JP6832639B2 - Fiber-reinforced propylene resin composition and its manufacturing method - Google Patents

Description

The present invention relates to a fiber-reinforced propylene resin composition and a method for producing the same.

Fiber-reinforced polypropylene resin is used in various fields such as daily necessities, kitchen utensils, packaging films, home appliances, mechanical parts, electrical parts, automobile parts, etc., and various modifications are made according to the required performance. A propylene-based resin composition containing materials and additives is used. In addition, as an initiative for the 3Rs (Reuse, Reuse, Recycle) to form a recycling-oriented society, weight reduction by thin-walled molded products has recently been attempted in each industrial field. Improvements in the fiber-reinforced propylene-based resin composition are being promoted so that sufficient rigidity and low-temperature impact resistance can be obtained even if the molded product is made lighter or thinner.

Generally, a soft olefin resin composed of an ethylene / α-olefin copolymer is blended as a modifier of a polypropylene resin. Application as a modifier of olefin block polymer in which crystalline polyethylene segment and amorphous or low crystalline ethylene / α-olefin copolymer segment are chemically bonded to further improve performance. Has expectations.

Examples of the technique relating to such an olefin-based block polymer include a technique relating to a linear block polymer composed of a polyethylene segment obtained by using the living polymerization catalyst disclosed in Patent Document 1 and an ethylene / α-olefin copolymer segment. , Patent Document 2 includes a technique for producing a polymer having a multi-block structure utilizing a reversible chain transfer reaction between two types of catalysts disclosed in Patent Document 2.

Apart from such a linear block polymer, Patent Documents 3 to 8 describe a graft-type copolymer consisting of a main chain and a side chain, one of which is a soft segment and the other of which is a hard segment. A method of obtaining coalescence has been proposed. In these disclosures, as a whole, a hard segment such as polyethylene having a vinyl group at the terminal is synthesized, and then, or at the same time as the synthesis thereof, the hard segment such as polyethylene is subjected to ethylene or α- with 3 or more carbon atoms. The present invention relates to a technique for introducing into a soft segment, which is a main chain, by copolymerizing with an olefin.

For example, Patent Documents 3 and 4 disclose a method for obtaining a graft-type olefin polymer by copolymerizing terminal vinyl polyethylene produced using a specific metallocene catalyst with ethylene. In the present disclosure technique, although polyethylene having a vinyl group at the terminal can be obtained, the efficiency of producing terminal vinyl is low, and therefore, a large amount of polyethylene that has not been incorporated as a side chain remains. When this graft polymer is blended with polypropylene resin, unreacted polyethylene contained in a large amount lowers mechanical properties such as low temperature impact resistance, so there is room for improvement in the performance of this graft polymer as a modified resin. However, even if this graft polymer is used, a polypropylene resin composition exhibiting desired physical properties has not been obtained.

On the other hand, Patent Documents 5 to 7 disclose a technique for synthesizing terminal vinyl polyethylene for a side chain at a high production rate by using a specific non-metallocene complex catalyst. The present inventors conducted a follow-up test using the catalyst for forming the main chain disclosed in the examples of Patent Document 5 or 7, and found that a certain amount of terminal vinyl polyethylene was copolymerized in the main chain. , It has been confirmed that the uptake of terminal vinyl polyethylene is insufficient. Since the amount of side chains introduced in the block polymer thus obtained is limited, the modification performance is insufficient even if the block polymer is used as a polypropylene modification resin.

Patent Document 8 discloses a method of introducing a side chain with high efficiency by using a co-supporting catalyst system, but the main chain is limited to a crystalline polymer and is suitable for modification of a propylene resin. It is difficult to produce polymers in the amorphous or low crystalline region.

JP-A-2007-84806 Japanese Unexamined Patent Publication No. 2012-237013 Special Table No. 8-502303 Japanese Unexamined Patent Publication No. 2001-527589 JP-A-2002-105132 JP-A-2007-39540 Japanese Unexamined Patent Publication No. 2007-39541 JP-A-2009-144148

As described above, even if the block polymer or graft polymer in which dissimilar polymers are chemically linked, which is disclosed in the patent document, is applied as a modifier of polypropylene resin, the balance of performance is still insufficient. That is, it is desired to develop a fiber-reinforced propylene-based resin composition having excellent low-temperature impact resistance while maintaining high rigidity.

An object of the present invention is to provide a fiber-reinforced propylene-based resin composition having high rigidity and excellent low-temperature impact resistance.

The fiber-reinforced propylene-based resin composition according to the present invention relates to the following [1] to [8].

[1] 1 to 99 parts by mass of a propylene-based polymer (α) having a melt flow rate (MFR) of 0.1 to 500 g / 10 min at 230 ° C. and a 2.16 kg load obtained in accordance with ASTM D1238E. In addition, 1 to 99 parts by mass of the olefin resin (β) satisfying the following requirements (I), (IV) and (V) other than the propylene polymer (α) (the propylene polymer (α) and the olefin). The total amount of the resin composition (β) is 100 parts by mass), and 100 parts by mass of the resin composition.
Reinforcing fiber 1 to 50 parts by mass and
A fiber-reinforced propylene-based resin composition characterized by containing.
(I) The olefin resin (β) contains a graft-type olefin polymer [R1] having a main chain composed of an ethylene / α-olefin copolymer and a side chain composed of an ethylene polymer.
(IV) The glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is in the range of −80 to −30 ° C.
(V) The ultimate viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 12.0 dl / g.

[2] The fiber-reinforced propylene resin composition according to [1], wherein the olefin resin (β) further satisfies the following requirements (II) and (III).
(II) The measurement by differential scanning calorimetry (DSC) shows a melting peak having a melting temperature in the range of 60 to 130 ° C., and the heat of fusion ΔH at the melting peak is in the range of 3 to 100 J / g.
(III) The ratio E of the orthodichlorobenzene-soluble component at 20 ° C. or lower as measured by a cross-separation chromatograph (CFC) is 60% by mass or less.

[3] The fiber-reinforced propylene-based resin composition according to [1] or [2], wherein the flexural modulus measured in accordance with JIS K7171 is in the range of 600 to 9000 MPa.

[4] The fiber-reinforced propylene resin composition according to any one of [1] to [3], wherein the weight average molecular weight of the side chain of the graft-type olefin polymer [R1] is in the range of 500 to 15,000.

[5] Any of [1] to [4] in which the side chain is present at an average frequency of 0.1 to 20 per 1000 carbon atoms contained in the main chain of the graft-type olefin polymer [R1]. The fiber-reinforced propylene-based resin composition according to.

[6] The fiber-reinforced propylene-based resin composition according to any one of [1] to [5], wherein the olefin-based resin (β) further satisfies the following requirement (VI).
The MFR of the olefin resin (β) obtained in accordance with (VI) ASTM D1238E at 190 ° C. and a load of 2.16 kg was Mg / 10 min, and the olefin resin was measured in decalin at 135 ° C. When the ultimate viscosity [η] of (β) is H g / dl, the value A represented by the following formula (Eq-1) is in the range of 30 to 280.

A = M / exp (-3.3H) ... (Eq-1).

[7] The method for producing a fiber-reinforced propylene-based resin composition according to any one of [1] to [6].
In the presence of an olefin polymerization catalyst containing the following components (A) to (C), ethylene is copolymerized with at least one α-olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms. A method for producing a fiber-reinforced propylene-based resin composition, which comprises a step of producing the olefin-based resin (β).
(A) Crosslinked metallocene compound represented by the following formula (I) (B) Transition metal compound represented by the following formula [B] (C) (C-1) Organometallic compound, (C-2) Organometallic oxy At least one compound selected from the group consisting of a compound and (C-3) a compound that reacts with the crosslinked metallocene compound (A) or the transition metal compound (B) to form an ion pair.

In formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are independently hydrogen atoms, hydrocarbon groups, silicon-containing groups or silicon-containing groups, respectively. Heteroatom-containing groups other than the above may be exhibited, and ^{two adjacent groups of R 1 to} R ⁴ may be bonded to each other to form a ring.

R ⁶ and R ¹¹ are the same atom or the same group selected from the group consisting of hydrogen atoms, hydrocarbon groups, silicon-containing groups and heteroatom-containing groups other than silicon-containing groups.

R ⁷ and R ¹⁰ are the same atom or the same group selected from the group consisting of hydrogen atoms, hydrocarbon groups, silicon-containing groups and heteroatom-containing groups other than silicon-containing groups.

R ⁶ and R ⁷ may be coupled to each other to form a ring, and R ¹⁰ and R ¹¹ may be coupled to each other to form a ring. However, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

R ¹³ and R ¹⁴ each independently represent an aryl group.

M represents a titanium atom, a zirconium atom or a hafnium atom.

Y ¹ represents a carbon atom or a silicon atom.

Q indicates a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or unconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. , J represents an integer of 1 to 4, and when j is an integer of 2 or more, the plurality of Qs may be the same or different. )

(In formula [B], M represents a transition metal atom of Group 4 or 5 of the Periodic Table.

m represents an integer of 1 to 4.

R ¹ represents a _{C n 'H 2n' + 1} (n ' is a is an integer of 1 to 8) hydrocarbon group having 1 to 8 carbon atoms represented by.

R ² to R ⁵ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, silicon-containing group, a germanium-containing group or shows a tin-containing group, may form a ring two groups adjacent to each other are connected to each other among the R ² to R ^5.

R ^{6 to} R ⁸ represent hydrocarbon groups, and ^{at least one of R 6 to} R ⁸ is an aromatic hydrocarbon group.

^{When m is an integer of 2 or more, two groups of R 2 to} R ⁸ may be connected to each other between the structural units of the formula [B].

n is a number that satisfies the valence of M.

X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, and a silicon-containing group. Indicates a group, a germanium-containing group, or a tin-containing group.

When n is an integer of 2 or more, the plurality of Xs may be the same as or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. ).

[8] The method for producing a fiber-reinforced propylene resin composition according to [7], wherein the copolymerization step is a step of copolymerizing by a solution polymerization method in a temperature range of 80 to 300 ° C.

According to the present invention, it is possible to provide a fiber-reinforced propylene-based resin composition having high rigidity and excellent low-temperature impact resistance.

[Fiber-reinforced propylene resin composition]
As a result of diligent studies to solve the above-mentioned problems, the present inventors have made a fiber-reinforced propylene resin containing an olefin resin containing a graft-type ethylene / α-olefin copolymer having an ethylene polymer in the side chain. It has been found that the composition has excellent low temperature impact resistance while keeping the decrease in rigidity to a minimum.

The graft-type ethylene / α-olefin copolymer contained in the olefin resin has a main chain having a low glass transition temperature (Tg) and a crystalline polyethylene having a specific molecular structure in the side chain. Therefore, when the olefin resin is added to polypropylene, low-temperature impact resistance is exhibited by the main chain having a low Tg, and at the same time, rigidity and hardness are satisfactorily exhibited by the side chain polyethylene component that acts as a physical cross-linking point. To. As a result, it is presumed that the balance with the low temperature impact resistance is remarkably improved while maintaining the rigidity of the fiber-reinforced propylene resin composition.

As described above, the present inventors have made a fiber-reinforced propylene resin composition containing an olefin resin containing a graft-type ethylene / α-olefin copolymer having an ethylene polymer in the side chain, thereby providing rigidity and low temperature resistance. Since the impact resistance could be realized at a high level in a well-balanced manner, the present invention was completed.

That is, the fiber-reinforced propylene-based resin composition according to the present invention includes 100 parts by mass of a resin composition containing 1 to 99 parts by mass of a propylene-based polymer (α) and 1 to 99 parts by mass of an olefin resin (β). Includes 1 to 50 parts by mass of reinforcing fibers. The total of the propylene-based polymer (α) and the olefin-based resin (β) is 100 parts by mass.

When the total of the propylene-based polymer (α) and the olefin-based resin (β) is 100 parts by mass, the content of the propylene-based polymer (α) is 1 to 99 parts by mass, and 30 to 90 parts by mass. It is preferably parts by mass, more preferably 50 to 80 parts by mass, and even more preferably 60 to 80 parts by mass. The content of the olefin resin (β) is 1 to 99 parts by mass, preferably 10 to 70 parts by mass, more preferably 20 to 50 parts by mass, still more preferably 20 to 40 parts by mass. When the content of the propylene-based polymer (α) and the olefin-based resin (β) is within the above range, the rigidity and low-temperature impact resistance are not lowered without lowering the rigidity of the fiber-reinforced propylene-based resin composition. Since the balance with the above is good, the fiber-reinforced propylene-based resin composition can be suitably used for various molded products.

The content of the reinforcing fibers is 1 to 50 parts by mass, preferably 3 to 45 parts by mass, based on 100 parts by mass of the total amount of the propylene-based polymer (α) and the olefin-based resin (β). 5 to 40 parts by mass is more preferable, and 15 to 35 parts by mass is further preferable. If the content of the reinforcing fibers is less than 1 part by mass, the high rigidity required for, for example, automobile module parts cannot be achieved. Further, when the content of the reinforcing fiber exceeds 50 parts by mass, the low temperature impact resistance is lowered and the specific gravity of the molded body is increased, so that it may not be applicable to, for example, automobile parts requiring weight reduction. ..

Hereinafter, the propylene-based polymer (α), the olefin-based resin (β), and the reinforcing fibers contained in the fiber-reinforced propylene-based resin composition according to the present invention will be described.

<Propylene polymer (α)>
As the propylene-based polymer (α), for example, a homopolymer of propylene, a copolymer of propylene and at least one selected from the group consisting of ethylene and an α-olefin having 4 or more carbon atoms can be used. it can. The copolymer may be a random copolymer or a block copolymer. Specific examples of the α-olefin having 4 or more carbon atoms include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, and 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-hexene, methylethyl-1-hexene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, 1 -Dodecene etc. can be mentioned. Of these, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.

The obtained melt flow rate (MFR) of the propylene polymer (α) according to ASTM D1238E at 230 ° C. and a load of 2.16 kg is 0.1 to 500 g / 10 minutes, and 0.2 to 400 g / g. 10 minutes is preferable, 0.3 to 300 g / 10 minutes is more preferable, and 10.0 to 200 g / 10 minutes is further preferable. When the MFR of the propylene-based polymer (α) is less than 0.1 g / 10 minutes, the dispersibility of the propylene-based polymer (α) and the olefin-based resin (β) in the fiber-reinforced propylene-based resin composition is lowered. However, the mechanical strength is reduced. When the MFR of the propylene-based polymer (α) exceeds 500 g / 10 minutes, the strength of the propylene-based polymer (α) itself decreases, and the mechanical strength of the obtained fiber-reinforced propylene-based resin composition decreases. ..

<Olefin resin (β)>
The olefin-based resin (β) is an olefin-based resin other than the propylene-based polymer (α), satisfies the following requirements (I), (IV) and (V), and meets the following requirements (I) to (VI). It is preferable to satisfy all. The olefin-based resin (β) may be composed of one kind or two or more kinds of olefin-based resins.
(I) The olefin resin (β) contains a graft-type olefin polymer [R1] having a main chain composed of an ethylene / α-olefin copolymer and a side chain composed of an ethylene polymer.
(II) The measurement by differential scanning calorimetry (DSC) shows a melting peak having a melting temperature in the range of 60 to 130 ° C., and the heat of fusion ΔH at the melting peak is in the range of 3 to 100 J / g.
(III) The ratio E of the orthodichlorobenzene-soluble component at 20 ° C. or lower as measured by a cross-separation chromatograph (CFC) is 60% by mass or less.
(IV) The glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is in the range of −80 to −30 ° C.
(V) The ultimate viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 12.0 dl / g.
The MFR of the olefin resin (β) obtained in accordance with (VI) ASTM D1238E at 190 ° C. and a load of 2.16 kg was Mg / 10 min, and the olefin resin was measured in decalin at 135 ° C. When the ultimate viscosity [η] of (β) is H g / dl, the value A represented by the following formula (Eq-1) is in the range of 30 to 280.

A = M / exp (-3.3H) ... (Eq-1)
Hereinafter, the requirements (I) to (VI) will be specifically described.

(Requirement (I))
The olefin-based resin (β) contains a graft-type olefin-based polymer [R1] (hereinafter, also referred to as an olefin-based polymer [R1]). The olefin polymer [R1] is a graft copolymer having a main chain composed of an ethylene / α-olefin copolymer and a side chain composed of an ethylene polymer. In the present invention, the "graft copolymer" is a T-type polymer or comb-shaped polymer in which one or more side chains are bonded to the main chain. However, the side chain may contain repeating units other than ethylene as long as the gist of the present invention is not deviated.

Since the olefin-based polymer [R1] has a crystalline side-chain structure even though the main chain structure is an amorphous or low-crystalline ethylene-based copolymer, the olefin-based polymer according to the present invention. The resin (β) is less sticky and has better handleability of product pellets than general ethylene-based elastomers such as ethylene / propylene copolymers, ethylene / butene copolymers, and ethylene / octene copolymers. is there.

The olefin polymer [R1] preferably satisfies the following requirements (i) to (v) with respect to the main chain and the side chain.
(I) The main chain is composed of a copolymer of ethylene and at least one α-olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms, and the repeating unit derived from ethylene is 60 to 60 to. It contains 97 mol% and 3 to 40 mol% of the repeating unit derived from the α-olefin.
(Ii) The weight average molecular weight of the main chain is 20000-400000.
The (iii) side chain consists of repeating units that are substantially derived from ethylene.
(Iv) The weight average molecular weight of the side chain is 500 to 15,000.
(V) For every 1000 carbon atoms contained in the main chain, side chains are present at an average frequency of 0.1 to 20.

Hereinafter, the requirements (i) to (v) will be specifically described.

[Requirement (i)]
The main chain of the olefin polymer [R1] is composed of an ethylene / α-olefin copolymer, and is a site that bears properties such as flexibility and low temperature characteristics as a modifier. Therefore, the main chain of the olefin-based polymer [R1] is preferably composed of a copolymer of ethylene and at least one α-olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms. ..

Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, and the like. 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-decene, 1- Undesen, 1-dodesen and the like can be mentioned.

The α-olefin having 3 to 20 carbon atoms is preferably an α-olefin having 3 to 10 carbon atoms, and more preferably an α-olefin having 3 to 8 carbon atoms. Specific examples of the α-olefin having 3 to 10 carbon atoms include linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene, and 4-methyl-. Examples thereof include branched olefins such as 1-pentene, 3-methyl-1-pentene, and 3-methyl-1-butene. Among these, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.

The molar ratio of ethylene-derived repeating units to all repeating units in the main chain of the olefin polymer [R1] is preferably 60 to 97 mol%, more preferably 60 to 95 mol%, still more preferably 65 to 90 mol%. 65-85 mol% is particularly preferable. The molar ratio of the repeating unit derived from the α-olefin to all the repeating units is preferably 3 to 40 mol%, more preferably 5 to 40 mol%, further preferably 10 to 35 mol%, and particularly preferably 15 to 35 mol%.

When the molar ratio of the repeating unit derived from ethylene and the α-olefin in the main chain is within the above range, the olefin resin (β) is highly flexible and has excellent low temperature characteristics, so that the fiber is reinforced. The low temperature impact resistance of the propylene resin composition is improved. On the other hand, if the molar ratio of the repeating unit derived from the α-olefin falls below the above range, the olefin resin (β) becomes a resin inferior in flexibility and low temperature characteristics, so that the fiber reinforced propylene resin composition has low temperature impact resistance. Sex tends to be slightly reduced. Further, when the molar ratio of the repeating unit derived from the α-olefin exceeds the above range, it works disadvantageously in copolymerizing the macromonomer forming the side chain described later, so that the effect of the graft polymer described later is fully exhibited. However, the balance between low-temperature impact resistance and rigidity of the fiber-reinforced propylene-based resin composition tends to be slightly lowered.

The molar ratio of ethylene in the main chain and the repeating unit derived from the α-olefin controls the ratio of the concentration of ethylene present in the polymerization reaction system in the step of producing the main chain to the concentration of the α-olefin. It can be adjusted by.

The molar ratio (mol%) of the α-olefin-derived unit in the main chain, that is, the α-olefin composition ratio in the main chain shall be calculated or defined by the following method (1) or (2). Can be done.

(1) The α-olefin composition of a component composed of an ethylene / α-olefin copolymer produced as a by-product in the production process of an olefin resin (β) is defined as a unit derived from the α-olefin of the main chain. The ethylene / α-olefin copolymer produced as a by-product corresponds to an elution component at a temperature of 20 ° C. or lower when an olefin resin (β) is charged into orthodichlorobenzene. The α-olefin composition can be determined by a known method using carbon nuclear magnetic resonance analysis ( ^{13 C-NMR).}

(2) A polymer serving as a main chain site is separately synthesized under reasonable conditions in light of the production conditions of the olefin resin (β), and the α-olefin composition of the obtained ethylene / α-olefin copolymer is analyzed. Thereby, it is indirectly defined as the α-olefin composition of the main chain of the olefin polymer [R1]. Reasonable conditions include the concentration of ethylene and α-olefin in the polymerization system, the molecular abundance ratio of ethylene and hydrogen, and the like, in principle, a polymer equivalent to the main chain moiety of the olefin polymer [R1] is produced. It is a condition to do. In particular, as a method for producing an olefin resin (β), a method in which an ethylene polymer moiety (macromonomer) corresponding to a side chain is synthesized in advance and the macromonomer, ethylene and α-olefin are copolymerized to produce the olefin resin (β). In the case of adopting, indirectly carry out polymerization under the same conditions except that no macromonomer is added, and analyze the α-olefin composition of the obtained ethylene / α-olefin copolymer. It is defined as the α-olefin composition of the main chain of the olefin polymer [R1].

[Requirements (ii)]
The weight average molecular weight of the main chain of the olefin polymer [R1] is preferably 20000 to 400000, more preferably 30,000 to 300,000, and even more preferably 50,000 to 200,000.

When the weight average molecular weight of the main chain of the olefin polymer [R1] is within the above range, the balance between the low temperature impact resistance and the rigidity of the fiber-reinforced propylene resin composition becomes good. On the other hand, when the weight average molecular weight is less than 20000, the low temperature impact resistance and toughness may decrease. Further, when the weight average molecular weight exceeds 400,000, poor dispersion in the propylene-based polymer (α) may occur, and a desired balance of physical properties may not be obtained.

The weight average molecular weight of the main chain of the olefin-based polymer [R1] can be adjusted by controlling the ethylene concentration in the polymerization system in the production process described later. Examples of the ethylene concentration control method include ethylene partial pressure adjustment and polymerization temperature adjustment. The weight average molecular weight of the main chain can also be adjusted by supplying hydrogen into the polymerization system.

For the weight average molecular weight of the main chain, an ethylene / α-olefin copolymer was obtained according to the method for calculating or defining the molar ratio (mol%) of the α-olefin-derived unit described in the above requirement (i). , The weight average molecular weight of the polymer can be determined by a conventional method. For example, the weight average molecular weight of the main chain can be obtained from the polyethylene-equivalent weight average molecular weight obtained by gel permeation chromatography (GPC).

[Requirements (iii)]
The side chain of the olefin polymer [R1] is made of an ethylene polymer, but it is preferably made of a repeating unit derived from ethylene, and preferably made of a crystalline ethylene polymer chain. The side chain of the olefin polymer [R1] acts as a physical cross-linking point in the olefin resin (β), and plays a role of improving the surface hardness and increasing the rigidity in the fiber-reinforced propylene resin composition.

An ethylene polymer composed of repeating units substantially derived from ethylene has a molar ratio of repeating units derived from ethylene of 95.0 to 100.0 mol% with respect to all repeating units contained in the ethylene polymer. It is preferably 98.0 to 100.0 mol%, more preferably 99.5 to 100.0 mol%, and even more preferably 99.5 to 100.0 mol%. That is, it may contain an α-olefin other than ethylene as long as its role and characteristics are not impaired.

The fact that the side chain of the olefin polymer [R1] is a crystalline ethylene polymer chain indicates that the melting temperature (RSC) in the differential scanning calorimetry (DSC) of the olefin resin (β) is within the range of 60 to 130 ° C. It can be confirmed by observing a melting peak having Tm).

[Requirements (iv)]
The weight average molecular weight of the side chain of the olefin polymer [R1] is preferably 500 to 15,000, more preferably 500 to 10000, further preferably 500 to 5000, and particularly preferably 500 to 3000.

When the weight average molecular weight is within the above range, the fiber-reinforced propylene-based resin composition can exhibit high low-temperature impact resistance while having high rigidity and high surface hardness. On the other hand, when the weight average molecular weight is less than 500, the role of the side chain component as a physical cross-linking point is reduced, and the surface hardness and rigidity of the fiber-reinforced propylene-based resin composition tend to be lowered. If the weight average molecular weight exceeds 15,000, the number of side chains with respect to the main chain may decrease, resulting in a decrease in mechanical properties such as rigidity, surface hardness, and toughness of the fiber-reinforced propylene resin composition. In addition, since the relative amount of the ethylene / α-olefin copolymer moiety decreases, the low temperature impact resistance may decrease.

The olefin polymer [R1] can be obtained, for example, by copolymerizing a macromonomer, which is an ethylene polymer chain, with ethylene and an α-olefin. That is, the weight average molecular weight of the macromonomer corresponds to the weight average molecular weight of the side chain of the olefin polymer [R1]. Therefore, the weight average molecular weight of the side chain is determined by analyzing the molecular weight of the ethylene polymer moiety (macromonomer) separated as the elution component on the low molecular weight side by GPC measurement of the olefin resin (β), or by synthesizing it in advance. It can be calculated by performing GPC measurement of the ethylene polymer site (macromonomer).

Examples of the method for adjusting the weight average molecular weight of the side chain include a method for changing the type of the transition metal compound used as a catalyst for producing a vinyl-terminated macromonomer, which will be described later, and a method for adjusting the polymerization conditions.

[Requirement (v)]
The side chain of the olefin polymer [R1] preferably exists at an average frequency of 0.1 to 20 per 1000 carbon atoms contained in the main chain, and may be present at an average frequency of 0.1 to 10. More preferably, it is more preferably present at an average frequency of 0.2-5.

Since the side chains are introduced into the main chain at an average frequency within the above range, the fiber-reinforced propylene-based resin composition can exhibit high low-temperature impact resistance while maintaining high surface hardness and rigidity. it can. On the other hand, when the average frequency is less than 0.1, the effect of the physical cross-linking point by the side chain is reduced, so that the rigidity of the fiber-reinforced propylene-based resin composition may decrease. Further, when the average frequency exceeds 20, the relative amount of the crystal component composed of the ethylene polymer moiety becomes large, so that the low temperature impact resistance of the fiber-reinforced propylene resin composition may decrease.

The average frequency of the side chains can be calculated, for example, by [a] a ^{method using an isotope carbon nuclear magnetic resonance spectrum (13} C-NMR) described later, or [b] a method by gel permeation chromatography (GPC). ..

[A] The olefin-based polymer [R1] is composed of a repeating unit derived from at least one α-olefin selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms in the main chain, and isotope carbon. In the measurement by the nuclear magnetic resonance spectrum ( ¹³ C-NMR), in the range of 37.8 to 38.1 ppm, apart from the methine carbon derived from the α-olefin, the methine carbon at the junction between the side chain and the main chain It is preferable that a signal that can be assigned is observed. When the signal is observed, the average frequency of side chains can be calculated by the following equation.

[Average frequency of side chains] = 1000 × [I _PE-methine ] / {[I _all-C ] × (100- [R2']-[M]) / 100}
[I _PE-massine ]: Integral value of methine carbon at the junction of side chain and main chain [I _all-C ]: Integral value of total carbon [R2']: [R1] Other than polymer [R1] produced during production The mass ratio (mass%) of the polymer [R2] to the olefin resin (β)
[M]: [R1] The mass ratio (mass%) of the macromonomer added or produced during production to the olefin resin (β).

[B] As described above, the peak on the low molecular weight side obtained when the olefin resin (β) is analyzed by gel permeation chromatography (GPC) is an ethylene polymer that remains without copolymerization during the copolymerization reaction. Derived from the site (macromonomer). Therefore, the mass ratio of the remaining macromonomer contained in the olefin resin (β) can be obtained from the area ratio. [R1] When the mass composition of the macromonomer added or produced during production is clear, the average frequency of side chains can be determined from the difference in the mass ratio between the mass composition and the remaining macromonomer. Specifically, it can be calculated by the following equation.

[Average frequency of side chains] = ([M]-[M']) / (100- [M']) x (1 / [Mn- _M ]) x 14 / {1-([M]-[M] ']) / (100- [M'])} x (1/1000)
[M]: Mass ratio (mass%) of macromonomer added or produced during the production of [R1] to the total amount of resin [R'] obtained during the production of [R1].
[M']: Mass ratio (mass%) of the remaining macromonomer obtained from GPC to the total amount of resin [R'] obtained during the production of [R1].
[Mn _−M ]: Number average molecular weight of macromonomer.

The average frequency determined by the methods [a] and [b] is the value when the by-produced ethylene / α-olefin copolymer is counted as 0 side chains when the copolymer is present. is there.

The number of side chains can be adjusted by controlling the molar concentration of macromonomers in the polymerization system. For example, when the side chain molecular weight is constant under certain polymerization conditions, increasing the charged mass or the produced mass of the macromonomer increases the molar concentration of the macromonomer and increases the number of side chains of the produced graft polymer. .. Further, when the charged mass or the produced mass of the macromonomer is constant, the molar concentration of the macromonomer can be increased by reducing the side chain molecular weight, and the number of side chains of the produced graft polymer can be increased.

The number of side chains can also be adjusted by selecting the type of the transition metal compound (A) described later. For example, the number of side chains can be increased by selecting a catalyst for olefin polymerization containing a transition metal compound that exhibits high copolymerizability at high temperature and produces a high molecular weight polymer.

The olefin polymer [R1] satisfies the requirements (i) to (v) above, so that the fiber-reinforced propylene resin composition meets all the requirements of rigidity, hardness, and low-temperature impact resistance at a high level. It is preferable because it can be satisfied. It is more preferable that the olefin polymer [R1] further satisfies the following requirement (vi).

[Requirements (vi)]
The number of methyl branches in the side chain of the olefin polymer [R1] is less than 0.1 per 1000 carbon atoms contained in the side chain. When the number of methyl branches in the side chain is within the above range, the crystallinity of the ethylene polymer portion of the side chain is further enhanced, and the surface hardness and rigidity of the fiber-reinforced propylene resin composition are increased.

The number of methyl branches is determined by the ethylene polymer moiety (macromonomer) corresponding to the side chain separated as the elution component on the low molecular weight side in GPC in the method described in the requirement (iv), or pre-synthesized. ^{, A known method using isotope carbon nuclear magnetic resonance analysis (13} C-NMR) for an ethylene polymer site (macromonomer) corresponding to a side chain, for example, Japanese Patent Application Laid-Open No. 2006-233207. It can be measured by the method. The side chain ethylene-based polymer moiety satisfying this requirement can be obtained by specifying the type of the transition metal compound used in the catalyst for producing a vinyl-terminated macromonomer, which will be described later.

(Requirement (II))
The olefin resin (β) shows a melting peak having a melting temperature (Tm) in the range of 60 to 130 ° C. as measured by differential scanning calorimetry (DSC), and the heat of fusion ΔH at the melting peak is 3 to 100 J /. It is preferably in the range of g. The melting temperature (Tm) is more preferably 80 to 125 ° C, even more preferably 90 to 120 ° C. The heat of fusion ΔH is more preferably 4 to 80 J / g, further preferably 5 to 70 J / g, and particularly preferably 8 to 60 J / g.

Tm and ΔH are crystallized by a cooling step up to 30 ° C. after the sample is melted once through a heating step by DSC, and endothermic peaks appearing in the second heating step (heating rate 10 ° C./min) are obtained. It is an analysis.

The melting temperature (Tm) and heat of fusion ΔH observed within the above range are mainly derived from the side chain ethylene polymer of the olefin polymer [R1] constituting the olefin resin (β). When the melting temperature (Tm) and the heat of fusion ΔH are within the above ranges, the balance between rigidity, heat resistance, and toughness of the fiber-reinforced propylene resin composition is improved. On the other hand, when the melting temperature (Tm) or the heat of fusion ΔH is lower than the above range, the rigidity, heat resistance, and toughness of the fiber-reinforced propylene resin composition may decrease. Further, when the heat of fusion ΔH exceeds the above range, the low temperature impact resistance of the fiber-reinforced propylene resin composition may decrease.

Examples of the method for adjusting the melting temperature (Tm) include a method for appropriately selecting the type of transition metal compound used for the catalyst for producing a vinyl-terminated macromonomer, which will be described later.

Further, as a method for adjusting the heat of fusion ΔH, a method of controlling the abundance ratio of the vinyl-terminated macromonomer in the manufacturing process described later can be mentioned. Specific examples thereof include a method of controlling the feed amount of the vinyl-terminal macromonomer feed, or a method of controlling the feed ratio of the transition metal compound (A) and the transition metal compound (B) described later.

(Requirement (III))
The olefin resin (β) preferably has an orthodichlorobenzene-soluble component ratio E (hereinafter, also referred to as E value) of 20 ° C. or lower as measured by a cross-separation chromatograph (CFC) of 60% by mass or less. , 50% by mass or less, and even more preferably 45% by mass or less.

Generally, commercially available ethylene / α-olefin copolymers such as ethylene / propylene copolymers, ethylene / butene copolymers, and ethylene / octene copolymers are α-— such as propylene, 1-butene or 1-octene. It is a polymer adjusted so that the composition of the olefin is about 10 to 50 mol%, exhibits amorphous or low crystalline properties, and dissolves well in a specific organic solvent even at a temperature of room temperature or lower. For example, Toughmer A-5055S (trade name), which is a commercially available ethylene / butene copolymer resin, is mostly soluble in orthodichlorobenzene at 20 ° C. or lower, and has an E value of 93% by mass or more.

On the other hand, in the olefin polymer [R1] constituting the olefin resin (β) according to the present invention, the main chain is the ethylene / α-olefin copolymer as described above, but the side chain is the crystalline ethylene weight. Since it can be coalesced, it is sparingly soluble in orthodichlorobenzene below room temperature. Therefore, the olefin resin (β) has a small E value. The fact that the olefin-based resin (β) has a small E value is indirect evidence that the main chain structure and the side chain structure of the olefin-based polymer [R1] are chemically bonded, and further, olefins. It is shown that the system resin (β) contains a considerable amount of the olefin polymer [R1].

In the fiber-reinforced propylene-based resin composition according to the present invention, the olefin-based resin (β) is a propylene-based polymer (similar to a commercially available ethylene / α-olefin copolymer resin generally used as a modifier). It disperses in α) and plays a role of imparting improvement in low temperature impact resistance. Here, when a commercially available ethylene / α-olefin copolymer resin is used, the low temperature impact resistance is improved according to the amount of addition, but the original rigidity and mechanical strength of polypropylene are lowered. On the other hand, when the olefin resin (β) according to the present invention is used, the polyethylene moiety, which is the side chain of the olefin polymer [R1], is the physical cross-linking point in the domain formed by the ethylene / α-olefin copolymer. As a result, the fiber-reinforced propylene-based resin composition according to the present invention has excellent surface hardness, and the balance between rigidity and low-temperature impact resistance is significantly improved as a result of the formation of high rigidity, hardness, and mechanical strength in the domain itself. Then it is inferred.

As described above, the olefin resin (β) can contain a considerable amount of a component in which the crystalline ethylene polymer moiety is chemically bonded to the ethylene / α-olefin copolymer, and therefore, the above requirement. (II) and the above requirement (III) can be satisfied at the same time. Such a resin can be obtained by selecting a catalyst used in the step of copolymerizing ethylene with an α-olefin and a terminal vinyl ethylene polymer. For example, a transition metal compound (A) described later is used. Can be done.

(Requirement (IV))
The glass transition temperature (Tg) of the olefin resin (β) measured by differential scanning calorimetry (DSC) is in the range of -80 ° C to -30 ° C and is in the range of -80 ° C to -40 ° C. The temperature is preferably in the range of −80 ° C. to −50 ° C., more preferably in the range of −80 ° C. to −60 ° C.

The glass transition temperature (Tg) is derived from the ethylene / α-olefin copolymer of the main chain of the olefin polymer [R1]. When the glass transition temperature (Tg) is in the range of −80 ° C. to −30 ° C., the low temperature impact resistance of the fiber-reinforced propylene resin composition is improved.

The glass transition temperature (Tg) can be set within the above range by controlling the type and composition of the α-olefin which is a comonomer.

(Requirement (V))
The olefin resin (β) has an ultimate viscosity [η] measured in decalin at 135 ° C. in the range of 0.1 to 12.0 dl / g and in the range of 0.2 to 10.0 dl / g. Is preferable, the range of 0.5 to 5.0 dl / g is more preferable, and the range of 0.7 to 2.0 dl / g is further preferable. When the ultimate viscosity [η] is within the above range, the fiber-reinforced propylene-based resin composition exhibits good rigidity and mechanical strength in addition to low-temperature impact resistance, and can also exhibit good molding processability. ..

(Requirements (VI))
The melt flow rate (MFR) of the olefin resin (β) obtained in accordance with ASTM D1238E at 190 ° C. and a load of 2.16 kg was Mg / 10 min, and the olefin resin was measured in decalin at 135 ° C. When the ultimate viscosity [η] of (β) is H g / dl, the value A (hereinafter, also referred to as A value) represented by the following formula (Eq-1) is in the range of 30 to 280. It is more preferably in the range of 60 to 250, and even more preferably in the range of 70 to 200.

A = M / exp (-3.3H) ... (Eq-1)
The fact that the olefin resin (β) has an A value in such a range indicates that the macromonomer introduction rate is high. An olefin resin (β) that meets this requirement may cause deterioration of physical properties such as rigidity caused by the remaining macromonomer and non-grafted polymer even when applied for modification of a propylene resin. It is preferable because it does not exist.

(Other physical properties of olefin resin (β))
-Elastic modulus The elastic modulus of the olefin resin (β) is preferably in the range of 2 to 120 MPa, more preferably in the range of 3 to 100 MPa, and further preferably in the range of 5 to 90 MPa. preferable. When the elastic modulus is within the above range, the balance between the rigidity of the fiber-reinforced propylene resin composition and the low-temperature impact resistance becomes better. The olefin resin (β) is highly flexible because the main chain structure of the olefin polymer [R1] is composed of an ethylene / α-olefin copolymer. That is, the fiber-reinforced propylene-based resin composition containing the olefin-based resin (β) exhibits good low-temperature impact resistance. The elastic modulus can be a tensile elastic modulus according to ASTM D638.

-Phase separation structure In the olefin resin (β), it is preferable that the phase showing the crystalline component observed by the transmission electron microscope is a discontinuous phase on the order of micrometer. The determination as to whether or not the product has the above-mentioned phase structure can be performed, for example, as follows.

First, the fiber-reinforced propylene resin composition is molded in 1 minute under a pressure of 10 MPa after preheating for 5 minutes using a hydraulic hot press molding machine set at 170 ° C., and then under a pressure of 10 MPa at 20 ° C. By cooling for 3 minutes with a sheet, a test piece having a predetermined thickness is obtained. The test piece is made into small pieces of 0.5 mm square and stained with _{ruthenium acid (RuO 4).} Further, with an ultramicrotome equipped with a diamond knife, the obtained small pieces are made into ultrathin sections having a film thickness of about 100 nm. Carbon is vapor-deposited on this ultrathin section and observed with a transmission electron microscope (acceleration voltage 100 kV). According to this observation method, the side chain ethylene polymer component of the olefin polymer [R1] is higher because the intercrystal amorphous portion of the lamellar structure formed by the component is selectively stained with osmium acid. Observed as contrast. The olefin resin (β) preferably has a discontinuous phase on the order of micrometer in which the phase showing the crystalline component composed of the side chain ethylene polymer of the olefin polymer [R1] observed in this manner is observed.

As described above, the olefin resin (β) contains an olefin polymer [R1] in which an amorphous or low crystalline main chain and a crystalline side chain are covalently linked as a main component, and therefore is an amorphous component. It is considered that the compatibility effect with the crystal component is large and the microphase-separated structure is formed.

The discontinuous phase observed in the olefin resin (β) is a physical cross-linking point composed of a side chain ethylene polymer, and is contained in the fiber-reinforced propylene resin composition according to the present invention using the olefin resin (β). It is considered that the physical cross-linking point is also formed in the ethylene / α-olefin copolymer domain formed in. Therefore, as described above, the fiber-reinforced propylene-based resin composition according to the present invention is considered to have an excellent balance between rigidity and low-temperature impact resistance.

On the other hand, when a polymer blend of an ethylene / α-olefin copolymer and an ethylene polymer is used, the microphase-separated structure is not formed and a coarse crystal phase is observed. Therefore, in the fiber-reinforced propylene-based resin composition using the polymer blend, no physical cross-linking point is formed in the olefin copolymer domain, and it is not possible to obtain a fiber-reinforced propylene-based resin composition showing a good physical property balance. ..

As described above, the peak on the low molecular weight side obtained when the olefin resin (β) is analyzed by gel permeation chromatography (GPC) is the ethylene polymer moiety (macro) that remains without copolymerization during the copolymerization reaction. The mass ratio of the remaining macromonomer contained in the olefin resin (β) can be obtained from the area ratio of the peak on the low molecular weight side to the total peak area derived from the monomer). The mass ratio of the remaining macromonomer calculated in this manner is preferably 0 to 30% by mass, more preferably 0 to 25% by mass, and further preferably 0 to 20% by mass. It is particularly preferably 2 to 15% by mass. The fact that the mass ratio of the remaining macromonomer is within the above range means that the component of the ethylene polymer alone that has not been incorporated into the main chain is sufficiently small, whereby the olefin resin (β) is effective. Can exhibit reforming performance. On the other hand, if the mass ratio of the remaining macromonomer exceeds 30% by mass, the modification effect and rigidity for low temperature impact resistance may decrease.

<Reinforcing fiber>
The fiber-reinforced propylene-based resin composition according to the present invention contains reinforcing fibers. The reinforcing fiber is not particularly limited, and examples thereof include organic fibers such as carbon and nylon, and inorganic fibers such as basalt and glass fibers, and glass fibers are preferable. Examples of the glass fiber include those obtained by melt-spinning glass such as E glass, C glass, S glass and alkali-resistant glass into filamentous fibers. As a raw material for glass fibers, particularly long glass fibers, a continuous glass fiber bundle is used, which is commercially available as glass roving. The average fiber diameter of the glass fiber is preferably 3 to 300 μm, more preferably 5 to 25 μm, and even more preferably 5 to 20 μm. The number of filaments focused on the glass fiber bundle is preferably 400 to 10,000, more preferably 1,000 to 6,000, and even more preferably 3,000 to 5,000. .. The fiber length of the glass fiber in the pellet is preferably 0.5 to 20.0 mm, more preferably 1.0 to 12.0 mm.

The fiber-reinforced propylene-based resin composition according to the present invention is a resin other than the propylene-based polymer (α) and the olefin-based resin (β), rubber, inorganic filler, and organic, as long as the object of the present invention is not impaired. It can contain fillers and the like. Further, the fiber-reinforced propylene resin composition according to the present invention is a weather-resistant stabilizer, a heat-resistant stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an antifogging agent, a lubricant, a pigment, a dye, a plasticizer, and an aging agent. Additives such as inhibitors, hydrochloric acid absorbers, antioxidants, and crystal nucleating agents can be included. The contents of the other resin, rubber, the inorganic filler, the organic filler, the additive and the like are not particularly limited as long as they do not impair the object of the present invention.

The flexural modulus of the fiber-reinforced propylene-based resin composition according to the present invention measured in accordance with JIS K7171 is preferably 600 to 9000 MPa, more preferably 1000 to 7000 MPa, still more preferably 1000 to 4000 MPa. If the elastic modulus exceeds 9000 MPa, the moldability may be poor or the molded product may become brittle.

[Manufacturing method of fiber-reinforced propylene resin composition]
The method for producing a fiber-reinforced propylene-based resin composition according to the present invention comprises ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing the following components (A) to (C). The step of producing the olefin resin (β) by copolymerizing with at least one α-olefin selected from the group is included. The production of the olefin resin (β) includes a step of polymerizing ethylene to produce the macromonomer and a step of copolymerizing ethylene, α-olefin and the macromonomer, and these steps may be carried out in this order. It may be carried out at the same time. Hereinafter, each component (A) to (C) will be described, and then a specific manufacturing method, manufacturing conditions, and the like will be described. Hereinafter, the component (A) is also referred to as a crosslinked metallocene compound (A), the component (B) is also referred to as a transition metal compound (B), and the component (C) is also referred to as a compound (C).

<Cross-linked metallocene compound (A)>
The crosslinked metallocene compound (A) used in the present invention is represented by the following formula (I) and functions as a catalyst for olefin polymerization in the presence of the compound (C) described later.

In formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are independently hydrogen atoms, hydrocarbon groups, silicon-containing groups or silicon-containing groups, respectively. Heteroatom-containing groups other than the above may be exhibited, and ^{two adjacent groups of R 1 to} R ⁴ may be bonded to each other to form a ring.

R ⁶ and R ¹¹ are the same atom or the same group selected from the group consisting of hydrogen atoms, hydrocarbon groups, silicon-containing groups and heteroatom-containing groups other than silicon-containing groups.

R ⁷ and R ¹⁰ are the same atom or the same group selected from the group consisting of hydrogen atoms, hydrocarbon groups, silicon-containing groups and heteroatom-containing groups other than silicon-containing groups.

R ⁶ and R ⁷ may be coupled to each other to form a ring, and R ¹⁰ and R ¹¹ may be coupled to each other to form a ring. However, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

R ¹³ and R ¹⁴ each independently represent an aryl group.

M represents a titanium atom, a zirconium atom or a hafnium atom.

Y ¹ represents a carbon atom or a silicon atom.

Q indicates a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or unconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. , J represents an integer of 1 to 4, and when j is an integer of 2 or more, the plurality of Qs may be the same or different. ).

The olefin polymerization catalyst containing the crosslinked metallocene compound (A) includes ethylene, α-olefin, and a vinyl-terminated macromonomer synthesized by an olefin polymerization catalyst composed of the components (B) and (C) described later. Plays a role in forming a site forming the main chain of the olefin polymer [R1].

That is, the catalyst for olefin polymerization containing the crosslinked metallocene compound (A) can copolymerize ethylene, α-olefin and vinyl-terminal macromonomer, and has particularly high copolymerizability with respect to α-olefin and vinyl-terminal macromonomer. It has the characteristics showing. Further, the catalyst for olefin polymerization containing the crosslinked metallocene compound (A) exhibits sufficiently high olefin polymerization activity even under relatively high temperature conditions such that the macromonomer which is an ethylene polymer chain is dissolved, and has a sufficiently high molecular weight for practical use. It has the characteristic of producing a polymer of.

Since the catalyst for olefin polymerization containing the crosslinked metallocene compound (A) has the above-mentioned characteristics, the olefin-based resin (β) contains a large amount of the olefin-based polymer [R1], and the above requirements (I). (IV) and (V) can be satisfied. As a result, the fiber-reinforced propylene-based resin composition according to the present invention has a high surface hardness and an excellent balance of physical properties between low-temperature impact resistance and rigidity. Hereinafter, the chemical structural features of the crosslinked metallocene compound (A) used in the present invention will be described.

The crosslinked metallocene compound (A) structurally has the following features [m1] to [m3].
[M1] Of the two ligands, one is a cyclopentadienyl group which may have a substituent, and the other one is a fluorenyl group having a substituent (hereinafter, also referred to as "substituted fluorenyl group"). It says.).
[M2] Two ligands are bonded by an aryl group-containing covalent bond cross-linking portion (hereinafter, also referred to as “cross-linking portion”) composed of a carbon atom or a silicon atom having an aryl group.
[M3] The transition metal (M) constituting the metallocene compound is an atom of Group 4 of the periodic table, specifically, a titanium atom, a zirconium atom or a hafnium atom.

Hereinafter, the cyclopentadienyl group which may have a substituent, the substituted fluorenyl group, the crosslinked portion and other features of the crosslinked metallocene compound (A) will be sequentially described.

(Cyclopentadienyl group which may have a substituent)
In formula (I), R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group, and represent a hydrogen atom and a hydrocarbon group. Alternatively, a silicon-containing group is preferable, and two adjacent groups may be bonded to each other to form a ring.

For example, R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms, or ^one or more of R 1, R ² , R ³ and R ⁴ are hydrocarbon groups (hereinafter "hydrocarbon groups (f1)". ) ”, Preferably a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group (hereinafter, may be referred to as“ silicon-containing group (f2) ”). Yes, more preferably a silicon-containing group having 1 to 20 carbon atoms. In addition, examples of R ¹ , R ² , R ³ and R ⁴ include heteroatom-containing groups (excluding silicon-containing groups (f2)) such as halogenated hydrocarbon groups, oxygen-containing groups and nitrogen-containing groups. ..

The hydrocarbon group (f1) is preferably a hydrocarbon group having 1 to 20 carbon atoms, for example, a linear or branched hydrocarbon group such as an alkyl group, an alkenyl group or an alkynyl group, a cycloalkyl group or the like. Examples thereof include cyclic unsaturated hydrocarbon groups such as cyclic saturated hydrocarbon groups and aryl groups. The hydrocarbon group (f1) also includes a group in which any two hydrogen atoms bonded to carbon atoms adjacent to each other are simultaneously substituted to form an alicyclic or aromatic ring among the above-exemplified groups.

Specific examples of the hydrocarbon group (f1) include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-octyl group. Linear hydrocarbon groups such as n-nonyl group, n-decanyl group, allyl group; isopropyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, 3-methylpentyl group, neopentyl group. Group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1- Branched hydrocarbon groups such as methyl-1-isopropyl-2-methylpropyl group; cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; phenyl group, naphthyl Cyclic unsaturated hydrocarbon groups such as groups, biphenyl groups, phenanthryl groups, anthracenyl groups and their nuclear alkyl substituents; at least one hydrogen atom of saturated hydrocarbon groups such as benzyl group and cumyl group is substituted with aryl groups. The group that was made is mentioned.

The silicon-containing group (f2) is preferably a silicon-containing group having 1 to 20 carbon atoms, and examples thereof include a group in which a silicon atom is directly covalently bonded to the ring carbon of the cyclopentadienyl group. Specific examples thereof include an alkylsilyl group such as a trimethylsilyl group and an arylsilyl group such as a triphenylsilyl group.

Specific examples of the hetero atom-containing group (excluding the silicon-containing group (f2)) include a methoxy group, an ethoxy group, a phenoxy group, an N-methylamino group, a trifluoromethyl group, a tribromomethyl group, and a pentafluoroethyl group. Examples include a group and a pentafluorophenyl group.

When ^{two or more of R 1} , R ² , R ³ and R ⁴ are substituents other than hydrogen atoms, the substituents may be the same or different from each other, and R ¹ , R ² , R ³ and two groups adjacent to each other of R ⁴ may form an alicyclic or aromatic ring bonded to each other.

(Substituted fluorenyl group)
In formula (I), R ⁵ , R ⁸ , R ⁹ and R ¹² independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group, and represent a hydrogen atom and a hydrocarbon group. Alternatively, a silicon-containing group is preferable. R ⁶ and R ¹¹ are the same atoms or the same groups selected from the group consisting of hydrogen atoms, hydrocarbon groups, silicon-containing groups and heteroatom-containing groups other than silicon-containing groups, and are hydrogen atoms, hydrocarbon groups or groups. A silicon-containing group is preferred. R ⁷ and R ¹⁰ are the same atom or the same group selected from the group consisting of hydrogen atom, hydrocarbon group, silicon-containing group and hetero atom-containing group other than silicon-containing group, and are hydrogen atom, hydrocarbon group or A silicon-containing group is preferred. R ⁶ and R ⁷ may be coupled to each other to form a ring, and R ¹⁰ and R ¹¹ may be coupled to each other to form a ring. However, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

From the viewpoint of polymerization activity, it is preferable that neither ^{R 6} nor R ¹¹ is a hydrogen atom, and it is more preferable that none of ^{R 6} , R ⁷ , R ¹⁰ and R ^{11 is a hydrogen atom, and R 6} and R ¹¹ are It is more preferred that they are the same groups selected from the group consisting of hydrocarbon groups and silicon-containing groups, and that R ⁷ and R ^{10 are the same groups selected from the group consisting of hydrocarbon groups and silicon-containing groups.} .. Further, it is preferable that R ⁶ and R ⁷ are bonded to each other to form an alicyclic or aromatic ring, and R ¹⁰ and R ¹¹ are bonded to each other to form an alicyclic or aromatic ring.

Examples of the hydrocarbon group in R ^{5 to} R ¹² and a preferable group include the hydrocarbon group (f1) defined in the place of the substituted cyclopentadienyl group. Examples of the silicon-containing group in R ^{5 to} R ¹² and a preferable group include the silicon-containing group (f2) defined in the place of the substituted cyclopentadienyl group. Examples of the heteroatom-containing group in R ^{5 to} R ¹² include the groups exemplified in the above-mentioned substituted cyclopentadienyl group.

The substituted fluorenyl group when R ⁶ and R ⁷ and R ¹⁰ and R ¹¹ are bonded to each other to form an alicyclic or aromatic ring is derived from the compounds represented by the formulas [II] to [VI] described later. A suitable example is the group to be used.

(Bridge)
In formula (I), R ¹³ and R ¹⁴ each independently represent an aryl group, and Y ¹ represents a carbon atom or a silicon atom. In the method according to the present invention, the bridging atom Y ¹ of the bridge, has an R ¹³ and R ¹⁴ is aryl (aryl) groups be the same as or different from each other. From the viewpoint of manufacturing ease, ^{it is preferable that R 13} and R ¹⁴ are the same as each other.

Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a group in which one or more of the aromatic hydrogens (sp2-type hydrogens) contained therein are substituted with a substituent. Examples of the substituent include a hydrocarbon group (f1) and a silicon-containing group (f2) defined in the place of the substituted cyclopentadienyl group, and a halogen atom and a halogenated hydrocarbon group.

Specific examples of the aryl group include an unsubstituted aryl group having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group; a trill group, an isopropylphenyl group, and an n-butylphenyl group. , T-butylphenyl group, alkyl group substituted aryl group such as dimethylphenyl group; cycloalkyl group substituted aryl group such as cyclohexylphenyl group; aryl halide group such as chlorophenyl group, bromophenyl group, dichlorophenyl group, dibromophenyl group; Examples thereof include alkyl halide-substituted aryl groups such as (trifluoromethyl) phenyl group and bis (trifluoromethyl) phenyl group. The position of the substituent is preferably the meta position and / or the para position. Of these, substituted phenyl groups in which the substituents are located at the meta and / or para positions are more preferable.

(Other features of crosslinked metallocene compound (A))
In formula (I), Q can be coordinated with a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or unconjugated diene having 4 to 10 carbon atoms, an anionic ligand or a lone electron pair. Indicates a sex ligand, j indicates an integer of 1 to 4, and when j is an integer of 2 or more, the plurality of Qs may be the same or different.

Specific examples of the halogen are fluorine, chlorine, bromine, and iodine, and the hydrocarbon groups include, for example, linear or branched aliphatic hydrocarbon groups having 1 to 10 carbon atoms and 3 to 10 carbon atoms. Aliphatic hydrocarbon groups can be mentioned. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group and 1,1-. Diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1,1,3 -Methylbutyl group, neopentyl group and examples. Examples of the alicyclic hydrocarbon group include a cyclohexyl group, a cyclohexylmethyl group, and a 1-methyl-1-cyclohexyl group.

Examples of the halogenated hydrocarbon group in Q include a group in which at least one hydrogen atom of the hydrocarbon group in Q is substituted with a halogen atom.

Specific examples of neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms include s-cis- or s-trans-η4-1,3-butadiene, s-cis- or s-trans-η4-1. 4-Diphenyl-1,3-butadiene, s-cis- or s-trans-η-4-3-methyl-1,3-pentadiene, s-cis- or s-trans-η4-1,4-dibenzyl-1, 3-butadiene, s-cis- or s-trans-η4-2,4-hexadiene, s-cis- or s-trans-η4-1,3-pentadiene, s-cis-or s-trans-η4-1 , 4-Ditril-1,3-butadiene, s-cis- or s-trans-η4-1,4-bis (trimethylsilyl) -1,3-butadiene and the like.

Specific examples of the anion ligand include an alkoxy group such as methoxy, tert-butoxy and phenoxy, a carboxylate group such as acetate and benzoate, and a sulfonate group such as mesylate and tosylate.

Specific examples of neutral ligands that can be coordinated with lone electron pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2-. Examples include ethers such as dimethoxyethane.

In the formula (I), M represents a titanium atom, a zirconium atom or a hafnium atom, which is preferable in that the hafnium atom can copolymerize the macromonomer with high efficiency and can control the high molecular weight.

In particular, in an industrial process in which polymerization is carried out under high pressure and high temperature conditions in order to ensure high productivity, it is preferable that M is a hafnium atom from the above characteristics. This is because the abundance ratio of ethylene and α-olefin is higher than that of the macromonomer under high pressure conditions, and the molecular weight generally decreases under high temperature conditions. Therefore, the macromonomer is efficiently copolymerized as described above and is heavy. This is because it is important to use a catalyst having the ability to control coalescence to a high molecular weight.

The characteristics of M being a hafnium atom are that (1) the Lewis acidity of the hafnium atom is smaller and the reactivity is lower than that of the zirconium atom or the titanium atom, and (2) the zirconium atom or the titanium atom. The fact that the bond energy between the hafnium atom and the carbon atom is large compared to the above is a chain transfer reaction including the β-hydrogen elimination reaction of the polymerization active species that is bonded to the product polymer chain, which is one of the molecular weight determinants. It is considered that this is due to the suppression of.

(Example of preferred crosslinked metallocene compound (A))
Specific examples of the substituted fluorenyl group constituting the crosslinked metallocene compound (A) are shown in the following formulas [II] to [VI]. In the exemplified compounds described later, octamethyloctahydrodibenzofluorenyl refers to a group derived from a compound having a structure represented by the formula [II]. Octamethyltetrahydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by the formula [III]. Dibenzofluorenyl refers to a group derived from a compound having a structure represented by the formula [IV]. 1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by the formula [V]. 1,3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by the formula [VI].

Examples of the crosslinked metallocene compound (A) include
Diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (Cyclopentadienyl) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) ( Dibenzofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, diphenylmethylene (Cyclopentadienyl) (1,3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7) -Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3 , 6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (1,1) ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (1,3,3', 6 , 6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-( Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,3,6,7-tetramethylfluorenyl) zirconium dichloride, Di (p-tolyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconide dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (1,1) ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (1,3,3', 6 , 6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-( Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium Dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium Dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (1,3,3', 6 , 6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-( Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium Zirconium,
Di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconide dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (3,6-dienyl) tert-Butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) ) (Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadi) Enyl) (1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (1) , 3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-diphenyl) -3,6-ditert-butylfluorenyl) zirconium Dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium Dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene ( Cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconide dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,3,6) , 7-Tetratert-butylfluorenyl) zirconium dichloride,
Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (m-) Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zyroxide dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium Dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride , Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) Methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7) -(Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-) Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zyroxide dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium Dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride , Di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) Methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7) -(Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-) tert-Butyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zyroxide dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium Dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (1,3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride , Di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) Methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7) -(Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-Ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-) n-Butyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zyroxide dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium Dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (1,3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride , Di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) Methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7) -(Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride,
Di (p-biphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (1,3,3', 6 , 6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7-( Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconide, di (p-biphenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium Dichloride,
Di (1-naphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (1,3,3', 6 , 6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-( Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium Zirconium,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (3,6-ditert- Butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (octamethyl Tetrahydrodicyclopentafluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (1,3,3', 6 , 6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-( Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium Zirconium,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethylfluore) Nyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride,
Di (p-isopropylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) ) Zyrosine dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (3) , 6-ditert-butylfluorenyl) zirconium dichloride,
Diphenylcilylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylcilylene (Cyclopentadienyl) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) ( Dibenzofluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (1,1', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, diphenylcilylene (Cyclopentadienyl) (1,3,3', 6,6', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7) -Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylcilylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3 , 6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride.

Examples of the crosslinked metallocene compound (A) include a compound obtained by changing "zirconium" of the above-exemplified compound to "hafnium" or "titanium", and "dichloride" being "difluorolide", "dibromid", "diaiodide", "dimethyl", and the like. Compounds changed to "methylethyl" or "dibenzyl", "cyclopentadienyl" changed to "3-tert-butyl-5-methyl-cyclopentadienyl", "3,5-dimethyl-cyclopentadienyl" , "3-tert-Butyl-cyclopentadienyl" or "3-methyl-cyclopentadienyl" and the like can also be mentioned.

The above crosslinked metallocene compound (A) can be produced by a known method, and the production method is not particularly limited. Known methods include, for example, the methods described in International Publication No. 01/27124 and International Publication No. 04/029062 by the applicant.

The crosslinked metallocene compound (A) as described above is used alone or in combination of two or more.

<Transition metal compound (B)>
The transition metal compound (B) used in the present invention is a compound having a structure represented by the following formula [B], and functions as a catalyst for olefin polymerization in the presence of the compound (C) described later.

(In formula [B], M represents a transition metal atom of Group 4 or 5 of the Periodic Table.

m represents an integer of 1 to 4.

R ¹ represents a _{C n 'H 2n' + 1} (n ' is a is an integer of 1 to 8) hydrocarbon group having 1 to 8 carbon atoms represented by.

R ² to R ⁵ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, silicon-containing group, a germanium-containing group or shows a tin-containing group, may form a ring two groups adjacent to each other are connected to each other among the R ² to R ^5.

R ^{6 to} R ⁸ represent hydrocarbon groups, and ^{at least one of R 6 to} R ⁸ is an aromatic hydrocarbon group.

^{When m is an integer of 2 or more, two groups of R 2 to} R ⁸ may be connected to each other between the structural units of the formula [B].

n is a number that satisfies the valence of M.

X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, and a silicon-containing group. Indicates a group, a germanium-containing group, or a tin-containing group.

When n is an integer of 2 or more, the plurality of Xs may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. ).

The catalyst for olefin polymerization containing the transition metal compound (B) plays a role of producing a vinyl-terminated macromonomer which is an ethylene polymer and forming a site forming a side chain of the olefin polymer [R1].

That is, the olefin polymerization catalyst containing the transition metal compound (B) has a characteristic that it mainly polymerizes ethylene to produce an ethylene polymer having a single-terminal vinyl group at a high selectivity. Further, the catalyst for olefin polymerization containing the transition metal compound (B) has a feature of producing a relatively low molecular weight ethylene polymer (with a weight average molecular weight in the range of 200 to 10,000). Since the catalyst for olefin polymerization containing the transition metal compound (B) has the above-mentioned characteristics, the side chain is efficiently introduced into the olefin-based polymer [R1], and the fiber-reinforced propylene-based resin composition according to the present invention. The object has a high surface hardness and has an excellent balance of physical properties between low temperature impact resistance and rigidity.

Further, the olefin polymerization catalyst containing the transition metal compound (B) has a characteristic of highly selectively polymerizing ethylene even under the condition that ethylene coexists with α-olefin and vinyl-terminated macromonomer. The side chain of the olefin-based polymer [R1] retains good mechanical and thermal properties as an ethylene polymer, and the fiber-reinforced propylene-based resin composition according to the present invention has high surface hardness and low-temperature impact resistance. The balance of physical properties between ethylene and rigidity becomes excellent. The above characteristics are also preferable in adopting the polymerization method [b] among the production methods described later.

Further, it is preferable that the catalyst for olefin polymerization containing the transition metal compound (B) has a performance of substantially not forming an olefin structure, so-called internal olefin, inside the polymer chain from the viewpoint of light resistance and color resistance. .. Hereinafter, the chemical structural features of the transition metal compound (B) used in the present invention will be described.

In the formula [B], N ... M generally indicate that they are coordinated, but in the present invention, they may or may not be coordinated.

In the formula [B], M represents a transition metal atom of Group 4 or Group 5 of the Periodic Table, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc., preferably a metal of Group 4 of the Periodic Table. It is an atom, specifically titanium, zirconium, hafnium, and more preferably zirconium.

m represents an integer of 1 to 4, preferably 1 to 2, and particularly preferably 2.

R ¹ _{is, C n 'H 2n' +} 1 (n ' is a is an integer of 1 to 8) represents a hydrocarbon group having 1 to 8 carbon atoms represented by, for example, methyl, ethyl radical, n Acyclic hydrocarbon groups such as -propyl group, n-butyl group, iso-propyl group, iso-butyl group, tert-butyl group, neopentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, Examples include a cyclic hydrocarbon group such as a cyclohexyl group. It is preferably a linear hydrocarbon group, and specifically, a methyl group, an ethyl group, an n-propyl group, or an n-butyl group. Among these, a methyl group, an ethyl group and an n-propyl group are more preferable. More preferably, it is a methyl group or an ethyl group. By selecting the hydrocarbon group, an ethylene polymer having a relatively low molecular weight, for example, a weight average molecular weight in the range of 200 to 10,000 can be produced, and as described above, a fiber-reinforced propylene resin having an excellent balance of physical properties. It becomes easy to obtain the composition.

R ² to R ⁵ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, silicon-containing It represents a group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring.

When m is 2 or more, two of the groups represented by ^{R 2 to} R ⁸ may be linked between the structural units of the formula [B].

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group and the like. A linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20; a linear or branched alkyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms such as a vinyl group, an allyl group, and an isopropenyl group. Alkenyl group; ethynyl group, propargyl group, etc. Linear or branched alkynyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, etc. Cyclic saturated hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms; cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl group, indenyl group and fluorenyl group; phenyl group, naphthyl group, An aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as a biphenyl group, a terphenyl group, a phenanthryl group, and an anthrasenyl group; Examples thereof include an alkyl-substituted aryl group such as a butylphenyl group.

The hydrocarbon group may have a hydrogen atom substituted with a halogen. For example, a halogenated hydrocarbon having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as a trifluoromethyl group, a pentafluorophenyl group and a chlorophenyl group. The group is mentioned. Further, the hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include an aryl group-substituted alkyl group such as a benzyl group and a cumyl group.

Further, the hydrocarbon group is a heterocyclic compound residue; an oxygen such as an alcoholic group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group and a carboxylic acid anhydride group. Containing groups: Amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group as ammonium salt Nitrogen-containing groups such as those that have become; boron-containing groups such as bolangyl group, bolantriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanic acid ester group, Sulfur-containing groups such as isothian acid ester group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group, sulfinyl group, sulfenyl group; phosphide group, phosphoryl group, thiophosphoryl group, phosphat It may have a phosphorus-containing group such as a group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

Of these, in particular, the number of carbon atoms of 1 such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group and n-hexyl group ~ 30, preferably 1-20 linear and branched alkyl groups; 6-30 carbon atoms, preferably 6-20 carbon atoms such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthracenyl group. Alyl groups: These aryl groups include halogen atoms, alkyl or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20, and aryl groups and aryloxy groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms. A substituted aryl group in which 1 to 5 substituents are substituted is preferable.

Examples of the oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, and phosphorus-containing group include those similar to those exemplified above. Heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, and sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. Examples of the compound residue include an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and a group further substituted with a substituent such as an alkoxy group.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, and the like, specifically, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, and a triethylsilyl group. , Diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group and the like. Among these, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a triphenylsilyl group and the like are preferable. Particularly, a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group and a dimethylphenylsilyl group are preferable. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

Examples of the germanium-containing group and the tin-containing group include those in which the silicon of the silicon-containing group is replaced with germanium and tin. Next, the examples of ^{R 2 to} R ⁶ described above will be described more specifically. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.

Specific examples of the alkylthio group include a methylthio group and an ethylthio group. Specific examples of the allyloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group. Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, a naphthylthio group and the like.

Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group. Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group.

Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group. Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group. Specific examples of the imide group include an acetoimide group and a benzimide group. Specific examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group.

Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, a phenylimino group and the like. Specific examples of the sulfonic acid ester group include a methyl sulfonic acid group, an ethyl sulfonic acid group, and a phenyl sulfonic acid group. Specific examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, and an N-methyl-p-toluenesulfonamide group.

In R ^{2 to} R ⁵ , two or more of these groups, preferably adjacent groups, are linked to each other to form an alicyclic ring, an aromatic ring, or a hydrocarbon ring containing a foreign atom such as a nitrogen atom. Also, these rings may further have substituents.

n is a number that satisfies the valence of M, and is specifically an integer of 0 to 5, preferably 1 to 4, and more preferably 1 to 3. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, and a silicon-containing group. Indicates a group, a germanium-containing group, or a tin-containing group. When n is 2 or more, they may be the same or different from each other.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the hydrocarbon group include the same groups as those exemplified by the R ² to R ^5. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, nonyl group, dodecyl group and icosyl group; carbon such as cyclopentyl group, cyclohexyl group, norbornyl group and adamantyl group. Cycloalkyl group of number 3 to 30; alkenyl group such as vinyl group, propenyl group, cyclohexenyl group; arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethyl Examples thereof include, but are not limited to, an aryl group such as a phenyl group, an ethylphenyl group, a propylphenyl group, a biphenyl group, a naphthyl group, a methylnaphthyl group, an anthryl group and a phenanthryl group. Further, these hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of hydrocarbon groups having 1 to 20 carbon atoms is replaced with halogen.

Of these, those having 1 to 20 carbon atoms are preferable. Examples of the heterocyclic compound residues include the same ones as exemplified for the R ² to R ^5. The oxygen-containing group, wherein R ² to R ⁵ are the same as those exemplified can be mentioned, specifically, hydroxy group, phenoxy group; methoxy group, an ethoxy group, a propoxy group, an alkoxy group such as butoxy , Methylphenoxy group, dimethylphenoxy group, naphthoxy group and other allyloxy groups; phenylmethoxy group, phenylethoxy group and other arylalkoxy groups; acetoxy group; carbonyl group and the like, but are not limited thereto.

Examples of the sulfur-containing group, said include the same ones as exemplified for R ² to R ^5, specifically, methyl sulfonate group, trifluoromethane sulfonate group, phenyl sulfonate group, Benjirusuru Sulfonate groups such as phonate group, p-toluene sulfonate group, trimethylbenzene sulphonate group, triisobutylbenzene sulphonate group, p-chlorobenzene sulphonate group, pentafluorobenzene sulphonate group; methyls Sulfinate groups such as ruffinate group, phenylsulfinate group, benzylsulfinate group, p-toluenesulfinate group, trimethylbenzenesulfinate group, pentafluorobenzenesulfinate group; alkylthio group; arylthio group etc. However, it is not limited to these.

Specific examples of nitrogen-containing groups, the include the same ones as exemplified for R ² to R ^5, specifically, amino group, methylamino group, dimethylamino group, diethylamino group, dipropylamino group , Alkylamino group such as dibutylamino group, dicyclohexylamino group; arylamino group such as phenylamino group, diphenylamino group, ditrilamino group, dinaphthylamino group, methylphenylamino group or alkylarylamino group. It is not limited to these.

Specific examples of the boron-containing group include BR ₄ (R indicates a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like). Specifically, the phosphorus-containing group includes a trialkylphosphin group such as a trimethylphosphine group, a tributylphosphine group and a tricyclohexylphosphin group; a triarylphosphine group such as a triphenylphosphine group and a tritrylphosphin group; a methylphosphite group and an ethyl. Examples thereof include, but are not limited to, a phosphite group (phosphide group) such as a phosphite group and a phenylphosphite group; a phosphonic acid group; and a phosphinic acid group.

Specific examples the silicon-containing group, said include the same ones as exemplified for R ² to R ^5, specifically, a phenyl silyl group, diphenyl silyl group, a trimethylsilyl group, triethylsilyl group, tripropylsilyl Hydrocarbon-substituted silyl groups such as groups, tricyclohexylsilyl groups, triphenylsilyl groups, methyldiphenylsilyl groups, tritrylsilyl groups, trinaphthylsilyl groups; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether groups; trimethylsilylmethyl groups, etc. Silicon-substituted alkyl group; Silicon-substituted aryl group such as trimethylsilylphenyl group and the like.

Specific examples germanium-containing group, wherein the same ones as exemplified for R ² to R ⁵ can be mentioned, specifically, include groups obtained by substituting silicon of the silicon-containing group to the germanium. Specific examples of tin-containing group, wherein R ² to R ⁵ are the same as those exemplified are exemplified by, more specifically, it includes groups obtained by substituting silicon of the silicon-containing group to tin.

Specific examples of the halogen-containing group include fluorine-containing groups such as _{PF 6} and BF ₄ , chlorine-containing groups such as _{ClO 4 and SbC l6, and iodine-containing groups such as IO 4} , but the halogen-containing groups are not limited thereto. Absent. Specific examples of the aluminum-containing group include, but are not limited to, AlR ₄ (R indicates a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

R ^{6 to} R ⁸ are hydrocarbon groups, at least one of which is an aromatic hydrocarbon group.

Specifically, the hydrocarbon group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, an n-hexyl group and the like. A linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20; a linear or branched alkyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms such as a vinyl group, an allyl group, and an isopropenyl group. Branched alkenyl group; ethynyl group, propargyl group, etc. Linear or branched alkynyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, etc. Cyclic saturated hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms; cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl group, indenyl group and fluorenyl group; phenyl group and naphthyl group. , Biphenyl group, terphenyl group, phenanthryl group, anthracenyl group and other aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms; tolyl group, isopropylphenyl group, t-butylphenyl group, dimethylphenyl group, di-t. Examples thereof include alkyl substituted aryl groups such as a butylphenyl group.

The hydrocarbon group may have a hydrogen atom substituted with a halogen, and such a hydrocarbon group preferably has 1 to 30 carbon atoms such as a trifluoromethyl group, a pentafluorophenyl group and a chlorophenyl group. Examples include 1 to 20 halogenated hydrocarbon groups. Further, the hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include an aryl group-substituted alkyl group such as a benzyl group and a cumyl group.

Specific examples of the aromatic hydrocarbon group include an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group and an anthrasenyl group; a trill group. , Alkyl-substituted aryl groups such as isopropylphenyl group, t-butylphenyl group, dimethylphenyl group and di-t-butylphenyl group. In the aromatic hydrocarbon group, a hydrogen atom may be substituted with a halogen, or another hydrocarbon group may be substituted.

Since ^{at least one of the hydrocarbon groups of R 6 to} R ⁸ is an aromatic hydrocarbon group, the polymerization catalyst containing the transition metal compound (B) gives good activity even under high temperature polymerization conditions. , Suitable for the production of the olefin resin (β) according to the present invention, and the fiber-reinforced propylene resin composition according to the present invention exhibits good performance.

When m is 2 or more, two of the groups represented by ^{R 2 to} R ⁸ may be linked between the structural units of the formula [B]. Further, m is ^{R 1} each other if 2 or more, ^{R 2} together, ^{R 3} together, ^{R 4} together, ^{R 5} each other, ^{R 6} to each other, each other ^{R 7,} even among ^{R 8} are mutually the same or different Good.

When n is an integer of 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring.

Further, the transition metal compound (B) represented by the above formula [B] can be used alone or in combination of two or more.

<Compound (C)>
The compound (C) used in the present invention reacts with the crosslinked metallocene compound (A) and the transition metal compound (B) to function as a catalyst for olefin polymerization. Specifically, the compound (C) includes (C-1) an organometallic compound, (C-2) an organoaluminum oxy compound, and (C-3) a crosslinked metallocene compound (A) or a transition metal compound (B). It is at least one compound selected from the group consisting of compounds that react to form an ion pair. Such compounds (C-1) to (C-3) have been filed by the applicant of the present application and have already been published as WO2015 / 147186, and the compounds (C-1) to (C-1) to (C-1). C-3) can be used as it is without any restrictions. In the examples described later, triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate are used, but the present invention is not limited to these compounds.

Hereinafter, a step of polymerizing an olefin in the presence of an olefin polymerization catalyst containing the components (A) to (C) to produce an olefin resin (β) will be described.

The polymerization can be carried out by any of a solution polymerization method, a bulk polymerization method, a liquid phase polymerization method such as suspension polymerization, and a gas phase polymerization method, but the post-process [a-2] and the polymerization method of the polymerization method [a] described later [B] is carried out by a liquid phase polymerization method.

Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method are aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Aliphatic hydrocarbons such as; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane or mixtures thereof, and the olefin itself may be used as a solvent. it can.

When the above-mentioned catalyst for olefin polymerization is used in the production of the olefin resin (β), the crosslinked metallocene compound (A) is preferably used in an amount of ^{10-8 to 1 mol per liter of the reaction volume, preferably 10-7} to 10. More preferably, 0.5 mol is used. The transition metal compound (B) is preferably used in an amount of ^10-12 to ^10-2 mol, more preferably ^10-10 to ^{10-3 mol, per liter of the reaction volume.} The molar ratio (B / A) of the transition metal compound (B) to the crosslinked metallocene compound (A) is preferably 0.00001 to 100, more preferably 0.00005 to 10 and 0. It is more preferably .0001 to 5.

When the organometallic compound (C-1) is used, the transition metal atom (M) in the organometallic compound (C-1), the crosslinked metallocene compound (A) and the transition metal compound (B) (crosslinked metallocene compound (A)) The molar ratio (C-1 / M) with titanium atom, zirconium atom or hafnium atom) is preferably 0.01 to 100,000, more preferably 0.05 to 50,000.

When the organic aluminum oxy compound (C-2) is used, the aluminum atom in the organic aluminum oxy compound (C-2) and the transition metal atom (M) in the crosslinked metallocene compound (A) and the transition metal compound (B) ( In the crosslinked metallocene compound (A), the molar ratio (C-2 / M) with titanium atom, zirconium atom or hafnium atom) is preferably 10 to 500,000, more preferably 20 to 100,000.

When the ionized ionic compound (C-3) is used, the ionized ionic compound (C-3) and the transition metal atom (M) in the crosslinked metallocene compound (A) and the transition metal compound (B) (crosslinked metallocene compound (C-3)). In A), the molar ratio (C-3 / M) with titanium atom, zirconium atom or hafnium atom) is preferably 1 to 10, and more preferably 1 to 5.

The polymerization temperature of the olefin using such a catalyst for olefin polymerization is preferably −50 to 300 ° C., more preferably 0 to 170 ° C. The polymerization pressure is preferably normal pressure to 9.8 MPa (100 kg / cm ² ), more preferably normal pressure to 4.9 MPa (50 kg / cm ² ). The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type.

The molecular weight of the obtained olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Further, it can be adjusted by selecting the components (A) to (C) to be used or by selecting a combination.

Examples of the olefin used for the polymerization include ethylene and the α-olefin having 3 to 20 carbon atoms. For these olefins, ethylene can be used as an essential monomer, and one or more other monomers can be used in combination.

In the present invention, the olefin resin (β) can be produced, for example, by the following polymerization method [a] or polymerization method [b].

-Polymerization method [a]
Cross-linking in the presence of the reaction products of the pre-step [a-1] and the pre-step [a-1] of polymerizing ethylene to obtain a vinyl-terminated macromonomer in the presence of the transition metal compound (B) and the compound (C). A post-step of copolymerizing ethylene with at least one α-olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms in the presence of the metallocene compound (A) and the compound (C) [a- 2] and a method including.

-Polymerization method [b]
In the presence of the crosslinked metallocene compound (A), the transition metal compound (B), and the compound (C), ethylene and at least one α-olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms are copolymerized. Method of polymerization.

Hereinafter, preferred forms of the polymerization method [a] and the polymerization method [b] will be described.

-Polymerization method [a]
Pre-process [a-1]
This is a step of polymerizing ethylene mainly with a catalyst for olefin polymerization composed of the transition metal compound (B) and the compound (C) to obtain a vinyl-terminated macromonomer which is substantially an ethylene polymer, and the polymerization method is in the above range. There are no particular restrictions. In the case of liquid phase polymerization, the obtained reaction solution may be introduced into the subsequent step as it is, or after the vinyl-terminated macromonomer is taken out, the vinyl-terminated macromonomer is introduced into the subsequent step as a lump or as a powder. Alternatively, it may be slurry or redissolved and introduced into a subsequent process.

Post-process [a-2]
In the presence of the crosslinked metallocene compound (A) and compound (C), at least one α-olefin selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms and the previous step [a-1]. This is a step of copolymerizing the obtained vinyl-terminal macromonomer. The polymerization method is not particularly limited within the above range, but a liquid phase polymerization method is preferable because it is a step of forming an amorphous or low crystallinity ethylene / α-olefin copolymer moiety, and the concentration of each monomer is particularly adjusted. Solution polymerization is preferable in order to control and obtain an olefin resin (β) having a desired structure.

In the polymerization reaction, the pre-step [a-1] may be carried out in a batch manner and the post-step [a-2] may also be carried out in a batch formula, or the pre-step [a-1] may be carried out in a batch formula and the vinyl ends taken out. By introducing a macromonomer, the subsequent step [a-2] may be carried out continuously. Further, by performing the pre-step [a-1] in a continuous manner and introducing the product as it is, the post-step [a-2] can also be carried out in a continuous manner. Further, the pre-step [a-1] can be performed continuously and the post-step [a-2] can be performed in batches.

-Polymerization method [b]
In the presence of the crosslinked metallocene compound (A), the transition metal compound (B), and the compound (C), ethylene and at least one α-olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms are used. It is a method of polymerizing in a single stage, and can be performed by one polymerizer. The olefin polymerization catalyst composed of the transition metal compound (B) and the compound (C) tends to polymerize ethylene with high selectivity even if an α-olefin other than ethylene is present in the polymerization system. Further, the catalyst tends to produce a polymer having a relatively small molecular weight, and the obtained polymer has a vinyl terminal. Therefore, the catalyst for olefin polymerization composed of the transition metal compound (B) and the compound (C) can produce a vinyl-terminated macromonomer which is a substantial ethylene polymer.

On the other hand, the catalyst for olefin polymerization composed of the crosslinked metallocene compound (A) and the compound (C) can produce a polymer having a large molecular weight, and can produce ethylene, α-olefin, transition metal compound (B), and compound ( The vinyl-terminated macromonomer obtained by using the olefin polymerization catalyst composed of C) can be copolymerized. In this way, the olefin polymer [R1] can be contained in the olefin resin (β) under one polymerization reaction condition.

In the method for producing the olefin resin (β), the subsequent steps [a-2] of the polymerization method [a] and the polymerization steps of the polymerization method [b] are carried out by a solution polymerization method in a temperature range of 80 to 300 ° C. Is preferable.

The above-mentioned "solution polymerization" is a general term for a method of polymerizing in a state where a polymer is dissolved by using an inert hydrocarbon described later as a polymerization solvent. Examples of the polymerization solvent used in the subsequent step [a-2] of the polymerization method [a] and the polymerization step of the polymerization method [b] include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, benzene, toluene and xylene. Examples thereof include aromatic hydrocarbons such as, ethylene chloride, chlorobenzene, and halogenated hydrocarbons such as dichloromethane, and these can be used alone or in combination of two or more. Of these, aliphatic hydrocarbons such as hexane and heptane are preferable from the viewpoint of industry, and hexane is more preferable from the viewpoint of separation and purification from the olefin resin (β).

Further, the polymerization temperature of the subsequent step [a-2] of the polymerization method [a] and the polymerization step of the polymerization method [b] is preferably in the range of 80 ° C. to 300 ° C., more preferably in the range of 80 ° C. to 200 ° C. The range of 90 ° C to 200 ° C is more preferable. Such a temperature is preferable because it is higher than the temperature at which the vinyl-terminated macromonomer is satisfactorily dissolved in an aliphatic hydrocarbon such as hexane and heptane, which is industrially preferably used as the polymerization solvent. It is preferable that the polymerization temperature is higher in order to improve the introduction efficiency of the polyethylene side chain. Further, it is preferable that the temperature is higher from the viewpoint of improving productivity.

The polymerization pressure in the subsequent steps [a-2] of the polymerization method [a] and the polymerization step in the polymerization method [b] is preferably normal pressure to 10 MPa gauge pressure, more preferably normal pressure to 5 MPa gauge pressure, and normal pressure to 3 MPa. Gauge pressure is more preferred. From the viewpoint of improving productivity, the polymerization pressure is particularly preferably 0.5 to 3 MPa gauge pressure.

The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions. Among these, in the present invention, it is preferable to adopt a method in which monomers are continuously supplied to the reactor to carry out copolymerization.

The reaction time (average residence time when copolymerization is carried out by a continuous method) of the post-step [a-2] of the polymerization method [a] and the polymerization step of the polymerization method [b] is determined by the catalyst concentration, polymerization temperature, etc. Although it depends on the conditions of the above, 0.5 minutes to 5 hours is preferable, and 5 minutes to 3 hours is more preferable.

The polymer concentration in the subsequent steps [a-2] and the polymerization method [b] of the polymerization method [a] is preferably 5 to 50% by mass, more preferably 10 to 40% by mass during steady operation. The polymer concentration is more preferably 15 to 35% by mass from the viewpoint of viscosity limitation in polymerization ability, post-treatment step (desolvent) load and productivity.

The molecular weight of the obtained olefin resin (β) can be adjusted by changing the hydrogen concentration and the polymerization temperature in the polymerization system. Furthermore, it can be adjusted according to the amount of compound (C) used. When hydrogen is added, the amount thereof is preferably 0.001 to 5,000 NL per 1 kg of the olefin resin (β) produced.

The method for preparing the fiber-reinforced propylene-based resin composition according to the present invention is not particularly limited, such as a melting method and a solution method, but a melt-kneading method is practically preferable. As the melt-kneading method, a melt-kneading method generally used for thermoplastic resins can be applied. For example, powdery or granular components are uniformly mixed with other additives if necessary by a Henschel mixer, a ribbon blender, a V-type blender, or the like, and then a uniaxial or multiaxial kneading extruder, a kneading roll, etc. It can be prepared by kneading with a batch kneader, a kneader, a ribbon mixer or the like.

The melt-kneading temperature of each component (for example, the cylinder temperature in the case of an extruder) is preferably 170 to 250 ° C, more preferably 180 to 230 ° C. The kneading order and method of each component are not particularly limited.

[Molded product]
The fiber-reinforced propylene resin composition according to the present invention can improve low-temperature impact resistance while maintaining rigidity, and has an excellent balance between rigidity and low-temperature impact resistance. Therefore, injection molding, extrusion molding, Various molded products can be molded by known molding methods such as inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, and foam molding. The molded product can be applied to various known applications such as automobile parts, containers for food and medical applications, and packaging materials for food and electronic materials.

The molded product made of the fiber-reinforced propylene resin composition according to the present invention has an excellent balance between rigidity and low-temperature impact resistance, high surface hardness, and excellent chemical resistance, and thus can be used for various automobile parts. .. For example, automobile exterior parts such as bumpers, side moldings and aerodynamic undercovers, automobile interior parts such as instrument panels and interior trims, exterior panel parts such as fenders, door panels and steps, and engine surroundings such as engine covers, fans and fan shrouds. It can be used for parts and the like.

Containers for food and medical applications include, for example, tableware, retort containers, frozen storage containers, retort pouches, microwave heat-resistant containers, frozen food containers, chilled confectionery cups, cups, beverage bottles and other food containers, retort containers, bottles. Examples include containers, blood transfusion sets, medical bottles, medical containers, medical hollow bottles, medical bags, infusion bags, blood storage bags, infusion bottles, chemical containers, detergent containers, cosmetic containers, perfume containers, toner containers and the like.

Examples of packaging materials include food packaging materials, meat packaging materials, processed fish packaging materials, vegetable packaging materials, fruit packaging materials, fermented food packaging materials, confectionery packaging materials, oxygen absorber packaging materials, retort food packaging materials, and freshness. Retention film, pharmaceutical packaging material, cell culture bag, cell test film, bulb packaging material, seed packaging material, vegetable / mushroom cultivation film, heat-resistant vacuum-molded container, side dish container, side dish lid material, commercial wrap film, household use Examples include plastic wrap and baking cartons.

Examples of films, sheets and tapes include protective films for polarizing plates, protective films for liquid crystal panels, protective films for optical parts, protective films for lenses, protective films for electrical parts and electrical appliances, protective films for mobile phones, and personal computers. Protective films such as protective films, masking films, condenser films, reflective films, laminates (including glass), radiation resistant films, γ-ray resistant films, and porous films can be mentioned.

Other uses include, for example, housings for home appliances, hoses, tubes, wire coating materials, gaskets for high-pressure wires, tubes for cosmetics / perfume sprays, medical tubes, infusion tubes, pipes, wire harnesses, motorcycles / railways. Interior materials for vehicles, aircraft, ships, etc., instrument panel skin, door trim skin, rear package trim skin, ceiling skin, rear pillar skin, seat back garnish, console box, armrest, airbag case lid, shift knob, assist grip, side step Mats, reclining covers, seats in trunks, seat belt buckles, inner / outer moldings, roof moldings, belt moldings and other molding materials, door seals, body seals and other automotive sealing materials, glass run channels, mudguards, kicking plates, steps Mats, number plate housings, automobile hose members, air duct hoses, air duct covers, air intake pipes, air dam skirts, timing belt cover seals, bonnet cushions, door cushions and other automobile interior / exterior materials, vibration damping tires, static tires, cars Special tires such as race tires and radiocon tires, packing, automobile dust cover, lamp seal, automobile boot material, rack and pinion boot, timing belt, wire harness, grommet, emblem, air filter packing, furniture, footwear, clothing, bags・ Skin materials such as building materials, sealing materials for buildings, waterproof sheets, building material sheets, building material gaskets, window films for building materials, iron core protective members, gaskets, doors, door frames, window frames, peripheral edges, skirts, opening frames, etc. , Floor materials, ceiling materials, wallpaper, health products (eg non-slip mats / sheets, fall prevention films / mats / sheets), health equipment parts, shock absorbing pads, protectors / protective equipment (eg helmets, guards), sports Supplies (eg sports grips, protectors), sports armor, rackets, mouth guards, balls, golf balls, transport equipment (eg transport shock absorbing grips, shock absorbing sheets), vibration damping pallets, shock absorbing dampers, insulators , Shock absorbers for footwear, shock absorbers, shock absorbers such as shock absorbing films, grip materials, miscellaneous goods, toys, shoe soles, sole soles, shoe midsole / inner soles, soles, sandals, suckers, toothbrushes , Floor materials, gym mats, power tool parts, agricultural machinery parts, heat dissipation materials, transparent substrates, soundproofing materials, gaskets After filling the bottle with non-woven fabric, wire cable, shape memory material, medical gasket, medical cap, drug stopper, gasket, baby food, dairy products, pharmaceuticals, sterilized water, etc., high temperature treatment such as boiling treatment, high pressure steam sterilization, etc. Packing materials for applications, industrial sealing materials, industrial sewing tables, number plate housings, cap liners such as PET bottle cap liners, stationery, office supplies, OA printer legs, fax legs, sewing legs, motor support mats, audio Precision equipment such as anti-vibration materials, OA equipment support members, heat-resistant packing for OA, animal cages, beakers, physics and chemistry experimental equipment such as female cylinders, optical measurement cells, clothes cases, clear cases, clear files, clear sheets, desk mats As a fiber, for example, non-woven fabric, elastic non-woven fabric, fiber, waterproof cloth, breathable fabric or cloth, paper diaper, sanitary goods, sanitary goods, filter, bag filter, dust collecting filter, air cleaner, hollow thread Examples include filters, water purification filters, and gas separation membranes.

Among these, the molded product obtained from the fiber-reinforced propylene resin composition according to the present invention can improve low-temperature impact resistance while maintaining rigidity, and has an excellent balance between rigidity and low-temperature impact resistance. Therefore, it can be particularly suitably used for automobile interior / exterior materials such as bumpers and instrument panels, outer panel materials, food containers, and beverage containers.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded.

In the following examples, the physical properties of the olefin resin (β), the propylene polymer (α) and the fiber-reinforced propylene resin composition were measured by the following methods.

<< Method for measuring physical properties of olefin resin (β) >>
The method for measuring the physical properties of the olefin resin (β) is shown below.

(1) Measurement of melting temperature (Tm) and heat of fusion ΔH The melting temperature (Tm) and heat of fusion ΔH were measured by DSC measurement under the following conditions. Using a differential scanning calorimeter (trade name: RDC220, manufactured by SII), a sample of about 10 mg was heated from 30 ° C. to 200 ° C. at a heating rate of 50 ° C./min in a nitrogen atmosphere, and the temperature was raised for 10 minutes. Retained. Further, the temperature was cooled to 30 ° C. at a temperature lowering rate of 10 ° C./min, held at that temperature for 5 minutes, and then raised to 200 ° C. at a temperature rising rate of 10 ° C./min. The endothermic peak observed during this second temperature rise was defined as the melting peak, and the temperature was determined as the melting temperature (Tm). The heat of fusion ΔH was obtained by calculating the area of the melting peak. When the melting peak was multimodal, the area of the entire melting peak was calculated and calculated.

(2) Measurement of glass transition temperature (Tg) The glass transition temperature (Tg) was measured by DSC measurement under the following conditions. Using a differential scanning calorimeter (trade name: RDC220, manufactured by SII), a sample of about 10 mg was heated from 30 ° C. to 200 ° C. at a heating rate of 50 ° C./min in a nitrogen atmosphere, and the temperature was raised for 10 minutes. Retained. Further, the temperature was cooled to −100 ° C. at a temperature lowering rate of 10 ° C./min, held at that temperature for 5 minutes, and then raised to 200 ° C. at a temperature rising rate of 10 ° C./min. The glass transition temperature (Tg) is perceived as the DSC curve bends due to the change in specific heat and the baseline moves in parallel during the second temperature rise. The temperature at the intersection of the tangent of the baseline, which is lower than this bending, and the tangent of the point where the inclination is maximum at the bending portion is defined as the glass transition temperature (Tg).

(3) Measurement of Ratio E of Orthodichlorobenzene Soluble Component The ratio E (mass%) of orthodichlorobenzene soluble component at 20 ° C. or lower was determined by CFC measurement under the following conditions.

Equipment: Cross fractionation chromatograph CFC2 (Polymer ChAR)
Detector (built-in): Infrared spectrophotometer IR ⁴ (Polymer ChAR)
Detection wavelength: 3.42 μm (2,920 cm ^-1 ); Fixed sample concentration: 120 mg / 30 mL
Injection volume: 0.5 mL
Temperature down time: 1.0 ° C / min
Elution classification: 4.0 ° C interval (-20 to 140 ° C)
GPC column: Shodex HT-806M x 3 (trade name, manufactured by Showa Denko KK)
GPC column temperature: 140 ° C
GPC column calibration: monodisperse polystyrene (Tosoh)
Molecular weight calibration method: General-purpose calibration method (polystyrene conversion)
Mobile phase: o-dichlorobenzene (with BHT added)
Flow rate: 1.0 mL / min.

(4) Elastic modulus measurement (tensile test)
The elastic modulus was measured in accordance with ASTM D638 with a test piece obtained by press-molding an olefin resin (β) at 200 ° C. for 5 minutes.

(5) ¹³ C-NMR measurement For the purpose of analyzing the composition of the α-olefin of the polymer, confirming the number of methyl branches and the graft structure of the macromonomer, ¹³ C-NMR measurement was carried out under the following conditions.

Device: AVANCE III500 CryoProbe Product type nuclear magnetic resonance device (trade name, manufactured by Bruker Biospin)
Measurement nucleus: ¹³ C (125 MHz)
Measurement mode: Single pulse Proton broadband decoupling Pulse width: 45 ° (5.00 μsec)
Number of points: 64k
Measuring range: 250ppm (-55-195ppm)
Repeat time: 5.5 seconds Accumulation number: 512 times Measurement solvent: Ortodichlorobenzene / benzene-d ₆ (4/1 v / v)
Sample concentration: ca. 60mg / 0.6mL
Measurement temperature: 120 ° C
Window function: exponential (BF: 1.0Hz)
Chemical shift criteria: Benzene-d ₆ (128.0 ppm).

(6) GPC analysis In order to analyze the molecular weight of the polymer and estimate the amount of residual macromonomer, GPC analysis was performed under the following conditions.

Equipment: Alliance GPC 2000 type (trade name, manufactured by Waters)
Column: 2 TSKgel GMH6-HT, 2 TSKgel GMH6-HTL (trade name, both manufactured by Tosoh, inner diameter 7.5 mm, length 30 cm)
Column temperature: 140 ° C
Mobile phase: Ortodichlorobenzene (containing 0.025% dibutylhydroxytoluene)
Detector: Differential refractometer Flow rate: 1.0 mL / min
Sample concentration: 0.15% (w / v)
Injection volume: 0.5 mL
Sampling time interval: 1 second Column calibration: Monodisperse polystyrene (manufactured by Tosoh).

(7) Measurement of Extreme Viscosity ([η] [dl / g]) The ultimate viscosity was measured at 135 ° C. using a decalin solvent. Specifically, after about 20 mg of the resin was dissolved in 25 ml of decalin, the specific viscosity ηsp was measured in an oil bath at 135 ° C. using an Ubbelohde viscometer. After adding 5 ml of decalin to this decalin solution and diluting it, the specific viscosity ηsp was measured in the same manner as described above. This dilution operation was repeated twice more, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the ultimate viscosity [η] (unit: dl / g) (see the following formula).

[Η] = lim (ηsp / C) (C → 0).

(8) Melt flow rate (MFR [g / 10min])
The melt flow rate was measured under a 2.16 kg load according to ASTM D1238E. The measurement temperature was 190 ° C.

(9) Composition Ratio of Olefin Polymer [R1] The composition ratio (% by mass) of the olefin polymer [R1] is 20 ° C. or less with the remaining macromonomer composition ratio (mass%) calculated from GPC analysis. The composition ratio (mass%) of the ethylene / α-olefin copolymer having no side chain, which is estimated from the ratio E of the orthodichlorobenzene-soluble component in the above, was estimated by subtracting the total amount from 100% by mass.

<< Method for measuring physical properties of propylene-based polymer (α) and fiber-reinforced propylene-based resin composition >>
The method for measuring the physical properties of the propylene-based polymer (α) and the fiber-reinforced propylene-based resin composition is shown below. The ultimate viscosity was measured by the method shown in (8) above.

(10) Melt flow rate (MFR [g / 10min])
The melt flow rate was measured under a 2.16 kg load according to ASTM D1238E. The measurement temperature was 230 ° C.

(11) Amount of n-decane-soluble (insoluble) component at 23 ° C. Approximately 3 g of propylene-based polymer (α), 500 ml of decane, and a small amount of a heat-resistant stabilizer soluble in decane were charged into a glass measuring container. Under a nitrogen atmosphere, the temperature was raised to 150 ° C. in 2 hours while stirring with a stirrer to dissolve the propylene-based polymer (α). After holding at 150 ° C. for 2 hours, the mixture was slowly cooled to 23 ° C. over 8 hours. The obtained liquid containing the precipitate of the propylene-based block copolymer was filtered under reduced pressure with a 25G-4 standard glass filter manufactured by Iwata Glass Co., Ltd. 100 ml of the filtrate was collected and dried under reduced pressure to obtain a part of the decan-soluble component. After this operation, the n-decane soluble component (Dsol) content and the n-decane insoluble component (Dinsol) content were determined by the following formulas. The propylene-based polymer (α) was ^{measured up to a unit of 10 -4} g, and this mass was expressed as b (g) in the following formula. In addition, the mass of a part of the decan-soluble component ^{was measured to the unit of 10-4} g, and this mass was expressed as a (g) in the following formula.

Content of n-decane soluble component (Dsol) at 23 ° C. (% by mass) = 100 × (500 × a) / (100 × b)
N-decane insoluble component (Dinsol) content (mass%) at 23 ° C. = 100-100 × (500 × a) / (100 × b).

(12) Measurement of pentad fraction mmmm Pentado fraction mmmm [%], which is one of the indexes of stereoregularity of the polymer and whose microtacticity was investigated, is Macromolecules 8,687 in the propylene polymer (α). It was calculated from the peak intensity ratio of ^{the 13} C-NMR spectrum assigned based on (1975). ^{13 The} C-NMR spectrum was measured using EX-400 (trade name, manufactured by JEOL Ltd.), using TMS as a reference, at a temperature of 130 ° C., and using an o-dichlorobenzene solvent.

(13) Measurement of skeleton content derived from propylene and ethylene In order to measure the skeleton concentration derived from ethylene in Dsol, 1,2,4-trichlorobenzene / heavy benzene (mass ratio: 2 /) of 20 to 30 mg of a sample was taken. 1) After dissolving in 0.6 ml of the solution, carbon nuclear magnetic resonance analysis ( ¹³ C-NMR) was performed. The quantification of propylene and ethylene was determined from the diad chain distribution. In the case of the propylene-ethylene copolymer, PP = Sαα, EP = Sαγ + Sαβ, and EE = 1/2 (Sβδ + Sδδ) + 1/4 Sγδ were used, and the calculation was performed by the following formula.

Propene (mol%) = (PP + 1 / 2EP) x 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)]
Ethylene (mol%) = (1 / 2EP + EE) x 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)].

(14) Tensile breaking strength and tensile breaking strain measurement test The tensile breaking strength [MPa] and the tensile breaking strain [%] were measured under the following conditions according to JIS K7162.

<Measurement conditions>
Specimen: JIS K7162-BA dumbbell
5 mm (width) x 2 mm (thickness) x 75 mm (length)
Tensile speed: 20 mm / min Chuck distance: 58 mm.

(15) Measurement of bending strength and elastic modulus The bending strength and elastic modulus FM [MPa] were measured under the following conditions according to JIS K7171.

<Measurement conditions>
Specimen: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Bending speed: 2 mm / min Bending span: 64 mm.

(16) Charpy impact test The Charpy impact value [kJ / m ² ] was measured under the following conditions according to JIS K7111.

<Test conditions>
Temperature: 23 ° C and -30 ° C
Specimen: 10 mm (width) x 80 mm (length) x 4 mm (thickness)
The notch is machined.

(17) Rockwell hardness measurement Rockwell hardness (R scale) was measured under the following conditions according to JIS K7202.

<Measurement conditions>
Specimen: 30 mm (width) x 30 mm (length) x 2 mm (thickness)
Two test pieces were stacked and measured.

(18) Measurement of Thermal Deformation Temperature (HDT) The thermal deformation temperature was measured according to JIS K7191-1. That is, both ends of the test piece are supported in a heating bath, and the temperature of the heating medium is set at a rate of 2 ° C./min while applying a predetermined bending stress (constant load of 0.45 MPa) to the test piece by a load rod in the center below. The temperature of the heating medium when the deflection of the test piece reached a predetermined amount was defined as the thermal deformation temperature.

(19) Measurement of high-speed surface impact strength (HRIT) For high-speed surface impact strength, the total fracture energy was measured under the following conditions.

<Test conditions>
Temperature: -30 ° C
Specimen: 30 mm (width) x 30 mm (length) x 2.0 mm (thickness) (square plate)
Speed: 3m / s
Strike core: 1/2 inch φ
Cradle: 1 inch φ.

[Production Example 1] The following compound (1) and the following compound (3) used as a catalyst for producing an olefin resin (β-1) were synthesized by a known method.

In a stainless steel polymerizer having an internal volume of 100 L (stirring rotation speed = 250 rpm, internal temperature 110 ° C., polymerization pressure 1.0 MPa · G) equipped with stirring blades, dehydrated hexane was placed at 23 L / hr, and the compound (1) was placed. Continuously at 0.0130 mmol / hr, the compound (3) at 0.00136 mmol / hr, triphenylcarbenium tetrakis (pentafluorophenyl) borate at 0.057 mmol / hr, and triisobutylaluminum at 2.0 mmol / hr. Supplyed. In addition, 1-butene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerizer is 0.32 (molar ratio) as 1-butene / ethylene and 0.042 (molar ratio) as hydrogen / ethylene. Supplyed. The generated polymerization liquid was continuously discharged through a discharge port provided on the side wall of the polymerizer while adjusting the opening degree of the liquid level control valve so as to maintain the amount of solution in the polymerizer of 28 L. The obtained polymerization solution is guided to a heater to raise the temperature to 180 ° C., 80 mL of methanol is added every hour as a catalyst deactivator to stop the polymerization, and the mixture is continuously transferred to a devolatile step to dry. By doing so, an olefin resin (β-1) was obtained at a production rate of 5.6 kg / hr. The analysis results of the obtained olefin resin (β-1) are shown in Table 1.

[Production Example 2] Production of Olefin Resin (β'-1) In a stainless steel polymerizer with an internal volume of 100 L (stirring speed = 250 rpm, internal temperature 110 ° C., polymerization pressure 1.0 MPa · G) equipped with stirring blades. , Dehydrated hexane at 23 L / hr, compound (1) at 0.00775 mmol / hr, triphenylcarbenium tetrakis (pentafluorophenyl) borate at 0.031 mmol / hr, triisobutylaluminum at 2.31 mmol / hr, Continuously supplied at the speed of. In addition, 1-butene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerizer is 0.23 (molar ratio) as 1-butene / ethylene and 0.04 (molar ratio) as hydrogen / ethylene. Supplyed. The generated polymerization liquid was continuously discharged through a discharge port provided on the side wall of the polymerizer while adjusting the opening degree of the liquid level control valve so as to maintain the amount of solution in the polymerizer of 28 L. The obtained polymerization solution is guided to a heater to raise the temperature to 180 ° C., and methanol is added at 80 mL per hour as a catalyst deactivating agent to stop the polymerization, and the mixture is continuously transferred to a devolatile step. By drying, an olefin resin (β'-1) was obtained at a production rate of 3.1 kg / hr. The analysis results of the obtained olefin resin (β'-1) are shown in Table 1.

[Production Example 3] Production of propylene-based polymer (α-1) (1) Preparation of solid titanium catalyst component 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol are heated at 130 ° C. for 2 hours. The reaction was carried out to obtain a uniform solution. 21.3 g of phthalic anhydride was added to this solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

After cooling the uniform solution thus obtained to room temperature, 75 ml of this uniform solution was added dropwise over 200 ml of titanium tetrachloride kept at −20 ° C. for 1 hour. After completion of charging, the temperature of this mixed solution was raised to 110 ° C. over 4 hours, 5.22 g of diisobutyl phthalate (DIBP) was added when the temperature reached 110 ° C., and the mixture was stirred and held at the same temperature for 2 hours. And reacted.

Then, the solid part was collected by hot filtration, the solid part was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was collected again by hot filtration and washed thoroughly with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution. As a result, a solid titanium catalyst component was obtained.

Here, the detection of this free titanium compound was carried out by the following method. 10 ml of the supernatant liquid of the solid titanium catalyst component was collected with a syringe and charged into 100 ml of Schlenk with branches which had been replaced with nitrogen in advance. Next, the solvent hexane was dried in a nitrogen stream and vacuum dried for another 30 minutes. 40 ml of ion-exchanged water and 10 ml of (1 + 1) sulfuric acid were charged therein, and the mixture was stirred for 30 minutes. This aqueous solution is transferred to a 100 ml volumetric flask through a filter paper, then 1 ml of a concentrated phosphoric acid aqueous solution as a masking agent for iron (II) ions and 5 ml of a 3% hydrogen peroxide solution as a titanium coloring reagent are added, and the volume is further increased with ion-exchanged water. It was made into 100 ml. The volumetric flask was shaken, and after 20 minutes, UV was used to observe the absorbance at 420 nm. Free titanium was washed and removed until this absorption was no longer observed.

The solid titanium catalyst component prepared as described above was stored as a decan slurry, and a part of the solid titanium catalyst component was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component thus obtained was 2.3% by mass of titanium, 61% by mass of chlorine, 19% by mass of magnesium, and 12.5% by mass of DIBP.

(2) Production of Prepolymerization Catalyst 100 g of the solid titanium catalyst component, 39.3 mL of triethylaluminum, and 100 L of heptane were inserted into an autoclave with a stirrer having an content of 200 L. The internal temperature was maintained at 15 to 20 ° C., 600 g of propylene was inserted, and the reaction was carried out with stirring for 60 minutes to obtain a catalyst slurry containing a prepolymerization catalyst.

(3) Main Polymerization In a circulating tubular polymerizer with a jacket having a content of 58 L, propylene was 43 kg / hour, hydrogen was 300 NL / hour, and the catalyst slurry produced in (2) above was 0.55 g / hour as a solid catalyst component. Triethylaluminum was continuously supplied at 2.9 ml / hour and dicyclopentyldimethoxysilane at 3.1 ml / hour, and polymerization was carried out in a fully liquid state in which no gas phase was present. The temperature of the tubular polymerizer was 70 ° C. and the pressure was 3.74 MPa / G.

The obtained slurry was sent to a Vessel polymerizer with a stirrer having an content of 100 L, and further polymerization was carried out. Propylene was supplied to the polymerizer at 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 8.7 mol%. Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 3.49 MPa / G.

The obtained slurry is transferred to a liquid transfer tube having an internal volume of 2.4 L, the slurry is gasified, air-solid separation is performed, and then polypropylene homopolymer powder is sent to a gas phase polymerizer having an internal volume of 480 L to carry ethylene. / Propylene block copolymerization was performed. A part of the powder was sampled before copolymerization to measure MFR and mm mm. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerizer is 0.23 (molar ratio) as ethylene / (ethylene + propylene) and 0.031 (molar ratio) as hydrogen / ethylene. Supplied. Polymerization was carried out at a polymerization temperature of 70 ° C. and a pressure of 1.0 MPa / G.

The obtained propylene-based block copolymer was vacuum-dried at 80 ° C. Table 2 shows the physical characteristics of the obtained propylene-based polymer (α-1).

[Example 1]
20 parts by mass of olefin resin (β-1) prepared in Production Example 1, 60 parts by mass of propylene polymer (α-1) prepared in Production Example 3, glass fiber as reinforcing fiber (trade name: T) -480, manufactured by Nippon Electric Glass Co., Ltd., glass chopped strand, diameter 13 μm) 20 parts by mass, heat stabilizer IRGANOX1010 (trade name, manufactured by Ciba Geigy Co., Ltd.) 0.2 parts by mass, modified propylene resin POLYBOND3200 (trade name, Made by Chemitura, MFR: 250 g / 10 minutes, content of constituent units derived from maleic anhydride in 100% by mass of MAH-PP: 1.0% by mass) 1.0 part by mass, sulfur-based antioxidant DMTP Yoshitomi (commodity) Name, manufactured by Mitsubishi Chemical Corporation) 0.3 parts by mass was uniformly mixed with a tumbler. Then, it was melt-kneaded under the following conditions with a twin-screw extruder to prepare a pellet-shaped fiber-reinforced propylene resin composition, and a test piece was prepared under the following conditions with an injection molding machine. Table 3 shows the physical characteristics of the obtained fiber-reinforced propylene resin composition.

<Melting and kneading conditions>
Biaxial kneader in the same direction: Part number NR-2-36, manufactured by Nakatani Machinery Co., Ltd. Cylinder temperature: 280-280-280-250-250-250 ° C
Screw rotation speed: 100 rpm
Feeder speed: 700 rpm.

<JIS small test piece / injection molding conditions>
Injection molding machine: Part number EC40, manufactured by Toshiba Machine Co., Ltd. Cylinder temperature: 190 ° C
Mold temperature: 40 ° C
Injection time-holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds Screw rotation: 80 rpm
Holding pressure: 60 MPa
Back pressure: 3 MPa.

[Comparative Example 1]
In Example 1, pellet-shaped fiber-reinforced propylene was used in the same manner as in Example 1 except that the olefin resin (β'-1) prepared in Production Example 2 was used instead of the olefin resin (β-1). A based resin composition was prepared, and a test piece was prepared by an injection molding machine. Table 3 shows the physical characteristics of the obtained fiber-reinforced propylene resin composition.

[Comparative Example 2]
In Comparative Example 1, a pellet-shaped fiber-reinforced propylene resin composition was prepared in the same manner as in Comparative Example 1 except that the amount of the olefin resin (β'-1) used was changed to 23 parts by mass, and the injection molding machine was used. To prepare a test piece. Table 3 shows the physical characteristics of the obtained fiber-reinforced propylene resin composition.

From Table 3, the fiber-reinforced propylene resin composition of Example 1 containing the propylene-based polymer (α) and the olefin-based resin (β) satisfying the requirements according to the present invention and the reinforcing fibers in a predetermined compounding ratio is It was found that the balance between rigidity and low temperature impact resistance was good.

Claims (7)

1 to 99 parts by mass of a propylene-based polymer (α) having a melt flow rate (MFR) of 0.1 to 500 g / 10 min at 230 ° C. and a 2.16 kg load obtained in accordance with ASTM D1238E, and the above. 1 to 99 parts by mass of an olefin resin (β) satisfying the following requirements (I), (IV) , (V) and (VI) other than the propylene polymer (α) (the propylene polymer (α) and the above 100 parts by mass of the resin composition containing (the total of the olefinic resin (β) is 100 parts by mass) and
Reinforcing fiber 1 to 50 parts by mass and
A fiber-reinforced propylene-based resin composition characterized by containing.
(I) The olefin resin (β) contains a graft-type olefin polymer [R1] having a main chain composed of an ethylene / α-olefin copolymer and a side chain composed of an ethylene polymer.
(IV) The glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) is in the range of −80 to −30 ° C.
(V) The ultimate viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 12.0 dl / g.
The MFR of the olefin resin (β) obtained in accordance with (VI) ASTM D1238E at 190 ° C. and a load of 2.16 kg was Mg / 10 min, and the olefin resin was measured in decalin at 135 ° C. When the ultimate viscosity [η] of (β) is H g / dl, the value A represented by the following formula (Eq-1) is in the range of 30 to 280.
A = M / exp (-3.3H) ... (Eq-1) The fiber-reinforced propylene-based resin composition according to claim 1, wherein the olefin-based resin (β) further satisfies the following requirements (II) and (III).
(II) The measurement by differential scanning calorimetry (DSC) shows a melting peak having a melting temperature in the range of 60 to 130 ° C., and the heat of fusion ΔH at the melting peak is in the range of 3 to 100 J / g.
(III) The ratio E of the orthodichlorobenzene-soluble component at 20 ° C. or lower as measured by a cross-separation chromatograph (CFC) is 60% by mass or less. The fiber-reinforced propylene-based resin composition according to claim 1 or 2, wherein the flexural modulus measured in accordance with JIS K7171 is in the range of 600 to 9000 MPa. The fiber-reinforced propylene resin composition according to any one of claims 1 to 3, wherein the weight average molecular weight of the side chain of the graft-type olefin polymer [R1] is in the range of 500 to 15,000. The fiber reinforcement according to any one of claims 1 to 4, wherein the side chain is present at an average frequency of 0.1 to 20 per 1000 carbon atoms contained in the main chain of the graft-type olefin polymer [R1]. Propylene resin composition. The method for producing a fiber-reinforced propylene-based resin composition according to any one of claims 1 to 5.
In the presence of an olefin polymerization catalyst containing the following components (A) to (C), ethylene is copolymerized with at least one α-olefin selected from the group consisting of α-olefins having 3 to 20 carbon atoms. A method for producing a fiber-reinforced propylene-based resin composition, which comprises a step of producing the olefin-based resin (β).
(A) Crosslinked metallocene compound represented by the following formula (I) (B) Transition metal compound represented by the following formula [B] (C) (C-1) Organometallic compound, (C-2) Organometallic oxy At least one compound selected from the group consisting of a compound and (C-3) a compound that reacts with the crosslinked metallocene compound (A) or the transition metal compound (B) to form an ion pair.

In formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹² are independently hydrogen atoms, hydrocarbon groups, silicon-containing groups or silicon-containing groups, respectively. Heteroatom-containing groups other than the above may be exhibited, and ^{two adjacent groups of R 1 to} R ⁴ may be bonded to each other to form a ring.
R ⁶ and R ¹¹ are the same atom or the same group selected from the group consisting of hydrogen atoms, hydrocarbon groups, silicon-containing groups and heteroatom-containing groups other than silicon-containing groups.
R ⁷ and R ¹⁰ are the same atom or the same group selected from the group consisting of hydrogen atoms, hydrocarbon groups, silicon-containing groups and heteroatom-containing groups other than silicon-containing groups.
R ⁶ and R ⁷ may be coupled to each other to form a ring, and R ¹⁰ and R ¹¹ may be coupled to each other to form a ring. However, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.
R ¹³ and R ¹⁴ each independently represent an aryl group.
M represents a titanium atom, a zirconium atom or a hafnium atom.
Y ¹ represents a carbon atom or a silicon atom.
Q indicates a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or unconjugated diene having 4 to 10 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. , J represents an integer of 1 to 4, and when j is an integer of 2 or more, the plurality of Qs may be the same or different. )

(In formula [B], M represents a transition metal atom of Group 4 or 5 of the Periodic Table.
m represents an integer of 1 to 4.
R ¹ represents a _{C n 'H 2n' + 1} (n ' is a is an integer of 1 to 8) hydrocarbon group having 1 to 8 carbon atoms represented by.
R ² to R ⁵ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, silicon-containing group, a germanium-containing group or shows a tin-containing group, may form a ring two groups adjacent to each other are connected to each other among the R ² to R ^5.
R ^{6 to} R ⁸ represent hydrocarbon groups, and ^{at least one of R 6 to} R ⁸ is an aromatic hydrocarbon group.
When m is an integer of 2 or more, two groups of R2 to R8 may be connected to each other between the structural units of the formula [B].
n is a number that satisfies the valence of M.
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, and a silicon-containing group. Indicates a group, a germanium-containing group, or a tin-containing group.
When n is an integer of 2 or more, the plurality of Xs may be the same as or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. ) The method for producing a fiber-reinforced propylene-based resin composition according to claim 6 , wherein the copolymerization step is a step of copolymerizing by a solution polymerization method in a temperature range of 80 to 300 ° C.