭素繊維強化プロピレン系複合材料を調製した。

[Example 4]
Propylene homopolymer (A-2) produced in the presence of a Ziegler-Natta catalyst (Prime Polypro J13B (trademark) (Tm = 161 ° C., MFR = 200 g / min), manufactured by Prime Polymer Co., Ltd.) 80 parts by weight, 10 parts by weight of the maleic anhydride-modified propylene polymer (B-1) produced in Production Example 4, chopped fiber carbon fiber (C-1) (epoxy resin sizing) (HTA-C6-SR (trademark), Toho Tenax (Manufactured by Co., Ltd.) 10 parts by weight, heat stabilizer IRGANOX 1010 (trademark, Ciba Geigy) 0.1 part by weight, heat stabilizer IRGAFOS168 (trademark, Ciba Geigy) 0.1 part by weight and calcium stearate 0.1 After mixing parts by weight with a tumbler, the mixture was melt-kneaded with a single screw extruder under the following conditions to prepare a pellet-like carbon fiber reinforced propylene-based composite material.

The obtained carbon fiber reinforced propylene-based composite material was molded with an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.] under the following conditions.
Table 4 shows the physical properties of the molded product.

<Melting and kneading conditions>
Single-shaft kneader: Part No. Laboplast Mill 10M100, manufactured by Toyo Seiki Co., Ltd. Kneading temperature: 220 ° C
Screw rotation speed: 60rpm
Pellet length: about 5mm <Injection molding conditions>
Injection molding machine: Part number EC40, Toshiba Machine Co., Ltd. cylinder temperature: 210 ° C
Mold temperature: 40 ℃

[Example 5]
In Example 4, it carried out similarly to Example 4 except having changed the propylene homopolymer (A-2) to 70 weight part and the maleic anhydride modified propylene polymer (B-1) to 20 weight part. .
Table 4 shows the physical properties of the molded product.

[Example 6]
In Example 4, it carried out like Example 4 except having changed the propylene homopolymer (A-2) to 60 weight part and the maleic anhydride modified propylene polymer (B-1) to 30 weight part. Table 4 shows the physical properties of the molded product.

[Example 7]
In Example 4, it carried out similarly to Example 4 except having changed the propylene homopolymer (A-2) to 50 weight part and the maleic anhydride modified propylene polymer (B-1) to 40 weight part. .
Table 4 shows the physical properties of the molded product.

[Example 8]
80 parts by weight of propylene homopolymer (A-2) (Prime Polypro J13B (trademark) (Tm = 161 ° C., MFR = 200 g / min), manufactured by Prime Polymer Co., Ltd.), maleic anhydride obtained in Production Example 5 10 parts by weight of modified propylene polymer (B-2), 10 parts by weight of chopped fiber carbon fiber (C-1) (epoxy resin sizing) (HTA-C6-SR (trademark), manufactured by Toho Tenax Co., Ltd.), heat Stirrer IRGANOX 1010 (trademark, Ciba Geigy Co., Ltd.) 0.1 parts by weight, heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Co., Ltd.) 0.1 part by weight and calcium stearate 0.1 part by weight were mixed in a tumbler. It was melt-kneaded under the same conditions as in Example 4 in a shaft extruder to prepare a pellet-like carbon fiber reinforced propylene-based composite material.

The obtained carbon fiber reinforced propylene-based composite material was molded using the injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.] under the same conditions as in Example 4.
Table 4 shows the physical properties of the molded product.

[Example 9]
In Example 8, it carried out similarly to Example 8 except having changed the propylene homopolymer (A-2) to 70 weight part and the maleic anhydride modified propylene polymer (B-2) to 20 weight part. .
Table 4 shows the physical properties of the molded product.

[Example 10]
70 parts by weight of propylene homopolymer (A-2) (Prime Polypro J13B ™ (Tm = 161 ° C., MFR = 200 g / min), Prime Polymer Co., Ltd.), maleic anhydride obtained in Production Example 7 Modified propylene polymer (B-4) 20 parts by weight, chopped fiber carbon fiber (C-1) (epoxy resin sizing) (HTA-C6-SR (trademark), manufactured by Toho Tenax Co., Ltd.), 10 parts by weight, heat Stirrer IRGANOX 1010 (trademark, Ciba Geigy Co., Ltd.) 0.1 parts by weight, heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Co., Ltd.) 0.1 part by weight and calcium stearate 0.1 part by weight were mixed in a tumbler. It was melt-kneaded under the same conditions as in Example 4 in a shaft extruder to prepare a pellet-like carbon fiber reinforced propylene-based composite material.

The obtained carbon fiber reinforced propylene-based composite material was molded using the injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.] under the same conditions as in Example 4.
Table 4 shows the physical properties of the molded product.

［比較例６］
実施例４において、プロピレン単独重合体（Ａ−２）を８５重量部、無水マレイン酸変性プロピレン系重合体（Ｂ−１）を５重量部に変更した以外は、実施例４と同様に行った。
成形品の物性を表５に示す。

[Comparative Example 6]
In Example 4, it carried out similarly to Example 4 except having changed the propylene homopolymer (A-2) into 85 weight part and the maleic anhydride modified propylene polymer (B-1) into 5 weight part. .
Table 5 shows the physical properties of the molded product.

[Comparative Example 7]
Propylene homopolymer (A-2) (Prime Polypro J13B (trademark) (Tm = 161 ° C., MFR = 200 g / min), manufactured by Prime Polymer Co., Ltd.) 80 parts by weight, maleic anhydride obtained in Production Example 8 10 parts by weight of modified propylene polymer (B′-1), 10 parts by weight of chopped fiber carbon fiber (C-1) (epoxy resin sizing) (HTA-C6-SR (trademark), manufactured by Toho Tenax Co., Ltd.), After mixing 0.1 parts by weight of heat stabilizer IRGANOX 1010 (trademark, Ciba-Geigy), 0.1 parts by weight of heat stabilizer IRGAFOS168 (trademark, Ciba-Geigy) and 0.1 part by weight of calcium stearate with a tumbler, A pellet-shaped composite material was prepared by melt-kneading in a single-screw extruder under the following conditions.

The obtained composite material was molded using an injection molding machine [product number EC40, manufactured by Toshiba Machine Co., Ltd.] under the following conditions.
Table 5 shows the physical properties of the molded product.

<Melting and kneading conditions>
Single-shaft kneader: Part No. Laboplast Mill 10M100, manufactured by Toyo Seiki Co., Ltd. Kneading temperature: 220 ° C
Screw rotation speed: 60rpm
Pellet length: about 5mm <Injection molding conditions>
Injection molding machine: Part number EC40, Toshiba Machine Co., Ltd. cylinder temperature: 210 ° C
Mold temperature: 40 ℃

[Comparative Example 8]
In Comparative Example 7, the same procedure as in Comparative Example 7 was conducted except that the propylene homopolymer (A-2) was changed to 70 parts by weight and the maleic anhydride-modified propylene polymer (B′-1) was changed to 20 parts by weight. It was.
Table 5 shows the physical properties of the molded product.

[Comparative Example 9]
In Comparative Example 7, the same procedure as in Comparative Example 7 was carried out except that the propylene homopolymer (A-2) was changed to 60 parts by weight and the maleic anhydride-modified propylene polymer (B′-1) was changed to 30 parts by weight. It was.
Table 5 shows the physical properties of the molded product.

[Comparative Example 10]
In Comparative Example 7, the same procedure as in Comparative Example 7 was carried out except that the propylene homopolymer (A-2) was changed to 50 parts by weight and the maleic anhydride-modified propylene polymer (B′-1) was changed to 40 parts by weight. It was.
Table 5 shows the physical properties of the molded product.

[Comparative Example 11]
45 parts by weight of propylene homopolymer (A-2) (Prime Polypro J13B ™ (Tm = 161 ° C., MFR = 200 g / min), Prime Polymer Co., Ltd.), maleic anhydride produced in Production Example 6 45 parts by weight of modified propylene polymer (B-3), 10 parts by weight of chopped fiber carbon fiber (C-1) (epoxy resin sizing) (HTA-C6-SR (trademark), manufactured by Toho Tenax Co., Ltd.), heat Stirrer IRGANOX 1010 (trademark, Ciba Geigy Co., Ltd.) 0.1 parts by weight, heat stabilizer IRGAFOS168 (trademark, Ciba Geigy Co., Ltd.) 0.1 part by weight and calcium stearate 0.1 part by weight were mixed in a tumbler. The mixture was melt-kneaded under the same conditions as in Comparative Example 7 using a shaft extruder to prepare a pellet-shaped composite material.

A molded product was obtained from the obtained composite material using an injection molding machine [Product No. EC40, manufactured by Toshiba Machine Co., Ltd.] under the same conditions as in Comparative Example 7.
Table 5 shows the physical properties of the molded product.

  The carbon fiber reinforced propylene-based composite material of the present invention and a molded product obtained therefrom are suitable for various structural members having excellent lightness and moldability because they exhibit good mechanical strength (bending strength and flexural modulus). . In particular, when used for automobile outer plates such as fenders and door panels, energy saving can be achieved by reducing the weight of the automobile body.

Claims (5)

A propylene polymer (A) produced in the presence of a Ziegler-Natta catalyst;
A modified propylene polymer (B) obtained by graft-modifying a propylene polymer (F) produced in the presence of a metallocene catalyst with an ethylenically unsaturated bond-containing monomer;
A carbon fiber reinforced propylene-based composite material formed from a surface-treated carbon fiber (C),
The carbon fiber reinforced propylene-based composite material satisfies the following requirements (i) to (iv):
The carbon fiber reinforced propylene composite material, wherein the modified propylene polymer (B) satisfies the following requirements (b-1) to (b-4).
(I) The amount of the carbon fiber (C) used is 1 to 80% by weight in a total of 100% by weight of the propylene polymer (A), the modified propylene polymer (B) and the carbon fiber (C). .
(Ii) Melting | fusing point (Tm) is 150-170 degreeC.
(Iii) The amount of the modified propylene polymer (B) used is 0.5 to 40% by weight in a total of 100% by weight of the propylene polymer (A) and the modified propylene polymer (B).
(Iv) The graft amount in the modified propylene polymer (B) is 0.2 to 2% by weight in a total of 100% by weight of the propylene polymer (A) and the modified propylene polymer (B).
(B-1) Melting | fusing point (Tm) is 135-170 degreeC.
(B-2) The graft amount is 1 to 5% by weight.
(B-3) Intrinsic viscosity [η] is 0.2 to 4 dl / g.
(B-4) The amount of components soluble in 70 ° C. o-dichlorobenzene is 3% by weight or less.   The carbon fiber-reinforced propylene-based composite material according to claim 1, wherein the modified propylene-based polymer (B) has a carboxyl group, an acid anhydride group, or a derivative thereof.   The carbon fiber-reinforced propylene composite material according to claim 1 or 2, wherein the surface treatment is a sizing treatment using an epoxy polymer, a nylon polymer, or a urethane polymer.   The carbon fiber reinforced propylene-based composite material according to any one of claims 1 to 3, wherein the carbon fiber (C) is a carbon fiber base fabric.   The molded object obtained by shape | molding the carbon fiber reinforced propylene-type composite material in any one of Claims 1-4.