JP2014208802A - Fiber-reinforced polypropylene-based flame retardant resin composition, and molding using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant polypropylene-based resin composition that has self-extinguishing properties and drip resistance, and thereby exhibits extremely high flame retardancy and achieves UL94-5VA, and is imparted with mechanical properties (rigidity and shock resistance), weather resistance and moldability, which have been difficult in conventional technologies, and to provide a molding using the same.SOLUTION: A polypropylene-based resin composition contains specific fibers (B), an organic flame retardant (C) and a polytetrafluoroethylene resin (D) in specified quantity ranges, in a polypropylene-based resin (A). A molding is formed by molding the same.

Description

  The present invention relates to a flame-retardant polypropylene resin composition containing fibers, and more specifically, a polypropylene-based resin such as polytetrafluoroethylene resin (hereinafter sometimes abbreviated as PTFE) and an organic material such as a phosphorus-based flame retardant. The present invention relates to a flame retardant polypropylene resin composition comprising a specific amount of a flame retardant and a fiber, and preferably a specific amount of a polypropylene resin having a specific long-chain branched structure.

In order to obtain flame-retardant polypropylene, it is widely practiced to blend a flame retardant composition comprising a halogen-based flame retardant and an antimony compound with various polypropylene resins. This is because these flame retardant compositions have the advantage that they can exhibit flame retardancy in a relatively small amount and do not easily impair the advantageous performance of the polypropylene resin.
However, when these flame retardant compositions are used, there is a problem that halogen gas is generated during combustion. Therefore, the use of a so-called non-halogen flame retardant containing no halogen has been studied.

In addition to the characteristic that the resin itself is difficult to burn (so-called self-extinguishing property), the flame retardancy evaluation standard is that the resin in a burned or molten state does not drip or is difficult to drip and spread to other things (So-called drip resistance or drip resistance) is required, and in recent years, a higher flame retardant level that satisfies both self-extinguishing properties and drip resistance has been required.
In recent years, EVs, HEVs, and home appliances of automobiles have also been advanced to IH, and in automobile parts and home appliance parts, the advanced “V-0” in “UL Standard (US Underwriters Laboratory Standard) -94V” Flame resistance is beginning to be required. In addition, the flame retardant of large-sized members is also progressing, and there is a demand for flame retardancy specialized in self-extinguishing and drip resistance more than conventional. Such flame retardancy satisfies a very high standard of “5VA” in “UL94-5V”.
As described above, flame retardant materials are required as materials for automobiles and home appliances, and these flame retardant materials are required to have mechanical properties equivalent to those of conventional non-flame retardant materials. That is, there is a current demand for materials that impart extremely high flame retardancy and that satisfy mechanical properties (rigidity, impact), weather resistance, and moldability.

  In Patent Document 1, by adding a small amount of tetrafluoroethylene resin (PTFE) to a thermoplastic resin, it is possible to exhibit a dripping prevention effect (drip resistance) during combustion of the thermoplastic resin and to improve flame retardancy. A flammable resin composition is described. However, when trying to maintain the flame retardancy using the technique described in Patent Document 1, there is a concern about the decrease in mechanical properties due to the added PTFE, while when trying to maintain the mechanical properties, the amount of PTFE added is not limited. It needs to be small. For this reason, a decrease in flame retardancy associated with a decrease in the amount of PTFE added is unavoidable, and it is difficult to maintain the flame retardancy without deteriorating mechanical properties.

  Patent Documents 2 and 3 describe techniques in which mechanical properties, flame retardancy, and weather resistance are imparted by adding glass fibers to a flame retardant material using polyolefin and a nitrogen-containing phosphate. However, in the techniques described in Patent Documents 2 and 3, it is possible to relatively increase the concentration of the flame retardant in the resin by adding glass fiber, and to express the self-extinguishing effect. Addition of large glass fibers makes it easy for the resin to drip during combustion, and it is difficult to develop high drip resistance.

JP 2003-026935 A JP 2011-088970 A Japanese Patent Laid-Open No. 10-338774

  An object of the present invention is to achieve extremely high flame retardancy by achieving both self-extinguishing properties and drip resistance, which has been difficult with the prior art, to achieve 5VA at UL94-5V, and to achieve mechanical properties (rigidity). , Impact), weather resistance and molding processability, and to provide a flame retardant polypropylene resin composition and a molded body using the same.

  As a result of intensive research to solve the above problems, the present inventors have made polytetrafluoroethylene resin into polypropylene resin, organic flame retardant, particularly non-halogen flame retardant such as phosphorus flame retardant, and fiber. Is blended with a specific amount, preferably a polypropylene resin having a specific long-chain branched structure, so that both self-extinguishing property and drip resistance at the time of combustion are achieved, and extremely high flame resistance (5VA in UL94-5V) And found that a flame-retardant polypropylene resin composition having mechanical properties (rigidity, impact), weather resistance and molding processability can be obtained, and the present invention has been completed.

That is, according to the first invention of the present invention, the polypropylene resin (A) that satisfies the following conditions (A-1) and (A-2) and the fiber that satisfies the following condition (B-1): Provided is a polypropylene resin composition comprising (B), an organic flame retardant (C), and a polytetrafluoroethylene resin (D) and satisfying the following condition (a): .
Condition (A-1)
The polypropylene resin (A) contains a polypropylene resin (Y) having the following properties (Yi) to (Y-ii).
Characteristic (Yi): at least one polypropylene resin selected from the group consisting of a propylene homopolymer, a propylene-α-olefin block copolymer and a propylene-α-olefin random copolymer, and the following long-chain branch It does not correspond to the polypropylene resin (X) having a structure.
Characteristic (Y-ii): The polypropylene resin (Y) has a melt flow rate (MFR) (230 ° C., 2.16 kg load) of 1.0 to 200 g / 10 min.
Condition (A-2)
The polypropylene resin (A) is at least selected from the group consisting of the polypropylene resin (Y) and a polypropylene resin (X) having a long chain branched structure having the following properties (Xi) to (X-iv): Contains one kind of polypropylene resin.
Characteristic (X-i): Melt flow rate (MFR) (230 ° C., 2.16 kg load) is 0.1 to 30.0 g / 10 min.
Characteristic (X-ii): GPC molecular weight distribution Mw / Mn is 3.0 to 10.0 and Mz / Mw is 2.5 to 10.0.
Characteristic (X-iii): Melt tension (MT) (unit: g) is
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy one of the following.
Characteristic (X-iv): 25 degreeC paraxylene soluble component amount (CXS) is less than 5.0 weight% with respect to polypropylene resin (X) whole quantity.
Condition (B-1)
The fiber (B) is at least one selected from the group consisting of glass fiber and carbon fiber.
Condition (A)
The content of each component is in the range of 20 to 77 parts by weight of polypropylene resin (A), 5 to 40 parts by weight of fiber (B) and 18 to 40 parts by weight of organic flame retardant (C) (provided that polypropylene resin ( A), fiber (B), and organic flame retardant (C) are 100 parts by weight), and polypropylene resin (A), fiber (B), and organic flame retardant (C) The polytetrafluoroethylene resin (D) is in the range of 0.01 to 1.5 parts by weight with respect to 100 parts by weight of the total amount.

Moreover, according to the 2nd invention of this invention, in the 1st invention, the said polypropylene resin (A) provides the polypropylene resin composition which satisfies the following conditions (A-3).
Condition (A-3)
The polypropylene resin (A) contains a polypropylene resin (Y) and a polypropylene resin (X) having a long chain branched structure, and the proportion thereof has a long chain branched structure of 70 to 99% by weight of the polypropylene resin (Y). 1 to 30% by weight of the polypropylene resin (X) (provided that the total of the polypropylene resin (Y) and the polypropylene resin (X) having a long chain branched structure is 100% by weight).

  In addition, according to the third invention of the present invention, there is provided a polypropylene resin composition in which the organic flame retardant (C) is a phosphorus flame retardant in the first or second invention.

  According to a fourth aspect of the present invention, there is provided a polypropylene resin composition according to any one of the first to third aspects, wherein the fiber (B) is a glass fiber.

  Moreover, according to the 5th invention of this invention, the molded object formed by shape | molding the polypropylene resin composition of any one of the 1st thru | or 4th invention is provided.

  The polypropylene resin composition of the present invention preferably comprises a polypropylene resin having a specific long-chain branched structure by blending a specific amount of polytetrafluoroethylene resin, organic flame retardant and fiber with the polypropylene resin. By blending, in addition to excellent mechanical properties (rigidity, impact), weather resistance, and molding processability, it has both self-extinguishing property and drip resistance during combustion, and has extremely high flame retardancy. Further, as the organic flame retardant, a halogen-free flame retardant such as a phosphorus flame retardant is preferably used, and since no chlorine, fluorine and bromine-containing compounds are used, the environmental load is extremely small.

The present invention includes a polypropylene resin (A) (hereinafter also simply referred to as component (Y)) containing polypropylene resin (Y) (hereinafter also simply referred to as component (Y)) 20 satisfying specific conditions. ~ 77 parts by weight, specific fiber (B) (hereinafter also simply referred to as component (B)), 5 to 40 parts by weight, and organic flame retardant (C) (hereinafter also simply referred to as component (C)). 18 to 40 parts by weight (however, the total amount of component (A), component (B) and component (C) is 100 parts by weight), polypropylene resin (A), fiber (B) and organic difficulty 0.01 to 1.5 parts by weight of polytetrafluoroethylene resin (D) (hereinafter also simply referred to as component (D)) with respect to 100 parts by weight of the total amount with the flame retardant (C), Polypropylene having a specific long-chain branched structure as a component that (A) is preferably used Polypropylene resins (X) 1 to 30 containing a len resin (X) (hereinafter, also simply referred to as component (X)), the proportion of which is 70 to 99% by weight of the polypropylene resin (Y) and a long chain branched structure. And a molding formed by molding the polypropylene-based resin composition, wherein the total of the polypropylene resin (Y) and the polypropylene resin (X) having a long-chain branched structure is 100% by weight) About the body.
The polypropylene resin composition of the present invention and a molded product formed from the same eliminate the problems of conventional polypropylene resin compositions and molded products formed from the same, and include various molded products, particularly fibers. In addition to excellent mechanical properties, weather resistance, and moldability, it has extremely high flame retardancy, so that it can be suitably used for automobile parts, electrical parts, container packaging members, building members, large members, and the like.

  Hereinafter, the polypropylene resin composition of the present invention and a molded body formed by molding the same will be described in detail for each item.

I. Component of polypropylene resin composition Polypropylene resin (A) (component (A))
The polypropylene resin (A) used in the present invention contains a specific polypropylene resin (Y) (condition (A-1)), and further in relation to a polypropylene resin (X) having a specific long-chain branched structure. Condition (A-2) is satisfied. Preferably, it contains a polypropylene resin (Y) and a polypropylene resin (X) having a long chain branched structure, and the proportion thereof is 70 to 99% by weight of the polypropylene resin (Y) and a polypropylene resin having a long chain branched structure (X 1-30 wt% (provided that the total of the polypropylene resin (Y) and the polypropylene resin (X) having a long-chain branched structure is 100 wt%) (condition (A-3)).

1). Polypropylene resin (Y)
Below, the detail of the polypropylene resin (Y) used for this invention is demonstrated.
1) -1. Characteristics (Yi): Polypropylene resin (Y) The polypropylene resin (Y) used in the present invention is composed of a propylene homopolymer, a propylene-α-olefin block copolymer, and a propylene-α-olefin random copolymer. It is at least one polypropylene resin selected from the group consisting of, and does not correspond to the polypropylene resin (X) having a long-chain branched structure described later. (Hereinafter, in this specification, the propylene-α-olefin block copolymer and the propylene-α-olefin random random copolymer may be simply referred to as “propylene-α-olefin copolymer”.)
The propylene-α-olefin copolymer preferably used is a copolymer comprising a C 2-8 α-olefin excluding propylene and propylene as a comonomer, and has a propylene content of 70 to 99% by weight (that is, the comonomer content is 0.00%). 01-30 wt%), and more preferably a random copolymer or block copolymer of propylene and an α-olefin having a propylene content of 90 wt% or more. Moreover, the mixture of the random copolymer or block copolymer from which an alpha olefin differs may be sufficient.

Moreover, the comonomer which is a C2-C8 alpha olefin except the propylene copolymerized with a propylene may be used 1 type, and may be used in combination of 2 or more type.
Specific examples of the propylene-α-olefin copolymer include propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-pentene-1 copolymer, propylene-hexene-1 copolymer, propylene. -Binary copolymers such as octene-1 copolymer, terpolymers such as propylene-ethylene-butene-1 copolymer, propylene-ethylene-hexene-1 copolymer, etc. A propylene-ethylene random copolymer, a propylene-ethylene-butene-1 random copolymer, and the like are preferable. The content of the α-olefin monomer in the propylene-α-olefin copolymer is usually about 0.01 to 30% by weight, preferably 1 to 30% by weight, more preferably about 1 to 10% by weight. be able to.

  Examples of the α-olefin having 2 to 8 carbon atoms excluding propylene include ethylene, 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene and 3-methyl-1-butene. 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3 -Dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, 1-octene and the like can be mentioned.

  From the viewpoint of moldability, the polypropylene resin (Y) preferably has a melting point of 100 to 170 ° C, more preferably 160 to 165 ° C. The melting point of the polypropylene resin can be appropriately controlled mainly by the type of propylene used as a raw material and the α-olefin other than propylene, the copolymerization ratio, MFR, and the like. The “melting point” in the present specification is a melting peak temperature measured by a differential scanning calorimeter (DSC).

1) -2. Characteristic (Y-ii): Melt flow rate of polypropylene resin (Y) The polypropylene resin (Y) used in the present invention is a melt flow rate (hereinafter also referred to as MFR) according to JIS K7210 [measurement temperature 230 ° C. , Load 2.16 kg (21.18 N)] is preferably 1.0 to 200 g / 10 minutes. It is still more preferable that it is 5.0-150 g / 10min, and 10-100 g / 10min is more preferable. By setting the MFR within such a range, the polypropylene resin composition of the present invention and a molded product obtained by molding the same can maintain good moldability and exhibit high drip resistance and high flame resistance. Can be achieved. That is, when the MFR is less than 1 g / 10 min, the load when molding the polypropylene resin composition of the present invention increases, the moldability deteriorates, and the molded article may be discolored and the appearance may deteriorate. On the other hand, if it exceeds 200 g / 10 minutes, appropriate drip resistance cannot be exhibited and flame retardancy may be deteriorated.

In addition, the polypropylene resin (Y) preferably has an isotactic pentad fraction (mmmm fraction) showing a crystallinity of 96% or more in the present invention, more preferably isotactic. The tic pentad fraction is 97% or more. It is preferable that the isotactic pentad fraction is 96% or more because rigidity, heat resistance, and the like are increased and the physical properties are further improved. This is because the orientational crystallinity of molecules is increased in the polypropylene resin (Y), and the orientation and uniform dispersion of the fibers (B) described later in the polypropylene resin composition of the present invention and a molded product formed from the same. This is presumed to be easier. Control of the crystallinity of the polypropylene resin (Y) can be adjusted by controlling the molecular weight distribution according to the copolymerization ratio of the raw materials and the catalyst used.
The isotactic pentad fraction (mmmm) is a value measured using ¹³ C-NMR (nuclear magnetic resonance method), and the nuclear magnetic resonance spectrum ( ¹³ C-NMR) of isotope carbon is obtained. It is the isotactic fraction in pentad units in the polypropylene molecular chain measured using. That is, the isotactic pentad fraction is a fraction of propylene units in which five propylene monomer units are continuously isotactically bonded. Specifically, the isotactic pentad unit is measured with the intensity fraction of the mmmm peak in the total absorption peak of the methyl carbon region of the ¹³ C-NMR spectrum. For example, a 270 MHz apparatus of FT-NMR manufactured by JEOL Ltd. Used.

  The catalyst used for obtaining the polypropylene resin (Y) used in the present invention is not particularly limited, and a known catalyst can be used. For example, a so-called Ziegler-Natta catalyst (for example, described in the polypropylene handbook (published on May 15, 1998, first edition)) or a metallocene catalyst (for example, Japanese Patent Laid-Open No. Hei 5-), which is a combination of a titanium compound and organoaluminum. 295022 publication etc.) can be used.

The polymerization process used for obtaining the polypropylene resin (Y) used in the present invention is not particularly limited, and a known polymerization process can be used. For example, a slurry polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used. Further, either batch polymerization method or continuous polymerization method can be used, and if desired, a multi-stage continuous polymerization method such as two-stage or three-stage may be used. It can also be produced by mechanically melting and kneading two or more propylene polymers.
In addition, as the polypropylene resin that can be used as the polypropylene resin (Y), various products are commercially available from many companies, and examples thereof include Novatec series manufactured by Nippon Polypro. It is also possible to purchase and use products having desired physical properties from these commercially available products.

2) Polypropylene resin (X) having a long-chain branched structure (component (X))
The polypropylene resin (X) having a long-chain branched structure used in the present invention is characterized by having the following properties (Xi) to (X-iv).
Characteristic (X-i): Melt flow rate (MFR) (230 ° C., 2.16 kg load) is 0.1 to 30.0 g / 10 min.
Characteristic (X-ii): GPC molecular weight distribution Mw / Mn is 3.0 to 10.0 and Mz / Mw is 2.5 to 10.0.
Characteristic (X-iii): Melt tension (MT) (unit: g) is
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy one of the following.
Characteristic (X-iv): 25 degreeC paraxylene soluble component amount (CXS) is less than 5.0 weight% with respect to polypropylene resin (X) whole quantity.
Hereinafter, the above-mentioned characteristic requirements specified in the present invention, a method for producing a polypropylene resin (X) having a long-chain branched structure, and the like will be specifically described.

2) -1. Characteristic (X-i): Melt flow rate (MFR)
The melt flow rate (MFR) of the polypropylene resin (X) having a long-chain branched structure used in the present invention needs to be in the range of 0.1 to 30.0 g / 10 minutes, preferably 0.3. ˜25.0 g / 10 minutes, more preferably 0.5 to 20.0 g / 10 minutes. By setting the MFR of the component (X) in such a range, the polypropylene resin composition of the present invention exhibits appropriate moldability while maintaining appropriate fluidity, and has an appropriate melt tension. In addition, the effect of having good drip resistance and high flame retardancy can be obtained. That is, when the MFR of the component (X) is below this range, the fluidity is insufficient, and production problems such as an excessively high load on the extruder arise for various types of molding. On the other hand, when the MFR of component (X) exceeds this range, the effect of drip resistance at the time of combustion becomes poor due to insufficient melt tension (viscosity), and the polypropylene resin composition is not suitable as a flame retardant material It becomes.
MFR is JIS K7210: 1999 “Method of plastic-thermoplastic melt mass flow rate (MFR) and melt volume flow rate (MVR) test method”, condition M (230 ° C., 2.16 kg load). Measured according to the standard, the unit is g / 10 minutes.

2) -2. Characteristic (X-ii): Molecular weight distribution by GPC In addition, the polypropylene resin (X) having a long chain branched structure needs to have a relatively wide molecular weight distribution, and the molecular weight obtained by gel permeation chromatography (GPC). The distribution Mw / Mn (where Mw is the weight average molecular weight and Mn is the number average molecular weight) needs to be 3.0 or more and 10.0 or less. The molecular weight distribution Mw / Mn of the polypropylene resin (X) having a long-chain branched structure is preferably in the range of 3.5 to 8.0, more preferably 4.1 to 6.0.
Furthermore, Mz / Mw (where Mz is the Z average molecular weight) needs to be 2.5 or more and 10.0 or less as a parameter that more significantly represents the width of the molecular weight distribution. The preferable range of Mz / Mw is 2.8 to 8.0, more preferably 3.0 to 6.0.
As the molecular weight distribution is wider, the moldability is improved, but those having Mw / Mn and Mz / Mw in this range are particularly excellent in moldability.

The definitions of Mn, Mw, and Mz are described in “Basics of Polymer Chemistry” (edited by Polymer Society, Tokyo Kagaku Dojin, 1978) and can be calculated from molecular weight distribution curves by GPC. The specific measurement method of GPC used in the examples is as follows.
Apparatus: GPC manufactured by Waters (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
-Mobile phase solvent: orthodichlorobenzene (ODCB)
・ Measurement temperature: 140 ℃
・ Flow rate: 1.0 ml / min
・ Injection volume: 0.2ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve it at 140 ° C. for about 1 hour.
Conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve prepared in advance by standard polystyrene (PS). The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method.
In addition, the following numerical value is used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78
Even if an equivalent apparatus, detector, column, or the like is used, the molecular weight distribution can be measured by GPC.

2) -3. Characteristic (X-iii): Melt tension (MT)
Furthermore, the polypropylene resin (X) having a long chain branched structure needs to satisfy the following condition (1).
・ Condition (1)
log (MT) ≧ −0.9 × log (MFR) +0.7
Or MT ≧ 15
Satisfy one of the following.
In the examples of the present specification, MT is a capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd., capillary: diameter 2.0 mm, length 40 mm, cylinder diameter: 9.55 mm, cylinder extrusion speed: 20 mm / min, The melt tension when measured under the conditions of take-off speed: 4.0 m / min and temperature: 230 ° C. is used, and the unit is grams, but it can also be measured using an equivalent apparatus. However, when the MT of the component (X) is extremely high, the resin may break at a take-up speed of 4.0 m / min. In such a case, the take-up speed is lowered and the maximum take-up can be achieved. The tension at the speed of is defined as MT. The measurement conditions and units of MFR are as described above.

This rule is an index for the polypropylene resin (X) having a long-chain branched structure to exhibit sufficient drip resistance at the time of a combustion test. Generally, MT has a correlation with MFR. It is described by the relational expression.
As described above, the method of defining MT by the relational expression with MFR is a normal method for those skilled in the art. For example, JP 2003-25425 discloses the following as the definition of polypropylene having high melt tension: A relational expression is proposed.
log (MS)> − 0.61 × log (MFR) +0.82 (230 ° C.)
(Here, MS is synonymous with MT.)
Japanese Unexamined Patent Application Publication No. 2003-64193 proposes the following relational expression as a definition of polypropylene having a high melt tension.
11.32 × MFR−0.7854 ≦ MT (230 ° C.)
Furthermore, Japanese Patent Laid-Open No. 2003-94504 proposes the following relational expression as a definition of polypropylene having a high melt tension.
MT ≧ 7.52 × MFR−0.576
(MT is a value measured at 190 ° C. and MFR at 230 ° C.)

If the polypropylene resin (X) having a long-chain branched structure satisfies the above condition (1), it can be said that the resin has a sufficiently high melt tension. That is, since the polypropylene resin (X) having a long-chain branched structure that satisfies the above condition (1) is a resin having excellent drip resistance, the fiber (B) and the organic flame retardant (C ) Is particularly useful as a flame retardant material. Further, it is more preferable to satisfy the following condition (1) ′, and it is further preferable to satisfy the condition (1) ″.
..Condition (1) '
log (MT) ≧ −0.9 × log (MFR) +0.9
Or MT ≧ 15
Satisfy one of the following.
..Condition (1)
log (MT) ≧ −0.9 × log (MFR) +1.1
Or MT ≧ 15
Satisfy one of the following.
There is no need to provide the upper limit value of MT. However, when MT exceeds 40 g, the take-up speed is remarkably slowed by the above-described measurement method, making measurement difficult. In such a case, since it is considered that the spreadability of the resin is also deteriorated, it is preferably 40 g or less, more preferably 35 g or less, more preferably 30 g or less.

2) -4. Characteristic (X-iv): 25 ° C. Paraxylene soluble component amount (CXS)
The polypropylene resin (X) having a long-chain branched structure used in the present invention is more sticky when the stereoregularity becomes the polypropylene-based resin composition of the present invention and a molded product formed by molding the same. And low crystalline components that cause bleed-out, and high rigidity can be maintained, which is preferable. This low crystallinity component is evaluated by the amount of xylene soluble component (CXS) at 25 ° C., and it must be less than 5.0% by weight, preferably 3. It is 0 weight% or less, More preferably, it is 1.0 weight% or less, More preferably, it is 0.5 weight% or less. The lower limit is not particularly limited, but is usually 0.01% by weight or more, preferably 0.03% by weight or more. By setting CXS in such a range, as described above, the rigidity of the polypropylene resin composition of the present invention and a molded product formed from the same can be increased, and at the same time, stickiness and bleed-out can be suppressed. Is possible.
The details of the CXS measurement method are as follows.
A 2 g sample is dissolved in 300 ml of p-xylene (containing 0.5 mg / ml BHT) at 130 ° C. to make a solution, and then left at 25 ° C. for 12 hours. Thereafter, the precipitated polymer is separated by filtration, p-xylene is evaporated from the filtrate, and further dried under reduced pressure at 100 ° C. for 12 hours to recover room temperature xylene-soluble components. The ratio [wt%] of the weight of the recovered component to the charged sample weight is defined as CXS.

As an additional characteristic of the polypropylene resin (X) having a long-chain branched structure used in the present invention, it is preferable to have the following characteristics (X-v), and further to have the characteristics (X-vi): Is more preferable.
Note that the characteristic (X-iv) and (X-v) and (X-vi) to be described below are both characteristics related to stereoregularity. In addition to the characteristic (X-iv), the characteristic (X-iv) It is particularly preferable that the requirements of -v) and (X-vi) are simultaneously satisfied.

2) -5. Characteristic (Xv): mm fraction of propylene unit 3 chain by ¹³ C-NMR The polypropylene resin (X) having a long-chain branched structure used in the present invention preferably has high stereoregularity. Stereoregularity of the ^height, can be evaluated by 13 ^C-NMR, mm fraction of the propylene unit triad sequences obtained by 13 C-NMR is preferably has a 95.0% or more stereoregular.
The upper limit of the mm fraction is the ratio of the three propylene units in the polymer chain, and the three propylene units in the same direction of the methyl branch in each propylene unit consisting of head-to-tail bonds is 100%. is there. This mm fraction is a value indicating that the steric structure of the methyl group in the polypropylene molecular chain is controlled isotactically, and the higher the value, the higher the degree of control. By setting the mm fraction within the range shown below, the flexural modulus, which is an index of rigidity of the polypropylene resin composition of the present invention and a molded product formed by molding the resin composition, can be increased. That is, if the mm fraction is smaller than the value shown below, the mechanical properties deteriorate, such as the bending elastic modulus, which is an index of rigidity of the polypropylene resin composition of the present invention and a molded product formed by molding the resin composition. Tend to.
Accordingly, the mm fraction is preferably 95.0% or more, more preferably 96.0% or more, still more preferably 97.0% or more, and the upper limit is 100% as described above.

In addition, the detail of the measuring method of mm fraction of the propylene unit 3 chain | strand by ¹³ C-NMR is as follows.
A sample of 375 mg is completely dissolved in 2.5 ml of deuterated 1,1,2,2, -tetrachloroethane in an NMR sample tube (10φ), and then measured at 125 ° C. by a proton complete decoupling method. The chemical shift sets the central peak of the three peaks of deuterated 1,1,2,2-tetrachloroethane to 74.2 ppm. The chemical shift of other carbon peaks is based on this.
Flip angle: 90 degrees Pulse interval: 10 seconds Resonance frequency: 100 MHz or more Integration frequency: 10,000 times or more Observation range: -20 ppm to 179 ppm
Number of data points: 32768
The analysis of the mm fraction is performed using a ¹³ C-NMR spectrum measured under the above conditions.
The spectrum is assigned with reference to Macromolecules, 8 pp. 687 (1975) and Polymer, 30 pages, 1350 (1989).
Note that a more specific method for determining the mm fraction is described in detail in paragraphs [0053] to [0065] of Japanese Patent Laid-Open No. 2009-275207, and the present invention is performed according to this method. .

2) -6. Characteristic (X-vi): branching index g ′
As a direct indicator that the polypropylene resin (X) having a long-chain branch structure has a branch, a branch index g ′ can be mentioned. g ′ is given by the ratio of the intrinsic viscosity [η] lin of the linear polymer having the same molecular weight as the intrinsic viscosity [η] br of the polymer having a long chain branched structure, that is, [η] br / [η] lin. When a long chain branched structure is present, the value is smaller than 1.
The definition is described in, for example, “Developments in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publishers, 1983), and is an index known to those skilled in the art.

g ′ can be obtained as a function of the absolute molecular weight Mabs, for example, by using a GPC equipped with a light scatterometer and viscometer as described below in the detector.
The polypropylene resin (X) having a long-chain branched structure used in the present invention preferably has a g ′ of 0.30 or more and less than 1.00 when the absolute molecular weight Mabs determined by light scattering is 1,000,000. Preferably they are 0.55 or more and 0.98 or less, More preferably, they are 0.75 or more and 0.96 or less, Most preferably, they are 0.78 or more and 0.95 or less.
As described in detail below, the polypropylene resin (X) having a long-chain branched structure used in the present invention is considered to generate a comb chain as a molecular structure from its polymerization mechanism. By making the range, it becomes possible to make the melt tension in an appropriate range, so that the drip resistance, which is one of the evaluation indexes of flame retardancy, can be increased, and good moldability can be expressed. It becomes possible. That is, when g ′ is less than 0.30, the main chain is few and the ratio of the side chain is extremely large. In such a case, the melt tension may not be improved or a gel may be formed. In addition, the drip resistance may be lowered and various mechanical strengths may be affected, which is not preferable in the flame retardant material having high flame retardancy that is the object of the present invention. On the other hand, in the case of 1.00, this means that there is no branching, the melt tension may be insufficient, and the drip resistance may be lowered. Not suitable for flame retardant flame retardant materials.

The lower limit of g ′ is preferably the above value for the following reason.
According to “Encyclopedia of Polymer Science and Engineering vol. 2” (John Wiley & Sons 1985 p.485), the g ′ value of the comb polymer is represented by the following formula.

  Here, g is a branching index defined by the rotation radius ratio of the polymer, and ε is a constant determined by the shape of the branched chain and the solvent. According to Table 3 of 487, a value of about 0.7 to 1.0 is reported for the comb chain in a good solvent. λ is the ratio of the main chain in the comb chain, and p is the average number of branches. According to this formula, the number of branches is extremely large for a comb chain, that is, p is infinite, and g ′ = gε = λε, which is not less than the value of λε. There will be a value.

On the other hand, the conventionally known random branched chain formula, which is considered to occur in the case of electron beam irradiation or peroxide modification, is given by the 485 page formula (19) in the same document. In the chain, as the number of branch points increases, the g ′ and g values monotonously decrease, especially without the lower limit. That is, in the present invention, the fact that the g ′ value has a lower limit means that the polypropylene resin (X) having a long chain branched structure used in the present invention has a structure close to a comb chain. Thus, the distinction from random branched chains generated by electron beam irradiation or peroxide modification becomes clearer.
Further, in a branched polymer having a structure close to a comb chain in which g ′ is in the above range, the degree of decrease in melt tension is small when kneading is repeated, and this occurs in the process of industrially producing a molded product. For example, when a sheet or film is formed by cutting an edge during film molding, or when a member such as an injection molding runner is subjected to molding again as a recycled material, a decrease in physical properties and moldability is reduced. It is preferable.

A specific method for calculating g ′ in the examples of the present specification is as follows.
Waters Alliance GPCV2000 is used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). Also, as the light scattering detector, a multi-angle laser light scattering detector (MALLS) DAWN-E manufactured by Wyatt Technology is used. The detectors are connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (added with an antioxidant Irganox 1076 manufactured by BASF Japan Ltd. at a concentration of 0.5 mg / mL).
The flow rate is 1 mL / min, and two columns of Tosoh Corporation GMHHR-H (S) HT are connected and used. The temperature of the column, sample injection section, and each detector is 140 ° C. The sample concentration is 1 mg / mL and the injection volume (sample loop volume) is 0.2175 mL.
In order to obtain the absolute molecular weight (Mabs) obtained from MALLS, the mean square inertia radius (Rg), and the intrinsic viscosity ([η]) obtained from Viscometer, the data processing software ASTRA (version 4.73.04) attached to MALLS is used. The calculation is performed with reference to the following documents.

References:
1. “Developments in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publishers, 1983. Chapter 1.)
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000)
4). Macromolecules, 33, 6945-6952 (2000)
Various other devices, columns, and the like can be used.

[Calculation of branching index (g ′)]
The branching index (g ′) is a ratio between the intrinsic viscosity ([η] br) obtained by measuring the sample with the above Viscometer and the intrinsic viscosity ([η] lin) obtained separately by measuring the linear polymer. Calculated as ([η] br / [η] lin).
When a long-chain branched structure is introduced into a polymer molecule, the radius of inertia becomes smaller than that of a linear polymer molecule having the same molecular weight. Since the intrinsic viscosity becomes smaller as the inertia radius becomes smaller, the intrinsic viscosity ([η] br) of the branched polymer with respect to the intrinsic viscosity ([η] lin) of the linear polymer having the same molecular weight as the long chain branched structure is introduced. The ratio ([η] br / [η] lin) becomes smaller.
Therefore, when the branch index (g ′ = [η] br / [η] lin) is a value smaller than 1, it means that a branch is introduced. Here, as a linear polymer for obtaining [η] lin, a commercially available homopolypropylene (Novatec PP (registered trademark) grade name: FY6 manufactured by Nippon Polypro Co., Ltd.) is used. The fact that the logarithm of [η] lin of a linear polymer has a linear relationship with the logarithm of molecular weight is known as the Mark-Houwink-Sakurada equation, so [η] lin is appropriately set on the low molecular weight side or the high molecular weight side. Extrapolation can be used to obtain numerical values.
In the present invention, the polypropylene resin satisfying g ′ <1 when the characteristic (X-iii) satisfies log (MT) ≧ −0.9 × log (MFR) +0.7 and the Mabs is 1,000,000 is a long chain It can be said that it has a branched structure.

2) -7. Method for Producing Polypropylene Resin (X) Having Long-Chain Branched Structure Polypropylene resin (X) having a long-chain branched structure is not particularly limited as long as it satisfies the characteristics (Xi) to (X-iv) described above. Although not limited, as described above, it satisfies all the conditions of high stereoregularity, low low crystalline component amount, and relatively wide molecular weight distribution range, preferably branching index g ′ range, high melting A preferable production method for satisfying conditions such as tension is a method using a macromer copolymerization method using a combination of metallocene catalysts. As an example of such a method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 2009-57542 can be given.
This method produces a polypropylene having a long-chain branched structure using a catalyst in which a catalyst component having a specific structure having macromer-producing ability and a catalyst component having a specific structure having high molecular weight and macromer copolymerization ability are combined. According to this, industrially effective methods such as bulk polymerization and gas phase polymerization, particularly single-stage polymerization under practical pressure-temperature conditions, and using hydrogen as a molecular weight regulator. It is possible to produce a polypropylene resin (X) having a long-chain branched structure having the desired physical properties.

In the past, it was necessary to increase the branching efficiency by lowering the crystallinity by using a polypropylene component having a low stereoregularity. However, in the above method, a polypropylene component having a sufficiently high stereoregularity is required. It can be introduced into the side chain by a simple method. Adopting such a production method is preferable for the polypropylene resin (X) having a long-chain branched structure used in the present invention, and (X-iv) and (X It is suitable for satisfying the characteristic of -v).
Moreover, if the said method is used, molecular weight distribution can be widened by using two types of catalysts from which polymerization characteristics differ greatly, and it is necessary for the polypropylene resin (X) having a long chain branched structure used in the present invention (X- The characteristics of i) to (X-iii) can be satisfied at the same time, which is preferable.

Therefore, a preferable method for producing a polypropylene resin (X) having a long chain branched structure used in the present invention will be described in detail below.
As a preferred method for producing the polypropylene resin (X) having a long-chain branched structure, a method for producing a propylene polymer using the following catalyst components (A), (B) and (C) as a propylene polymerization catalyst can be mentioned.
(A): at least one from component [A-1] which is a compound represented by the following general formula (a1) and at least from component [A-2] which is a compound represented by the following general formula (a2) Two or more Group 4 transition metal compounds selected from one type.
Component [A-1]: Compound represented by general formula (a1) Component [A-2]: Compound represented by general formula (a2) (B): Ion exchange layered silicate (C): Organoaluminum Compound

Hereinafter, the catalyst components (A), (B), and (C) will be described in detail.
(1) Catalyst component (A)
(I) Component [A-1]: Compound represented by general formula (a1)

(In the general formula (a1), each of R ¹¹ and R ¹² independently represents a heterocyclic group containing nitrogen, oxygen, or sulfur having 4 to 16 carbon atoms, and each of R ¹³ and R ¹⁴ represents Independently, halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a C6-C16 aryl group that may contain a plurality of heteroelements selected from these, C6-C16 nitrogen or Represents a heterocyclic group containing oxygen and sulfur, and each of X ¹¹ and Y ¹¹ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a silicon group having 1 to 20 carbon atoms. Represents a hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, and Q ¹¹ represents carbon Divalent hydrocarbons of 1 to 20 Group, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms.)

The heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms of R ¹¹ and R ¹² is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, It is a substituted 2-furfuryl group, and more preferably a substituted 2-furyl group.
Moreover, as a substituted 2-furyl group, a substituted 2-thienyl group, and a substituted 2-furfuryl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group, Examples thereof include halogen atoms such as fluorine atom and chlorine atom, alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group, and trialkylsilyl groups. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
Further, R ¹¹ and R ¹² are particularly preferably a 2- (5-methyl) -furyl group. R ¹¹ and R ¹² are preferably the same as each other.
Carbon atoms 6 to 16 of the R ¹³ and R ^14, halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or, as the aryl group which may contain a plurality of hetero elements selected from these, In the range of 6 to 16 carbon atoms, on the aryl cyclic skeleton, one or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, halogens having 1 to 6 carbon atoms You may have a containing hydrocarbon group as a substituent.

At least one of R ¹³ and R ¹⁴ is preferably a phenyl group, a 4-methylphenyl group, a 4-ipropylphenyl group, a 4-tbutylphenyl group, a 4-trimethylsilylphenyl group, or a 2,3-dimethylphenyl group. 3,5-di-t-butylphenyl group, 4-phenyl-phenyl group, chlorophenyl group, naphthyl group, or phenanthryl group, more preferably phenyl group, 4-ipropylphenyl group, 4-tbutylphenyl group, 4-trimethylsilylphenyl group and 4-chlorophenyl group. Further, it is preferable that R ¹³ and R ¹⁴ are the same.

In the general formula (a1), X ¹¹ and Y ¹¹ are auxiliary ligands, and react with the co-catalyst of the catalyst component (B) to generate an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ¹¹ and Y ¹¹ are not limited in the type of ligand, and are independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. A C1-C20 silicon-containing hydrocarbon group, a C1-C20 halogenated hydrocarbon group, a C1-C20 oxygen-containing hydrocarbon group, an amino group, or a C1-C20 nitrogen-containing hydrocarbon Group, an alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, and a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms.

In the general formula (a1), Q ¹¹ is a silylene that may have a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms that connects two five-membered rings. Represents either a group or a germylene group. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermylene Examples include groups. In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.

Of the compounds represented by the general formula (a1), preferred compounds are specifically exemplified below.
Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-thienyl) -4-phenyl -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2 -(5-Methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ] Hafnium, dichloro [1,1'-dimethylgermylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dic B [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5- Trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium dichloride, dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) ) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- ( -Methylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2 -Furfuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -indenyl}] Hough , Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene Bis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4 -(1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1 ′ -Dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- ( 5-methyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (9- Phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] ha Nitrogen, dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2- Furyl) -4- (9-phenanthryl) -indenyl}] hafnium, and the like.

Of these, more preferred are dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene. Bis {2- (5-methyl-2-furyl) -4- (4-methylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl} ] Hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, Chloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- ( 5-methyl-2-furyl) -4- (4-tert-butylphenyl) -indenyl}] hafnium.
Particularly preferred is dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2- (5-Methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl)- 4- (4-Trimethylsilylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} ] Hafnium.

(Ii) Component [A-2]: Compound represented by general formula (a2)

(In the general formula (a2), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R ²³ and R ²⁴ are each independently halogen, silicon, oxygen, S ²¹ is an aryl group having 6 to 16 carbon atoms which may contain sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements selected from these, X ²¹ and Y ²¹ each independently represent a hydrogen atom, halogen, Atom, hydrocarbon group having 1 to 20 carbon atoms, silicon-containing hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, amino group Or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, or a silylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms. or ^{.M 21} representing a germylene group, It is a Rukoniumu or hafnium.)

R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.
In addition, R ²³ and R ²⁴ each independently contain a halogen having 6 to 16 carbon atoms, preferably 6 to 12 carbon atoms, silicon, or a plurality of hetero elements selected from these. It is a good aryl group. Preferred examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4- (2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3,5 -Dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl and the like.

Further, the X ²¹ and Y ²¹ are auxiliary ligands, it reacts with the cocatalyst of the catalyst component (B) to form an active metallocene having olefin polymerizability. Therefore, as long as this object is achieved, X ²¹ and Y ²¹ are not limited to the type of ligand, and are independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. A C1-C20 silicon-containing hydrocarbon group, a C1-C20 halogenated hydrocarbon group, a C1-C20 oxygen-containing hydrocarbon group, an amino group, or a C1-C20 nitrogen-containing hydrocarbon Group, an alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, and a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms.

Q ²¹ is a binding group that bridges two conjugated five-membered ring ligands, and has a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms. A silylene group or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted silylene group or a substituted germylene group.

  The substituent bonded to silicon and germanium is preferably a hydrocarbon group having 1 to 12 carbon atoms, and two substituents may be linked. Specific examples include methylene, dimethylmethylene, ethylene-1,2-diyl, dimethylsilylene, diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylsilylene, diethylsilylene, Examples thereof include diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylgermylene, diethylgermylene, diphenylgermylene, methylphenylgermylene and the like.

Further, M ²¹ is zirconium or hafnium, preferably hafnium.
Non-limiting examples of the metallocene compound represented by the general formula (a2) include the following.
However, the following describes only typical exemplary compounds while avoiding many complicated examples, and the present invention is not construed as being limited to these compounds, and various ligands, cross-linking groups or It is self-evident that auxiliary ligands can optionally be used. Moreover, although the compound whose center metal is hafnium was described, the compound replaced with zirconium is also treated as disclosed in this specification.

  Dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazurenyl)} hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4 -Hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-t-butylphenyl)- 4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- ( -Methyl-4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl} ] Hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -Methyl-4- (1-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl)- -Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-Methyl-4- (2-chloro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (9-phenanthryl) -4-hydroazurenyl] }] Hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-n-propyl -4- (3-Chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] huff Nitrogen, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) ) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′- (9-silafluorene-9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] Funium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl -4- (2-fluoro-4-biphenylyl) -4-hydroazulenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3 5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, and the like.

  Of these, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- Methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4 -Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-Ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] ha Dichloro, [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, is there.

  Particularly preferably, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl -4- (2-Fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4- Hydroazurenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] Hafnium.

(2) Catalyst component (B)
The catalyst component (B) preferably used for producing the polypropylene resin (X) is an ion-exchange layered silicate.
(I) Types of ion-exchanged layered silicates Ion-exchanged layered silicates (hereinafter sometimes simply referred to as silicates) are surfaces in which ionic bonds and the like are stacked in parallel with each other with a binding force. This refers to a silicate compound having a crystal structure and containing exchangeable ions. Most silicates are naturally produced mainly as the main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. But you can. Depending on the type, amount, particle size, crystallinity, and dispersion state of these impurities, it may be preferable to pure silicate, and such a complex is also included in the catalyst component (B).
The silicate used in the present invention is not limited to a natural product, and may be an artificial synthetic product or may contain them.

Specific examples of the silicate include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
That is, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stemite and other smectites, vermiculite and other vermiculites, mica, illite, sericite and sea chlorite and other mica, attapulgite, sepiolite and palygorskite , Bentonite, pyrophyllite, talc, chlorite group, etc.
The silicate is preferably a silicate in which the main component silicate has a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. The type of interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easy and inexpensive to obtain as an industrial raw material.

(Ii) Chemical treatment of ion-exchange layered silicate The ion-exchange layered silicate of the catalyst component (B) according to the present invention can be used as it is without any particular treatment, but it is preferable to perform a chemical treatment. . Here, the chemical treatment of the ion-exchange layered silicate may be any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the structure of the clay. Treatment, alkali treatment, salt treatment, organic matter treatment and the like.

<Acid treatment>:
In addition to removing impurities on the surface, the acid treatment can elute part or all of cations such as Al, Fe, Mg, etc. having a crystal structure.
The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and oxalic acid.
Two or more salts (described in the next section) and acid may be used for the treatment. The treatment conditions with salts and acids are not particularly limited. Usually, the salt and acid concentrations are 0.1 to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the process under the condition of selecting and eluting at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchangeable layered silicates. In addition, salts and acids are generally used in an aqueous solution.
In addition, you may use what combined the following acids and salts as a processing agent. Moreover, the combination of these acids and salts may be sufficient.

<Salt treatment>:
40% or more, preferably 60% or more of the exchangeable Group 1 metal cation contained in the ion-exchange layered silicate before being treated with salts, cations dissociated from the following salts and ions It is preferable to exchange.
Salts used in such salt treatment for ion exchange are composed of a cation containing at least one atom selected from the group consisting of Group 1 to 14 atoms, a halogen atom, an inorganic acid, and an organic acid. A compound comprising at least one anion selected from the group, and more preferably a cation containing at least one atom selected from the group consisting of Group 2-14 atoms and Cl, Br, I, F , PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₅ H ₅ O ₇ Is a compound consisting of

Specific examples of such _{salts, LiF, LiCl, LiBr, LiI} , Li 2 SO 4, Li (CH 3 COO), LiCO 3, Li (C 6 H 5 O 7), LiCHO 2, LiC 2 O 4 , LiClO ₄ , Li ₃ PO ₄ , CaCl ₂ , CaSO ₄ , CaC ₂ O ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , MgCl ₂ , MgBr ₂ , MgSO ₄ , Mg ( PO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , MgC ₂ O ₄ , Mg (NO ₃ ) ₂ , Mg (OOCCH ₃ ) ₂ , MgC ₄ H ₄ O _{4 and the} like.

Also, Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , ZrF ₄ , ZrCl ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (ClO ₄ ) ₂ , ZrO (SO ₄ ), HF (OOCCH ₃ ) ₄ , HF (CO ₃ ) ₂ , HF (NO ₃ ) ₄ , HF (SO ₄ ) ₂ , HFOCl ₂ , HFF ₄ , HFCl ₄ , V (CH ₃ COCHCOCH ₃ ) ₃ , VOSO ₄ , VOCl ₃ , VCl ₃ , VCl ₄ , VBr _{3 and the} like.

Also, Cr (CH ₃ COCHCOCH ₃ ) ₃ , Cr (OOCCH ₃ ) ₂ OH, Cr (NO ₃ ) ₃ , Cr (ClO ₄ ) ₃ , CrPO ₄ , Cr ₂ (SO ₄ ) ₃ , CrO ₂ Cl ₂ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI ₃ , Mn (OOCCH ₃ ) ₂ , Mn (CH ₃ COCHCOCH ₃ ) ₂ , MnCO ₃ , Mn (NO ₃ ) ₂ , MnO, Mn (ClO ₄ ) ₂ , MnF ₂ , MnCl ₂ , Fe (OOCCH ₃ ) ₂ , Fe (CH ₃ COCHCOCH ₃ ) ₃ , FeCO ₃ , Fe (NO ₃ ) ₃ , Fe (ClO ₄ ) ₃ , FePO ₄ , FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , FeF ₃ FeCl ₃ , FeC ₆ H ₅ O _{7 and the} like.

In addition, Co (OOCCH ₃ ) ₂ , Co (CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co (NO ₃ ) ₂ , CoC ₂ O ₄ , Co (ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr _{2 and the} like.
Furthermore, Zn (OOCCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , GeBr ₄ , GeI _{4 and the} like.

<Alkali treatment>:
In addition to acid and salt treatment, the following alkali treatment or organic matter treatment may be performed as necessary. Examples of the treating agent used in the alkali treatment include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , Ba (OH) _{2 and the} like.

<Organic treatment>:
Examples of the organic treatment agent used for organic treatment include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium, and the like.
Examples of the anion constituting the organic treatment agent include hexafluorophosphate, tetrafluoroborate, and tetraphenylborate other than the anion exemplified as the anion constituting the salt treatment agent. It is not limited to these.

Moreover, these processing agents may be used independently and may be used in combination of 2 or more types. These combinations may be used in combination for the treatment agent added at the start of the treatment, or may be used in combination for the treatment agent added during the treatment. The chemical treatment can be performed a plurality of times using the same or different treatment agents.
These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water and use them as the catalyst component (B).

  The heat treatment method of the ion-exchange layered silicate adsorbed water and interlayer water is not particularly limited, but it is necessary to select conditions so that interlayer water does not remain and structural destruction does not occur. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, the water content of the catalyst component (B) after the removal is 3% by weight or less when the water content when dehydrating for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg is 0% by weight, It is preferably 1% by weight or less.

  As described above, in the present invention, the catalyst component (B) is particularly preferably an ion-exchange layered silicic acid having a water content of 3% by weight or less obtained by performing a salt treatment and / or an acid treatment. Salt.

  The ion-exchange layered silicate can be treated with a catalyst component (C) of an organoaluminum compound, which will be described later, before formation of a catalyst or use as a catalyst, which is preferable. Although there is no restriction | limiting in the usage-amount of the catalyst component (C) with respect to 1g of ion-exchange layered silicate, Usually, 20 mmol or less, Preferably it is 0.5 mmol or more and 10 mmol or less. There is no limitation on the treatment temperature and time, the treatment temperature is usually 0 ° C. or more and 70 ° C. or less, and the treatment time is 10 minutes or more and 3 hours or less. It is also possible and preferable to wash after the treatment. As the solvent, the same hydrocarbon solvent as that used in the preliminary polymerization and slurry polymerization described later is used.

The catalyst component (B) is preferably spherical particles having an average particle size of 5 μm or more. If the particle shape is spherical, a natural product or a commercially available product may be used as it is, or a particle whose particle shape and particle size are controlled by granulation, sizing, fractionation, or the like may be used.
Examples of the granulation method used here include agitation granulation method and spray granulation method, but commercially available products can also be used.
Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation.
The spherical particles obtained as described above desirably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and generation of fine powder in the polymerization process. In the case of such particle strength, the effect of improving the particle properties is effectively exhibited especially when prepolymerization is performed.

(3) Catalyst component (C)
The catalyst component (C) is an organoaluminum compound. Organic aluminum compounds used as the catalyst component (C) has the general ^{_{formula: (AlR 31 q Z 3-}} q) a compound represented by _p is suitable.
In the present invention, it goes without saying that the compounds represented by this formula can be used singly, mixed in plural or in combination. In this formula, R ³¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a halogen, hydrogen, an alkoxy group or an amino group. q represents an integer of 1 to 3, and p represents an integer of 1 to 2, respectively. R ³¹ is preferably an alkyl group, and Z is a chlorine atom when it is a halogen atom, a C 1-8 alkoxy group when it is an alkoxy group, and a C 1 atom when it is an amino group. Eight amino groups are preferred.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride.
Of these, trialkylaluminum and alkylaluminum hydride having p = 1 and q = 3 are preferable. More preferably, R ³¹ is trialkylaluminum having 1 to 8 carbon atoms.

(4) Catalyst formation / preliminary polymerization In the catalyst, the catalyst components (A) to (C) are brought into contact with each other in the (preliminary) polymerization tank simultaneously or continuously, or once or multiple times. Can be formed.
The contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. Although a contact temperature is not specifically limited, It is preferable to carry out between -20 degreeC and 150 degreeC. As the contact order, any desired combination can be used, but particularly preferable ones for each component are as follows.
When the catalyst component (C) is used, before the catalyst component (A) and the catalyst component (B) are contacted, the catalyst component (A), or the catalyst component (B), or the catalyst component (A) and the catalyst are used. Contacting catalyst component (C) with both components (B), or contacting catalyst component (C) with catalyst component (A) and catalyst component (B), or catalyst component Although it is possible to contact the catalyst component (C) after bringing the catalyst component (B) into contact with (A), it is preferable that the catalyst component be brought into contact with the catalyst component (A) before contacting the catalyst component (B). It is a method of contacting any of the component (C).
Moreover, after contacting each component, it is possible to wash with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of catalyst components (A), (B) and (C) used is arbitrary. For example, the amount of the catalyst component (A) used relative to the catalyst component (B) is preferably in the range of 0.1 μmol to 1,000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of the catalyst component (B). The amount of the catalyst component (C) with respect to the catalyst component (A) is preferably in the range of 0.01 to 5 × 10 ⁶ , particularly preferably 0.1 to 1 × 10 ⁴ in terms of the molar ratio of the transition metal. preferable.

The ratio of said component [A-1] (compound represented by general formula (a1)) and said component [A-2] (compound represented by general formula (a1)) used by this invention is a propylene type | system | group. Although it is arbitrary as long as the above properties of the polymer are satisfied, the molar ratio of the transition metal of [A-1] to the total amount of each component [A-1] and [A-2], preferably 0.30 or more 0.99 or less.
By changing this ratio, it is possible to adjust the balance between melt physical properties and catalyst activity. That is, from the component [A-1], a low molecular weight terminal vinyl macromer is produced, and from the component [A-2], a high molecular weight body obtained by copolymerizing a part of the macromer is produced. Therefore, by changing the ratio of the component [A-1], the average molecular weight, molecular weight distribution, bias of the molecular weight distribution toward the high molecular weight side, very high molecular weight component, branch (amount, length, Distribution) can be controlled, whereby the melt physical properties such as strain hardening degree, melt tension, and melt spreadability can be controlled.
In order to produce a higher strain hardening propylene polymer, 0.30 or more is required, preferably 0.40 or more, and more preferably 0.5 or more. Further, the upper limit is 0.99 or less, and in order to efficiently obtain polypropylene resin (X) with high catalytic activity, it is preferably 0.95 or less, and more preferably 0.90 or less. .
In addition, by using component [A-1] within the above range, it is possible to adjust the balance between the average molecular weight and the catalytic activity with respect to the amount of hydrogen.

  The catalyst according to the present invention is subjected to a prepolymerization treatment consisting of a small amount of polymerization by bringing an olefin into contact therewith. By performing the prepolymerization treatment, gel formation can be prevented when the main polymerization is performed. The reason is considered to be that long-chain branches can be uniformly distributed among the polymer particles when the main polymerization is performed, and the melt properties can be improved thereby.

The olefin used in the prepolymerization is not particularly limited, but propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, Styrene and the like can be exemplified. The olefin feed method may be any method such as a feed method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.
The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. The amount of prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 50 with respect to the catalyst component (B). Moreover, a catalyst component (C) can also be added or added at the time of prepolymerization. It is also possible to wash after the prepolymerization.

  In addition, a method of coexisting a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or titania, at the time of contacting or after contacting each of the above components is also possible.

(5) Use of Catalyst / Propylene Polymerization Any polymerization mode can be used as long as the olefin polymerization catalyst including the catalyst component (A), the catalyst component (B), and the catalyst component (C) is in efficient contact with the monomer. Can be adopted.
Specifically, a slurry method using an inert solvent, a so-called bulk method using a propylene as a solvent without using an inert solvent as a solvent, a solution polymerization method, or a monomer without using a liquid solvent substantially. A gas phase method can be used. Moreover, the method of performing continuous polymerization and batch type polymerization is also applied. In addition to single-stage polymerization, it is possible to carry out multistage polymerization of two or more stages.
In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent.

The polymerization temperature is 0 ° C. or higher and 150 ° C. or lower. In particular, when bulk polymerization is used, the temperature is preferably 40 ° C or higher, more preferably 50 ° C or higher. The upper limit is preferably 80 ° C. or lower, and more preferably 75 ° C. or lower.
Furthermore, when using vapor phase polymerization, 40 degreeC or more is preferable, More preferably, it is 50 degreeC or more. The upper limit is preferably 100 ° C. or lower, more preferably 90 ° C. or lower.
The polymerization pressure is preferably 1.0 MPa or more and 5.0 MPa or less. In particular, when bulk polymerization is used, the pressure is preferably 1.5 MPa or more, more preferably 2.0 MPa or more. The upper limit is preferably 4.0 MPa or less, more preferably 3.5 MPa or less.

Furthermore, when using vapor phase polymerization, 1.5 MPa or more is preferable, and 1.7 MPa or more is more preferable. Further, the upper limit is preferably 2.5 MPa or less, and more preferably 2.3 MPa or less.
Further, as a molecular weight regulator and for an activity improving effect, hydrogen is supplementarily used in a molar ratio of 1.0 × 10 ⁻⁶ or more and 1.0 × 10 ⁻² or less with respect to propylene. it can.

Also, by changing the amount of hydrogen used, in addition to the average molecular weight of the polymer to be produced, the molecular weight distribution, the deviation of the molecular weight distribution toward the high molecular weight side, very high molecular weight components, branching (amount, length, Distribution) can be controlled, whereby the melt properties characterizing polypropylene having a long chain branching structure such as MFR, strain hardening degree, melt tension MT, and melt spreadability can be controlled.
Therefore, hydrogen should be used at a molar ratio to propylene of 1.0 × 10 ⁻⁶ or more, preferably 1.0 × 10 ⁻⁵ or more, more preferably 1.0 × 10 ⁻⁴ or more. Is good. Moreover, regarding an upper limit, it is good to use at 1.0 * 10 ^<-2> or less, Preferably it is 0.9 * 10 ^<-2> or less, More preferably, it is 0.8 * 10 ^<-2> or less.

In addition to the propylene monomer, copolymerization using an α-olefin comonomer having 2 to 20 carbon atoms excluding propylene such as ethylene and / or 1-butene as a comonomer may be performed depending on the use.
Therefore, in order to obtain a polypropylene resin (X) used in the present invention having a good balance between catalytic activity and melt properties, ethylene and / or 1-butene should be used at 15 mol% or less with respect to propylene. Is more preferable, and it is 10.0 mol% or less, More preferably, it is 7.0 mol% or less.

  When propylene is polymerized using the catalyst and polymerization method exemplified here, one end of the polymer is mainly propenyl from the active species derived from the catalyst component [A-1] by a special chain transfer reaction generally called β-methyl elimination. The structure is shown and so-called macromers are produced. This macromer can generate a higher molecular weight and is taken into the active species derived from the catalyst component [A-2] having a better copolymerization property, and it is considered that the macromer copolymerization proceeds. Therefore, it can be considered that a comb-shaped chain is mainly used as a branched structure of a polypropylene resin having a long-chain branched structure.

2) -8. Other characteristics of the polypropylene resin (X) having a long-chain branch structure As an additional feature of the polypropylene resin (X) having a long-chain branch structure used in the present invention, which is produced by the above-described method, strain rate The strain hardening degree (λmax (0.1)) in the measurement of the extensional viscosity at 0.1 s ⁻¹ is 6.0 or more.
The strain hardening degree (λmax (0.1)) is an index indicating the viscosity at the time of melting. As a result, when a combustion test is performed, high drip resistance can be expressed. The strain hardening degree is preferably 6.0 or more because drip resistance can be expressed, and more preferably 8.0 or more. On the other hand, if this strain hardening degree is too high, the moldability may be adversely affected, so 30 or less is preferable and 20 or less is more preferable. When the strain hardening degree is in such a range, it is preferable because high drip resistance can be maintained, high flame retardancy can be achieved, and good moldability can be maintained.

Details of the method of calculating λmax (0.1) will be described below.
Λmax (0.1) calculation method Elongation viscosity at a temperature of 180 ° C. and strain rate = 0.1 s ⁻¹ , time t (second) on the horizontal axis and elongation viscosity η _E (Pa · second) on the vertical axis. Plot with a log-log graph. On the log-log graph, the viscosity immediately before strain hardening is approximated by a straight line.
Specifically, first, the slope at each time when the extensional viscosity is plotted against time is obtained. In this case, considering that the measurement data of the extensional viscosity is discrete, various averaging methods are used. Is used. For example, there is a method of obtaining the slope of adjacent data and taking a moving average of several surrounding points.
The extensional viscosity is a simple increasing function in the low strain region and gradually approaches a constant value, and if there is no strain hardening, it matches the Truton viscosity after a sufficient amount of time. In particular, the extensional viscosity starts to increase with time from a strain amount (= strain rate × time) of about 1. That is, the slope tends to decrease with time in the low strain region, but tends to increase from about 1 strain, and there is an inflection point on the curve when the extensional viscosity is plotted against time. . Therefore, a point where the slope of each time obtained above takes the minimum value in the range of the distortion amount of about 0.1 to 2.5 is obtained, and a tangent line is drawn at the point, and the straight line has a distortion amount of 4.0. Extrapolate until The maximum value (ηmax) of the extensional viscosity η _E until the strain amount becomes 4.0 is obtained, and the viscosity on the approximate straight line up to that time is η lin. ηmax / ηlin is defined as λmax (0.1). The apparatus and the like specifically used in the examples of the present specification are as described in the Examples section below.

The polypropylene resin (X) having a long-chain branched structure used in the present invention preferably has high stereoregularity as described above, whereby a molded article having high rigidity can be produced. As long as the polypropylene resin (X) having a long-chain branched structure is a homopolypropylene (propylene homopolymer) or satisfies the various characteristics described above, a small amount of ethylene, 1-butene, 1-hexene, etc. May be a propylene-α-olefin random copolymer with an α-olefin or other comonomer having about 2 to 8 carbon atoms. When the polypropylene resin (X) is homopolypropylene, the crystallinity is high and the melting point is high, but the melting point is also high when the polypropylene resin (X) is a propylene-α-olefin random copolymer. Is preferred.
More specifically, the melting point obtained by differential scanning calorimetry (DSC) is preferably 145 ° C. or higher, more preferably 150 ° C. or higher. When the melting point is higher than 145 ° C, it is preferable from the viewpoint of heat resistance of the product, but the upper limit of the melting point of the polypropylene resin (X) is usually 170 ° C.
The melting point is obtained by differential scanning calorimetry (DSC). After the temperature is temporarily increased to 200 ° C. and the thermal history is erased, the temperature is decreased to 40 ° C. at a temperature decreasing rate of 10 ° C./min, and the temperature is increased again. The temperature is the endothermic peak top temperature when measured at a rate of 10 ° C./min. The apparatus and the like specifically used in the examples of the present specification are as described in the Examples section below.

3). Compounding conditions (A-1)
It is essential that the polypropylene resin (A) contains the polypropylene resin (Y). By using the polypropylene resin (Y) as an essential component in the polypropylene resin composition of the present invention and a molded product obtained by molding the same, high moldability can be maintained while maintaining appropriate fluidity and good moldability. It is possible to satisfactorily maintain the basic physical properties of the polypropylene resin composition of the present invention and a molded product formed by molding the resin composition.

Condition (A-2)
Furthermore, the polypropylene resin (A) contains at least one polypropylene resin selected from the group consisting of the polypropylene resin (Y) and the polypropylene resin (X) having a long-chain branched structure. In particular, the polypropylene resin composition of the present invention and a molded product obtained by molding the polypropylene resin composition have good drip resistance by further enhancing the properties of the polypropylene resin (Y) or having an appropriate melt tension. In addition, when it is intended to provide a new feature of exhibiting high flame retardancy, the use of polypropylene resin (X) having a long-chain branched structure is effective.

  Since the polypropylene resin (A) satisfies both the conditions (A-1) and (A-2), the polypropylene resin (Y) is an essential component, but the polypropylene resin (X) having a long-chain branched structure. Need not be used depending on the purpose and desired performance. However, regardless of whether or not the polypropylene resin (X) having a long-chain branched structure is used, the polypropylene resin (A) has a composition range of the condition (a) described later, and the polypropylene resin composition of the present invention and In the molded product formed by molding it, it is necessary for solving the problems of the present invention.

Condition (A-3)
When the polypropylene resin (X) having a long chain branched structure is used in the present invention, the polypropylene resin is usually used with respect to a total of 100% by weight of the polypropylene resin (Y) and the polypropylene resin (X) having a long chain branched structure. (Y) 70-100% by weight of polypropylene resin (X) having a long chain branched structure (X) 0-30% by weight, polypropylene resin (Y) 70-99% by weight and polypropylene resin (X) having a long chain branched structure It is preferably 1 to 30% by weight. The polypropylene resin (Y) is more preferably 75 to 90% by weight. On the other hand, the polypropylene resin (X) having a long chain branched structure is more preferably 10 to 25% by weight. By setting the blending amount of the polypropylene resin (Y) and the polypropylene resin (X) having a long-chain branched structure in such a range, it becomes possible to maintain good molding processability as well as high rigidity and impact resistance. In addition, since it is possible to develop a high flame resistance by maintaining a higher drip resistance, it is possible to provide a higher level flame retardant material.

2. Fiber (B)
The fiber (B) used in the present invention is at least one fiber (fibrous filler) selected from the group consisting of glass fiber and carbon fiber. The fiber (B) not only improves physical properties such as rigidity and impact strength in the polypropylene resin composition of the present invention and a molded product formed from the same, but also has heat resistance and dimensional stability (reduction in linear expansion coefficient). Etc.), low shrinkage, scratch resistance, and other characteristics that contribute to improved physical properties.

(1) Kind, Production The fiber (B) is at least one fiber selected from the group consisting of glass fiber and carbon fiber as described above, and preferably the degree of the effect of the present invention and the polypropylene resin composition of the present invention. And it is glass fiber from the point of easiness of manufacture of the molded article formed by molding it and economical efficiency.
This fiber (B) can be used in combination of two or more for the purpose of further improving the effect of the present invention, and is a so-called master previously contained in the polypropylene resin (A) or the like at a relatively high concentration. It can also be used in batch form.
Further, for example, glass beads, glass balloons, mica, various inorganic or organic fillers that do not correspond to the fiber (B), which do not correspond to the fiber (B), can be used in combination as long as the effects of the present invention are not significantly impaired. .

(I) Glass fiber Glass fiber can be used without any particular limitation. Examples of the type of glass used for the fiber include E glass, C glass, A glass, and S glass. E glass is preferred.
The manufacturing method of this glass fiber is not specifically limited, It manufactures with a well-known various manufacturing method.

The fiber diameter of the glass fiber is preferably 3 μm to 25 μm, more preferably 6 μm to 20 μm. Moreover, it is preferable that the length shall be 2 mm-20 mm. The fiber diameter and length are obtained from values measured with a microscope, calipers, and the like.
When the fiber diameter is less than 3 μm, the glass fiber may be easily broken during the production and molding of the polypropylene resin composition of the present invention and a molded product formed from the resin composition. On the other hand, the glass fiber exceeds 25 μm. As the fiber aspect ratio decreases, the effects of improving the rigidity and impact strength of the polypropylene resin composition of the present invention and the molded product formed from the polypropylene resin composition may decrease.

  The fiber length is preferably 2 mm to 20 mm as described above, although it depends on the glass fiber used. If the thickness is less than 2 mm, the polypropylene resin composition of the present invention and the molded article formed by molding the same may deteriorate the physical properties such as rigidity and impact strength. On the other hand, if it exceeds 20 mm, the moldability (fluidity). May be reduced. In addition, the fiber length in this case can also be represented by the length in the case of using glass fiber as a raw material as it is. However, in the case of glass fiber-containing pellets in which a large number of continuous glass fibers are integrated by melt extrusion as described later, this is not the only case, and usually a roving-shaped one is used. Two or more kinds of glass fibers can be used in combination.

As the glass fiber, both surface treated and untreated can be used. For improving the dispersibility in the polypropylene resin (A), an organic silane coupling agent and a titanate coupling agent are used. It is preferable to use an aluminate coupling agent, a zirconate coupling agent, a silicone compound, a higher fatty acid, a fatty acid metal salt, a fatty acid ester, or the like.
Examples of the organic silane coupling agent used for the surface treatment include vinyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and 3-acryloxypropyl. And trimethoxysilane. Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, and isopropyl tri (N-aminoethyl) titanate. Moreover, as an aluminate coupling agent, acetoalkoxy aluminum diisopropylate etc. can be mentioned, for example. Examples of the zirconate coupling agent include tetra (2,2-diallyloxymethyl) butyl, di (tridecyl) phosphitozirconate; neopentyl (diallyl) oxy, and trineodecanoyl zirconate. Examples of the silicone compound include silicone oil and silicone resin.

Furthermore, examples of the higher fatty acid used for the surface treatment include oleic acid, capric acid, lauric acid, palmitic acid, stearic acid, montanic acid, kaleic acid, linoleic acid, rosin acid, linolenic acid, undecanoic acid, and undecenoic acid. Is mentioned. Examples of the higher fatty acid metal salt include fatty acids having 9 or more carbon atoms, such as sodium salts such as stearic acid and montanic acid, lithium salts, calcium salts, magnesium salts, zinc salts, and aluminum salts. Of these, calcium stearate, aluminum stearate, calcium montanate, and sodium montanate are preferred. Examples of fatty acid esters include polyhydric alcohol fatty acid esters such as glycerin fatty acid esters, alpha sulfone fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyethylene fatty acid esters, and sucrose fatty acid esters.
The amount of the surface treatment agent used is not particularly limited, but is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the glass fiber. .

Further, the glass fiber may be used that has been focused (surface) treated with a sizing agent, and the types of sizing agent include epoxy sizing agents, aromatic urethane sizing agents, aliphatic urethane sizing agents, Examples thereof include acrylic sizing agents and maleic anhydride-modified polyolefin sizing agents.
Since these sizing agents need to be melted in the melt-kneading with the polypropylene resin (A), it is preferable that they are melted at 200 ° C. or lower.

The glass fiber can also be used as a so-called chopped strand glass fiber obtained by cutting a fiber yarn into a desired length. It is preferable to use this chopped strand glass fiber in order to further enhance each effect of improving the rigidity and impact strength of the polypropylene resin composition of the present invention and a molded product formed by molding the same.
Specific examples of the glass fiber include Nippon Electric Glass Co., Ltd. (T480H).

  These glass fibers are formed into pellets in which an arbitrary amount of, for example, a polypropylene resin (A) and a number of glass fibers continuous by melt extrusion are assembled and integrated, and the glass fibers in the pellets The length is substantially the same as the length of one side (extrusion direction) of the pellet, which may be used as a “glass fiber-containing pellet”, and is formed by molding the polypropylene resin composition of the present invention. It is more preferable from the viewpoint of further improving physical properties such as rigidity and impact strength of the product. In this case, “substantially” specifically refers to a glass fiber-containing pellet whose length is 50% or more, preferably 90% or more, based on the total number of glass fibers in the glass fiber-containing pellet. This means that the fiber is hardly broken during the preparation of the pellets.

  The method for producing such glass fiber-containing pellets is not particularly limited. For example, an arbitrary amount of components (A) can be used while drawing a large number of continuous glass fibers from a fiber rack through a crosshead die using a resin extruder. ) And a method in which a large number of glass fibers are assembled and integrated (pultrusion molding method) by melt extrusion (impregnation) in a molten state, which is preferable because the fibers are hardly broken.

Although the length (extrusion direction) of this glass fiber containing pellet is based also on the glass fiber to be used, it is preferable to set it as 2 mm-20 mm like the above. If it is less than 2 mm, the polypropylene resin composition of the present invention and the molded article formed by molding the same may deteriorate the physical properties such as rigidity and impact strength. On the other hand, if it exceeds 20 mm, moldability (fluidity), etc. May be reduced.
Moreover, in this glass fiber containing pellet, it is preferable that content of glass fiber is 20 weight%-70 weight% on the basis of 100 weight% of this whole pellet.
When glass fiber-containing pellets having a glass fiber content of less than 20% by weight are used in the present invention, physical properties such as rigidity and impact strength of the polypropylene resin composition of the present invention and a molded product formed by molding the resin composition are obtained. On the other hand, when 70% by weight or more is used, moldability (fluidity) and the like may be reduced.

(Ii) Carbon fiber The carbon fiber is not particularly limited in size and type, and can be used including fine fibers having a fiber diameter of 500 nm or less, which are also referred to as fine carbon fibers. What is 2 micrometers-20 micrometers is preferable, and what is 3 micrometers-15 micrometers is more preferable. When the fiber diameter is less than 2 μm, the carbon fiber may be easily broken during the production or molding of the polypropylene resin composition of the present invention and a molded product formed from the composition, and the polypropylene resin of the present invention. The effects of improving physical properties such as rigidity and impact strength of the composition and a molded product formed from the composition may be reduced.
Further, when the fiber diameter exceeds 20 μm, the effect of improving the rigidity and impact strength of the polypropylene resin composition of the present invention and the molded product formed by molding the same decreases as the fiber aspect ratio decreases. There is a fear.
Here, the measuring method of a fiber diameter is a well-known method, for example, JIS R7607 (old JIS R7601) and a microscope observation method are mentioned.

Further, the fiber length of the carbon fiber is preferably 1 mm to 20 mm, and more preferably 3 mm to 10 mm.
In addition, the fiber length in this case represents the length in the case of using carbon fiber as a raw material as it is. However, in the case of “carbon fiber-containing pellets” in which a large number of continuous carbon fibers are aggregated and integrated by melt extrusion, which will be described later, this is not the only case, and usually a roving-shaped one is used.
When the fiber length is less than 1 mm, the final fiber length after the production and molding of the polypropylene resin composition of the present invention and a molded product formed from the composition is shorter, and the polypropylene resin composition of the present invention and There is a possibility that physical properties such as rigidity and impact strength of a molded product obtained by molding the molded product may be lowered. On the other hand, when the thickness exceeds 20 mm, moldability (fluidity) may be lowered. Two or more types of carbon fibers can be used in combination.

The type of carbon fiber is not particularly limited as described above. For example, PAN (polyacrylonitrile) carbon fiber mainly composed of acrylonitrile, pitch carbon fiber mainly composed of tar pitch, and rayon carbon fiber. Etc., and all are preferably used. Although these are highly suitable for the present invention, PAN-based carbon fibers are preferred from the viewpoints of composition purity and uniformity. These may be used alone or in combination. In addition, the manufacturing method of these carbon fibers is not specifically limited.
As specific examples of carbon fiber, in PAN-based carbon fiber, trade name "Pyrofil" manufactured by Mitsubishi Rayon Co., Ltd., trade name "Torayca" manufactured by Toray Industries, Inc., trade name "Beth Fight" manufactured by Toho Tenax Co., etc. Examples of the pitch-based carbon fiber include a product name “DIALEAD” manufactured by Mitsubishi Plastics, a product name “DonaCarbo” manufactured by Osaka Gas Chemicals, and a product name “Kureka” manufactured by Kureha Chemicals.

Carbon fiber usually has a tensile elastic modulus of about 200 GPa to 1000 GPa. However, in the present invention, from the strength and economy of the polypropylene resin composition of the present invention and a molded product formed by molding the same, in the present invention, it is 200 GPa to 900 GPa. It is preferable to use those, and those using 200 GPa to 300 GPa are more preferable.
Carbon fibers usually have a density of about 1.7 g / cm 3 to 5 g / cm 3, but those having a density of 1.7 g / cm 3 to 2.5 g / cm 3 are used in view of lightness and economy. preferable.
Here, the tensile modulus and density are measured by known methods. For example, the tensile modulus can be JIS R7606 (former JIS R7601), and the density can be JIS R7603 (former JIS R7601). Can be mentioned.

These carbon fibers can be used as so-called chopped (strand-like) carbon fibers (hereinafter also simply referred to as CCF) obtained by cutting the fiber yarn into a desired length, and various sizing agents can be used as necessary. It is also possible to use a focusing process. In the present invention, it is preferable to use this CCF in order to further enhance the effects of improving physical properties such as low shrinkage, scratch resistance, rigidity and impact strength in the fiber reinforced composition of the present invention and the molded product thereof. .
As specific examples of such CCF, in the case of PAN-based carbon fiber, the product name “Pyrofil Chop” manufactured by Mitsubishi Rayon Co., Ltd., the product name “Torayca Chop” manufactured by Toray Industries, Inc., the product name “Besfight Chop” manufactured by Toho Tenax Co., Ltd., etc. For pitch-based carbon fiber, the product name “Dialead Chopped Fiber” manufactured by Mitsubishi Plastics Co., Ltd., the product name “Donna Carbo Chop” manufactured by Osaka Gas Chemical Company, and the product name “Kureka Chop” manufactured by Kureha Chemical Co., Ltd. Can be mentioned.

These carbon fibers are formed into pellets in which an arbitrary amount of polypropylene resin (A) and a number of continuous carbon fibers obtained by melt extrusion processing are assembled and integrated, and the length of the carbon fibers in the pellets. Is substantially the same as the length of one side (extrusion direction) of the pellet, and is used as a “carbon fiber-containing pellet”. The polypropylene-based resin composition of the present invention and the molded product rigidity / It is more preferable from the viewpoint of enhancing physical properties such as impact strength. In this case, “substantially” specifically means that the length of the carbon fiber-containing pellet is 50% or more, preferably 90% or more, based on the total number of carbon fibers in the carbon fiber-containing pellet. This means that the fiber is hardly broken during the preparation of the pellets.
The method for producing such carbon fiber-containing pellets is not particularly limited. For example, an arbitrary amount of component (A) can be used while drawing a large number of continuous carbon fibers from a fiber rack through a crosshead die using a resin extruder. It is preferable to manufacture by a method (pultrusion molding method) in which a large number of carbon fibers are assembled and integrated by melt extrusion processing (impregnation) in a molten state because the fibers are hardly broken.

Although the length (extrusion direction) of this carbon fiber containing pellet is based also on the carbon fiber to be used, it is preferable to set it as 2 mm-20 mm. If it is less than 2 mm, the polypropylene-based resin composition of the present invention and the molded product formed by molding the resin composition may have reduced physical properties such as rigidity and impact strength. May decrease.
In the carbon fiber-containing pellet, the carbon fiber content is preferably 20% by weight to 70% by weight based on 100% by weight of the whole pellet.
When carbon fiber-containing pellets having a carbon fiber content of less than 20% by weight are used in the present invention, physical properties such as rigidity and impact strength of the polypropylene resin composition of the present invention and a molded product formed by molding the same are reduced. On the other hand, when more than 70% by weight is used, the moldability (fluidity) and the like may be reduced.

3. Organic flame retardant (C)
As the organic flame retardant (C) used in the present invention, various organic flame retardants generally used as a flame retardant for polyolefin, such as halogen-based, phosphorus-based, guanidine-based, melamine cyanuric acid derivatives, etc. Any of these organic flame retardants can be used.
Examples of the halogen flame retardant include organic halogenated aromatic compounds such as halogenated diphenyl compounds, halogenated bisphenol compounds, halogenated bisphenol-bis (alkyl ether) compounds, and halogenated phthalimide compounds. The halogenated bisphenol-bis (alkyl ether) compounds are often used.

  Examples of the halogenated diphenyl compound include a halogenated diphenyl ether compound, a halogenated diphenyl ketone compound, a halogenated diphenylalkane compound, and the like. Among them, a halogenated diphenylalkane compound such as decabromodiphenylethane is used. There are many cases.

  Examples of the halogenated bisphenol compounds include halogenated bisphenyl alkanes, halogenated bisphenyl ethers, halogenated bisphenyl thioethers, halogenated bisphenyl sulfones, etc. Among them, bis (3,5 Halogenated bisphenyl thioethers such as -dibromo-4-hydroxyphenyl) sulfone are often used.

  Examples of the halogenated bisphenol bis (alkyl ether) compounds include (3,5-dibromo-4-2,3-dibromopropoxyphenyl)-(3-bromo-4-2,3-dibromopropoxyphenyl) methane. 1- (3,5-dibromo-4-2,3-dibromopropoxyphenyl) -2- (3-bromo-4-2,3-dibromopropoxyphenyl) ethane, 1- (3,5-dibromo-4 -2,3-dibromopropoxyphenyl) -3- (3-bromo-4-2,3-dibromopropoxyphenyl) propane, 2,2-bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) ) Propane, (3,5-dichloro-4-2,3-dibromopropoxyphenyl)-(3-chloro-4-2,3-dibromopropoxyphenyl) 1- (3,5-dichloro-4-2,3-dibromopropoxyphenyl) -2- (3-chloro-4-2,3-dibromopropoxyphenyl) ethane, 1- (3,5-dichloro- 4-2,3-dibromopropoxyphenyl) -3- (3-chloro-4-2,3-dibromopropoxyphenyl) propane, bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) methane, 1,2-bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) ethane, 1,3-bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) propane, bis ( 3,5-dichloro-4-2,3-dibromopropoxyphenyl) methane, 1,2-bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) ethane, 1,3 Bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) propane, 2-bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) propane, (3,5-dibromo-4 -2,3-dibromopropoxyphenyl)-(3-bromo-4-2,3-dibromopropoxyphenyl) ketone, (3,5-dichloro-4-2,3-dibromopropoxyphenyl)-(3-chloro- 4-2,3-dibromopropoxyphenyl) ketone, bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) ketone, bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) Ketone, (3,5-dibromo-4-2,3-dibromopropoxyphenyl)-(3-bromo-4-2,3-dibromopropoxyphenyl) ether (3,5-dichloro-4-2,3-dibromopropoxyphenyl)-(3-chloro-4-2,3-dibromopropoxyphenyl) ether, bis (3,5-dibromo-4-2,3 -Dibromopropoxyphenyl) ether, bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) ether, (3,5-dibromo-4-2,3-dibromopropoxyphenyl)-(3-bromo- 4-2,3-dibromopropoxyphenyl) thioether, (3,5-dichloro-4-2,3-dibromopropoxyphenyl)-(3-chloro-4-2,3-dibromopropoxyphenyl) thioether, bis (3 , 5-Dibromo-4-2,3-dibromopropoxyphenyl) thioether, bis (3,5-dichloro-4-2,3-dibromopropo Siphenyl) thioether, (3,5-dibromo-4-2,3-dibromopropoxyphenyl)-(3-bromo-4-2,3-dibromopropoxyphenyl) sulfone, (3,5-dichloro-4-2, 3-dibromopropoxyphenyl)-(3-chloro-4-2,3-dibromopropoxyphenyl) sulfone, bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) sulfone, bis (3,5- Dichloro-4-2,3-dibromopropoxyphenyl) sulfone, among which brominated bisphenol A (brominated aliphatic ether), brominated bisphenol S (brominated aliphatic ether), chlorinated bisphenol A (chlorinated) Aliphatic ether), chlorinated bisphenol S (chlorinated aliphatic ether), Love Romo bisphenol A, it is often used etherification tetrabromobisphenol S.

  Examples of etherified tetrabromobisphenol A include tetrabromobisphenol A-bis (2,3-dibromopropyl ether) and 2,2-bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) propane. The Examples of etherified tetrabromobisphenol S include bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) sulfone.

These halogen flame retardants may be used alone or in combination of two or more. For example, a halogenated diphenyl compound and a halogenated bisphenol compound may be used in combination.
In addition to halogen flame retardants, other organic flame retardants that do not correspond to halogen flame retardants such as phosphorus flame retardants can also be used.
Among these halogen flame retardants, bromine flame retardants are often used because of their high flame retardant effect.

On the other hand, in recent years, the organic phosphoric acid has high effects on the environmental impact of halogenated flame retardants, and the dispersion effect and flame retardancy of the polypropylene resin composition of the present invention and molded products formed from the same are high. Phosphorus flame retardants composed of ester compounds, phosphate compounds and mixtures thereof are preferred, and phosphate compounds are particularly preferred.
Specifically, organic phosphate compounds such as triphenyl phosphate, tricresyl phosphate, bisphenol-A-bisdiphenyl phosphate, resorcinol-bisdiphenyl phosphate, ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, Examples thereof include a piperazine orthophosphate salt, a melamine pyrophosphate salt, a piperazine pyrophosphate salt, a melamine polyphosphate salt, a melamine orthophosphate salt, a phosphate compound such as calcium phosphate and magnesium phosphate, or a mixture thereof.

  In the examples of the phosphate compounds, N, N, N ′, N′-tetramethyldiaminomethane, ethylenedidiamine, N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine instead of melamine and piperazine N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-diethylethylenediamine, 1,2-propanediamine, , 3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, trans-2,5 -Dimethylpiperazine, 1,4-bis (2-aminoethyl) Piperazine, 1,4-bis (3-aminopropyl) piperazine, acetoguanamine, benzoguanamine, acrylic guanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-hydroxy -1,3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4- Diamino-6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine 2,4-diamino-6-mercapto-1,3,5-triazine, 2-amino-4,6-dimercapto-1,3,5-triazine, ammelin, benzguanamine Acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylene diguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3- Compounds in which hexylene dimeramine or the like is replaced can be used in the same manner. Examples of commercially available products include ADK STAB FP2000, FP2100, FP2200, and ammonium polyphosphate manufactured by Asahi Denka Co., Ltd.

4). Polytetrafluoroethylene resin (PTFE) (D)
The polytetrafluoroethylene resin (D) used in the present invention is a tetrafluoroethylene homopolymer or a copolymer containing tetrafluoroethylene as a main component. Comonomers copolymerized with tetrafluoroethylene include fluorine-containing olefins such as difluoroethylene, trifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, perfluoroalkyl vinyl ether, and perfluoroalkyl (meth) acrylate. The fluorine-containing alkyl (meth) acrylate can be used. The content of the copolymer component is preferably 10% by weight or less with respect to tetrafluoroethylene as a raw material.

  The component (D) used in the present invention can be used in various forms such as PTFE particles, an aqueous dispersion of PTFE particles, a so-called “master batch” in which PTFE is kneaded with, for example, a polypropylene resin (A). Among these, it is preferable to use PTFE particles because it is easy to obtain and handle and the amount used can be accurately grasped, and impurities can be excluded. As the PTFE particles, commercially available ones may be used, or after obtaining an aqueous dispersion of PTFE particles shown below, the PTFE particles may be dried by the method described later.

  Commercially available raw materials for aqueous dispersions of polytetrafluoroethylene particles include Asahi Glass's Fullon AD-1, AD-936, Daikin Industries' Polyflon D-1, D-2, Mitsui DuPont Fluorochemical's Teflon 30J (Teflon is a registered trademark) can be given as a representative example.

  An aqueous dispersion of PTFE particles can be obtained by polymerizing a tetrafluoroethylene monomer and, if necessary, an appropriate comonomer by an emulsion polymerization method using a fluorine-containing surfactant. The particle size of the aqueous dispersion of PTFE particles is preferably 0.05 to 1.0 μm.

  The aqueous dispersion of PTFE particles thus obtained can be poured into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, and salted out, solidified and then dried, or pulverized by spray drying. it can. It is preferable to use the powder obtained as described above as it is, but the PTFE masterbatch is prepared by blending into a matrix resin such as polypropylene together with a molding aid such as an antioxidant, a stabilizer and a lubricant, and melt-kneading. It may be prepared and used.

  In some cases, PTFE can be modified by polymerizing a polymerizable vinyl compound in an aqueous dispersion of PTFE particles. The PTFE-modified product obtained at this time forms a uniform mixture of PTFE and a polymer of a vinyl compound, and the mixing property with polypropylene may be improved.

  Examples of the polymerizable vinyl compound include styrene, α-methylstyrene, o-methylstyrene, t-butylstyrene, o-ethylstyrene, p-chlorostyrene, o-chlorostyrene, 2,4-dichlorostyrene, p-methoxy. Aromatic vinyl monomers such as styrene, o-methoxystyrene, 2,4-dimethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid-2 -(Meth) acrylic acid ester monomers such as ethylhexyl, dodecyl (meth) acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate; cyanation of acrylonitrile, methacrylonitrile, etc. Vinyl monomer; α, β-unsaturated carboxylic acid such as maleic anhydride; N Maleimide monomers such as phenylmaleimide, N-methylmaleimide and N-cyclohexylmaleimide; Epoxy group-containing monomers such as glycidyl methacrylate; Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; Vinyl acetate and vinyl butyrate And carboxylic acid vinyl monomers; α-olefin monomers such as ethylene, propylene, and isobutylene; and diene monomers such as butadiene, isoprene, and dimethylbutadiene. Of these, a (meth) acryl monomer having a polar group is preferred. These monomers can be used alone or in admixture of two or more. The PTFE content in the modified PTFE is usually selected from the range of 1 to 90% by weight.

  Examples of commercially available PTFE modified with an acrylic monomer include a modifier for thermoplastic resin (Methbrene A-3000) manufactured by Mitsubishi Rayon Co., Ltd.

  When PTFE is melt kneaded with the polypropylene resin (A), it fibrillates by a shearing force and adopts a fibrous network structure, and therefore has an effect of improving the melt tension of the molten resin. In order to efficiently generate and disperse this fibril, a product obtained by modifying PTFE with a special acrylic resin is preferable.

  In the present invention, the component (D) can be used in the form of a master batch obtained by melt-kneading together with a matrix resin. The master batch is mixed with an appropriate amount of modified or unmodified PTFE powder in a matrix component such as polypropylene resin, mixed with a tumbler mixer or Henschel mixer, and then suitable using a twin screw extruder or the like. It is manufactured by pelletizing under various melting conditions. If necessary, various additives such as an antioxidant, a lubricant, and a light stabilizer can be blended at the same time.

  The fiber (B) and the organic flame retardant (C) may be mixed in advance with the polypropylene resin (A) and then mixed with the master batch of the component (D). Component (A), component (B), component (C) and component (D) may be mixed simultaneously, and various additives may be mixed simultaneously.

5. Compounding amount of each component In the present invention, the content of each component is 20 to 77 parts by weight of the polypropylene resin (A), 5 to 40 parts by weight of the fiber (B), and 18 to 40 parts by weight of the organic flame retardant (C). And the total amount of polypropylene resin (A), fiber (B), and organic flame retardant (C) is 100 parts by weight, and further, polypropylene resin (A), fiber (B), It is essential that the total amount of the organic flame retardant (C) is in the range of 0.01 to 1.5 parts by weight with respect to 100 parts by weight of the polytetrafluoroethylene resin (D). By setting the blending amount of each component in such a range, the polypropylene resin composition of the present invention and the molded product obtained by molding the polypropylene resin composition of the present invention have a self-extinguishing property and a drip resistance that have been difficult with conventional techniques. By achieving both, it is possible to express extremely high flame retardancy, achieve 5VA at UL94-5V, and impart mechanical properties (rigidity, impact), weather resistance and molding processability.

  The polypropylene resin (A) is preferably 35 to 70 parts by weight, more preferably 38 to 65 parts by weight, more preferably 40 to 60 parts by weight, and particularly preferably 45 to 50% by weight.

The fiber (B) is preferably 7 to 38 parts by weight, more preferably 8 to 35 parts by weight, and more preferably 10 to 30 parts by weight. If the blending amount of the fiber (B) falls below the range specified in the present application, the mechanical properties (rigidity, impact) and the like of the polypropylene resin composition of the present invention and a molded product formed from the polypropylene resin composition may be lowered. On the other hand, if the range specified in the present application is exceeded, moldability (fluidity) and the like may be reduced.
Here, the blending amount of the fiber (B) is an actual amount. For example, when the glass fiber-containing pellet is used, it is calculated based on the actual content of the fiber (B) contained in the pellet.

The organic flame retardant (C) is preferably 19 to 38 parts by weight, more preferably 20 to 35 parts by weight, more preferably 23 to 32 parts by weight, and particularly preferably 25 to 30 parts by weight. If the blending amount of the organic flame retardant (C) is below the range specified in the present application, sufficient flame retardancy cannot be obtained. On the other hand, if it exceeds the range specified in the present application, the moldability is deteriorated and economically disadvantageous. It may become.
In addition, the compounding quantity of each component of a polypropylene resin (A), a fiber (B), and an organic flame retardant (C) is a polypropylene resin (A), a fiber (B), and an organic flame retardant (C). It can select from the range prescribed | regulated by this application of each component so that a total amount may be 100 weight part.

The polytetrafluoroethylene resin (D) is 0.01 to 1.5 parts by weight, preferably 100 parts by weight of the total amount of the polypropylene resin (A), fiber (B) and organic flame retardant (C). It is important to blend in the range of 0.02 to 1.0 parts by weight, more preferably 0.05 to 0.5 parts by weight. By setting the blending amount of the polytetrafluoroethylene resin (D) in such a range, the polypropylene resin composition of the present invention and the molded product formed by molding the resin composition can be kept good in flame resistance and proper. It is possible to manufacture a molded product under conditions. That is, if the amount is less than 0.01 part by weight, the dripping prevention effect (drip resistance) at the time of combustion is not sufficient. Tends to be difficult.
Here, the blending amount of the polytetrafluoroethylene resin (D) is an actual amount. For example, when the masterbatch is used, the actual content of the polytetrafluoroethylene resin (D) contained in the masterbatch is used. Calculate based on quantity.

6). Optional additive component (E)
In the present invention, in addition to the polypropylene resin (A), the fiber (B), the organic flame retardant (C) and the polytetrafluoroethylene resin (D), a range that does not significantly impair the effects of the present invention as necessary. Thus, for example, an optional additive component (E) that is usually used can be blended to further improve the effects of the invention or to impart other effects.
Specifically, molecular weight depressants such as peroxides, colorants such as pigments, modified polyolefins, phenolic, phosphorous, sulfur-based antioxidants, hindered amine-based light stabilizers, benzotriazole-based, etc. UV absorbers, sorbitol-based nucleating agents, non-ionic antistatic agents, organometallic salt-based dispersants, nitrogen compounds and other metal deactivators, thiazole-based antibacterial and antifungal agents, Flame retardant aids such as plasticizers, neutralizers, lubricants, elastomers (rubber components), metal oxides, polyolefin resins other than polypropylene resins (A) and polytetrafluoroethylene resins (D), polyamide resins and polyesters Examples include thermoplastic resins such as resins, fillers such as talc other than fibers (B), and flame retardants such as hydrated metal compounds other than organic flame retardants (C). It can be.

  These optional addition components may be used in combination of two or more thereof, may be added to the polypropylene resin composition of the present invention, or the components, polypropylene resin (A), fiber (B), organic It may be mixed and added to each component of the flame retardant (C) and the polytetrafluoroethylene resin (D), and two or more of these components may be used in combination. In the present invention, the amount of the optional additive component (E) is not particularly limited, but is usually 100 parts by weight with respect to the total amount of the polypropylene resin (A), the fiber (B), and the organic flame retardant (C). 0 to 4.0 parts by weight.

(1) Kinds As the molecular weight depressant, for example, various organic peroxides and so-called decomposition (oxidation) accelerators can be used, and organic peroxides are preferable.
Specific examples of the organic peroxide include benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl-2,5-di- ( Benzoylperoxy) hexane, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexyne-3, t-butyl-di-peradipate, t-butylperoxy-3,5,5- Trimethylhexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2,5-di- (t-butylperoxy) ) Hexane, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexyne-3,1,3-bis- ( -Butylperoxyisopropyl) benzene, t-butylcumyl peroxide, 1,1-bis- (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis- (t-butylper Oxy) cyclohexane, 2,2-bis-t-butylperoxybutane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide , 1,1,3,3-tetra-methylbutyl hydroperoxide and 2,5-di-methyl-2,5-di- (hydroperoxy) hexane selected from the group consisting of one or more Things can be mentioned. However, the present invention is not limited to these.

As a colorant, for example, an inorganic or organic pigment, the colored appearance, scratch resistance, appearance, texture, commercial value, weather resistance of the polypropylene resin composition of the present invention and a molded product formed by molding the same. It is effective for imparting and improving properties and durability.
Specific examples of inorganic pigments include carbon blacks such as furnace carbon and ketjen carbon; titanium oxide; iron oxide (such as Bengala); chromic acid (such as yellow lead); molybdic acid; selenide sulfide; ferrocyanide Examples of organic pigments include poorly soluble azo lakes; soluble azo lakes; insoluble azo chelates; condensable azo chelates; other azo chelates such as azo chelates; phthalocyanine blue; phthalocyanine pigments such as phthalocyanine green; anthraquinones; Examples include selenium pigments such as thioindigo; dye lakes; quinacridone systems; dioxazine systems; and isoindolinone systems. Moreover, in order to make a metallic tone or a pearl tone, an aluminum flake; a pearl pigment can be contained. Moreover, dye can also be contained.

Examples of light stabilizers and ultraviolet absorbers include hindered amine compounds, benzotriazoles, benzophenones, and salicylates, such as the weather resistance and durability of the polypropylene resin composition of the present invention and molded articles formed from the resin composition. Effective for granting and improving.
Specific examples of the hindered amine compound include a condensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine; poly [[6- (1, 1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2 , 2,6,6-tetramethyl-4-piperidyl) imino]]; tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate; tetrakis ( 1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate; bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebake Bis-2,2,6,6-tetramethyl-4-piperidyl sebacate and the like, and examples of the benzotriazole type include 2- (2′-hydroxy-3 ′, 5′-di-t-butyl) Phenyl) -5-chlorobenzotriazole; 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, and the like. As the benzophenone series, 2-hydroxy- 4-methoxybenzophenone; 2-hydroxy-4-n-octoxybenzophenone and the like. Examples of salicylates include 4-t-butylphenyl salicylate; 2,4-di-t-butylphenyl 3 ′, 5′- Examples include di-t-butyl-4′-hydroxybenzoate.
Here, the method in which the light stabilizer and the ultraviolet absorber are used in combination is preferable because the effect of improving weather resistance, durability and the like is large.

Examples of antioxidants include phenolic, phosphorus and sulfur antioxidants, heat resistance stability, processing stability and heat resistance of the polypropylene resin composition of the present invention and molded products formed from the resin composition. Effective for imparting and improving aging properties.
As the antistatic agent, for example, nonionic or cationic antistatic agents are effective for imparting and improving the antistatic properties of the polypropylene resin composition of the present invention and a molded product obtained by molding the same.

  Examples of the metal oxide (flame retardant aid) include zinc oxide, iron oxide, aluminum oxide, and molybdenum oxide. More preferable metal oxides are zinc oxide and iron oxide, and those having an average particle size of 30 μm or less, preferably 10 μm or less, and more preferably 1 μm or less are suitable. When the average particle diameter of the metal oxide is larger than 30 μm, dispersibility with respect to the polyolefin resin (A) is deteriorated, and high flame retardancy cannot be obtained. The compounding amount when using a metal oxide is preferably 0.05 to 5 parts by weight, more preferably 100 parts by weight of polypropylene resin (A), fiber (B), and organic flame retardant (C). Is 0.1 to 3 parts by weight. If the amount is less than 0.05 part by weight, the synergistic flame retardant effect due to sufficient addition cannot be obtained.

  The modified polyolefin is an acid-modified polyolefin and / or a hydroxy-modified polyolefin, and in the present invention, has a characteristic of imparting functions such as mechanical properties (particularly rigidity / impact strength) to a higher degree.

There is no restriction | limiting in particular as acid-modified polyolefin, A conventionally well-known thing can be used.
Examples of the acid-modified polyolefin include polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-α-olefin-nonconjugated diene compound copolymer (EPDM, etc.), ethylene-aromatic monovinyl compound-conjugated diene compound copolymer. A polyolefin such as rubber is modified by graft copolymerization with an unsaturated carboxylic acid such as maleic acid or maleic anhydride. This graft copolymerization is performed, for example, by reacting the polyolefin with an unsaturated carboxylic acid in a suitable solvent using a radical generator such as benzoyl peroxide. Moreover, the component of unsaturated carboxylic acid or its derivative can also be introduce | transduced in a polymer chain by random or block copolymerization with the monomer for polyolefin.

Examples of unsaturated carboxylic acids used for modification include carboxyl groups such as maleic acid, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid, and functional groups such as hydroxyl groups and amino groups as necessary. And a compound having a polymerizable double bond.
Examples of unsaturated carboxylic acid derivatives include acid anhydrides, esters, amides, imides, metal salts, and the like. Specific examples thereof include maleic anhydride, itaconic anhydride, methyl acrylate, and ethyl acrylate. , Butyl acrylate, methyl methacrylate, ethyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, fumaric acid monoamide , Maleimide, N-butylmaleimide, sodium methacrylate and the like. Maleic anhydride is preferred.

Examples of the graft reaction conditions include di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2, Dialkyl peroxides such as 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxyisopropylcarbonate, 2, Peroxyesters such as 5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexyne-3, diacyl peroxides such as benzoyl peroxide , Diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di (hydro -Oxy) An organic peroxide such as hydroperoxide such as hexane is used in a molten state or solution at a temperature of about 80 to 300 ° C. using about 0.001 to 10 parts by weight with respect to 100 parts by weight of the polyolefin. The method of making it react in a state is mentioned.
The acid-modified amount of the acid-modified polyolefin (sometimes referred to as graft ratio) is not particularly limited, but the acid-modified amount is preferably 0.05 to 10% by weight, more preferably 0.07, in terms of maleic anhydride. ~ 5% by weight.
Preferable acid-modified polyolefin includes maleic anhydride-modified polypropylene.

Further, the hydroxy-modified polyolefin is a modified polyolefin containing a hydroxyl group. The modified polyolefin may have a hydroxyl group at an appropriate site, for example, at the end of the main chain or at the side chain.
Examples of the olefin resin constituting the hydroxy-modified polyolefin include, for example, homo- or copolymers of α-olefins such as ethylene, propylene, butene, 4-methylpentene-1, hexene, octene, nonene, decene, dodecene, α -A copolymer of an olefin and a copolymerizable monomer can be exemplified.

  Preferred hydroxy-modified polyolefins include hydroxy-modified polyethylene (eg, low density, medium density or high density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, ethylene- (meth) acrylate copolymer, ethylene-acetic acid. Vinyl copolymers, etc.), hydroxy-modified polypropylene (eg, polypropylene homopolymers such as isotactic polypropylene), random copolymers of propylene and α-olefins (eg, ethylene, butene, hexane, etc.), propylene-α-olefins Examples thereof include a block copolymer) and hydroxy-modified poly (4-methylpentene-1). Examples of the monomer for introducing the reactive group include a monomer having a hydroxyl group (for example, allyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc.). It can be illustrated.

The amount of modification by the monomer having a hydroxyl group is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the olefin resin. The average molecular weight of the hydroxy-modified polyolefin is not particularly limited. For example, in the case of a low molecular weight system, the hydroxy-modified polyolefin can be obtained by a method in which a conjugated diene monomer is polymerized by a known method such as anionic polymerization, and a polymer obtained by hydrolyzing it is hydrogenated.
These modified polyolefins may be used in combination of two or more.

(2) Blending ratio The modified polyolefin is 0 to 10 parts by weight, preferably 0.01 to 7 parts by weight based on 100 parts by weight of the polypropylene resin (A), fiber (B), and organic flame retardant (C). Parts by weight, more preferably 0.5 to 5 parts by weight, still more preferably 1 to 3 parts by weight. When the blending amount of the modified polyolefin exceeds 10 parts by weight, there is a possibility that the impact strength is lowered or the economy is lowered.

II. 1. Production method of polypropylene resin composition, production method of molded article and application Method for Producing Polypropylene Resin Composition The polypropylene resin composition of the present invention comprises a polypropylene resin (A), a fiber (B), an organic flame retardant (C), and a polytetrafluoroethylene resin (D). Accordingly, an optional additive component (E) is added, and the mixture can be produced by a kneading step of blending by a conventionally known method at the above blending ratio and melt-kneading.
Mixing is usually performed using a mixing device such as a tumbler, V blender, or ribbon blender, and melt kneading is usually performed by a single screw extruder, twin screw extruder, Banbury mixer, roll mixer, Brabender plastograph, kneader, stirring. Using a kneading machine such as a granulator (semi) melt kneading and granulating. When manufacturing by (semi) melt kneading and granulating, the blend of the above components may be kneaded at the same time, and each component is divided and kneaded to improve performance. That is, for example, first, a part or all of the polypropylene resin (A), the organic flame retardant (C) and the polytetrafluoroethylene resin (D) and a part of the fiber (B) are kneaded, and then the rest A method of kneading and granulating these components can also be employed.

In the polypropylene resin composition of the present invention, the average length of the fibers (B) present in the resin composition pellets obtained through the kneading step of melt-kneading or in the molded body is 0.3 mm or more, preferably 0.8. It is preferable to manufacture by a composite method such that it is 4 mm or more and 2.5 mm or less.
In the present specification, the average length of the fibers (B) present in the resin composition pellets or in the molded product means a value obtained by calculating an average using a value measured by a digital microscope. Specifically, for example, when the fiber (B) is glass fiber, the resin composition pellet or molded body of the present invention is burned, the ashed glass fiber is mixed with the surfactant-containing water, and the mixed water After the liquid is dropped and diffused on the thin glass plate, the glass fiber length is measured using a digital microscope (VHX-900, manufactured by Keyence Corporation), and the average value is calculated.
In addition, as a preferable manufacturing method, for example, in a melt kneading by a twin screw extruder, for example, a polypropylene resin (A), an organic flame retardant (C), and a polytetrafluoroethylene resin (D) are sufficiently melt kneaded. Thereafter, the fiber (B) is fed by a side feed method or the like, and the bundled fibers are dispersed while minimizing fiber breakage.

Further, for example, a polypropylene resin (A), fiber (B), organic flame retardant (C), and polytetrafluoroethylene resin (D) are mixed in a semi-molten state by stirring them at high speed in a Henschel mixer. A so-called agitation granulation method in which the fibers (B) in the inside are kneaded is one of the preferable production methods because the fibers can be easily dispersed while minimizing fiber breakage.
Furthermore, the polypropylene resin (A) excluding the fiber (B), the organic flame retardant (C), and the polytetrafluoroethylene resin (D) are melt-kneaded with an extruder or the like to form pellets, A method for producing a fiber reinforced composition by mixing so-called “fiber (B) -containing pellets” such as glass fiber-containing pellets and carbon fiber-containing pellets is also one of the preferred production methods for the same reason as described above. .
As described above, a preferable method for producing the polypropylene resin composition of the present invention includes a method of adding the fiber (B) after kneading components other than the fiber (B) in the kneading step. The polypropylene resin composition of the present invention can be produced by the production method.

2. Manufacturing method and use of molded body The molded body of the present invention can be produced by, for example, injection molding (gas injection molding, two-color injection molding, core back injection molding, sandwich injection molding, etc.) Including), injection compression molding (press injection), extrusion molding, sheet molding, and hollow molding, and the like. Among these, it is preferable to obtain by injection molding or injection compression molding.

The polypropylene resin composition of the present invention exhibits flame retardancy and drip resistance superior to conventionally known flame retardant polyolefin resins, and not only satisfies the UL94-5V standard, but also mechanical properties and weather resistance, molding. Excellent in properties.
Although the expression mechanism of the action is not clear, the present inventors consider as follows.
That is, in the polypropylene resin composition of the present invention and a molded product obtained by molding it, the polytetrafluoroethylene resin (D) improves the melt tension, and when the component (X) is further used, Since the coalescence (X) is a long-chain branched type, its melt tension is remarkably improved, and the effect of drip resistance is exhibited.
In addition, since organic flame retardants are used as flame retardants, phosphorus flame retardants, especially phosphate flame retardants, are thermally decomposed into polymetaphosphoric acid during combustion, and are protected by the generated phosphate layer. As a result of the formation of the layer and the dehydrating action by polymetaphosphoric acid, the flame retardant effect is exhibited by blocking oxygen by forming a carbon film to be formed.

  The melt flow rate (MFR) of the entire polypropylene resin composition of the present invention is usually 0.05 to 100 g / 10 minutes, preferably 0.1 to 50 g / 10 minutes, more preferably 0.3 to 30 g / 10 minutes. The range is more preferably 0.5 to 20 g / 10 minutes, and particularly preferably 1 to 10 g / 10 minutes. By setting the melt flow rate (MFR) of the entire polypropylene resin composition of the present invention within such a range, the polypropylene resin composition of the present invention maintains good moldability, and particularly injection molding is used. In some cases, this characteristic is preferably exhibited. This MFR is in accordance with JIS K6921-2 “Plastic—Polypropylene (PP) molding and extrusion materials—Part 2: How to make test pieces and how to obtain properties”. It is a value measured at a load of 2.16 kg.

  That the polypropylene resin composition of the present invention has a good flexural modulus and flexural strength and has a high impact strength means that the molded product has a good mechanical strength. Yes. Since the polypropylene resin composition of the present invention contains the polytetrafluoroethylene resin (D) as an essential component, and preferably contains a polypropylene resin (X) having a long chain branch, these various mechanical properties are good. I think it will be balanced. The flexural modulus and bending strength in this specification are evaluated by values measured at 23 ° C. according to JIS K7203, and Charpy impact strength (with notch) is determined by values measured at 23 ° C. according to JIS K7111. Be evaluated.

  The fact that the polypropylene resin composition of the present invention is hardly discolored means that the molded article has good burning characteristics during molding. The polypropylene resin composition of the present invention contains a polytetrafluoroethylene resin (D) as an essential component, and preferably contains a polypropylene resin (X) having a long chain branch. And although organic flame retardant (C) is contained as an essential component, discoloration occurs when a phosphorous flame retardant is used as the organic flame retardant (C) without any deterioration in the burning characteristics. It is difficult to burn (does not deteriorate the burning characteristics). The evaluation method of discoloration (burning characteristics) in this specification is as shown in the example section described later.

  Furthermore, in addition to the excellent mechanical properties, weather resistance, and moldability by containing the polypropylene resin composition of the present invention, a molded product obtained by molding the same, and the fiber (B), it has extremely high flame retardancy. Therefore, it can be suitably used for automobile parts, electric parts, container packaging members, building members, large members, and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, various physical properties of the polypropylene resin composition or its constituent components were measured and evaluated according to the following evaluation methods.

1. Evaluation method 1) Flame retardancy 1) -1 UL94-5V
Using an injection molding machine [Toshiba Machine Co., Ltd. IS100], a flame retardant evaluation test piece was molded and evaluated according to UL standard 94-5V at a cylinder temperature of 200 to 230 ° C. and a mold temperature of 40 ° C. (Thickness 2.0 mmt) When the determination fails to satisfy the 5VA standard at UL94-5V, “NG” is indicated.
1) -2 UL94-V
A test piece for flame retardancy evaluation was molded and evaluated by an injection molding machine [IS100 manufactured by Toshiba Corporation] according to the UL94-V standard. (Thickness 1.5 mmt or 3.0 mmt) When the determination did not satisfy the UL94-V standard, “NG” was indicated.

2) Melt flow rate (MFR):
In accordance with JIS K6921-2, “Plastics—Polypropylene (PP) molding and extrusion materials—Part 2: How to make test pieces and properties” Test flow: 230 ° C., load 2 .16 kg). The unit is g / 10 minutes.

3) Measurement of molecular weight distribution (Mw / Mn and Mz / Mw) by GPC The specific measurement method of GPC used in the present invention is as follows.
Apparatus: GPC manufactured by Waters (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
-Mobile phase solvent: orthodichlorobenzene (ODCB)
・ Measurement temperature: 140 ℃
・ Flow rate: 1.0 ml / min
・ Injection volume: 0.2ml
Sample preparation: A 1 mg / mL solution was prepared using ODCB (containing 0.5 mg / mL BHT) and dissolved at 140 ° C. for about 1 hour.
Conversion from the retention capacity obtained by the GPC measurement to the molecular weight was performed using a calibration curve of standard polystyrene (PS) prepared in advance. The standard polystyrenes used are the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve was prepared by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each would be 0.5 mg / mL. For the calibration curve, a cubic equation obtained by approximation by the least square method was used.
In addition, the following numerical value is used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

4) Melt book tension (MT)
It measured on the following conditions using the Toyo Seiki Seisakusho Capillograph.
・ Capillary: Diameter 2.0mm, length 40mm
・ Cylinder diameter: 9.55mm
・ Cylinder extrusion speed: 20 mm / min ・ Pickup speed: 4.0 m / min ・ Temperature: 230 ° C.
When the MT is extremely high, the resin may break at a take-up speed of 4.0 m / min. In such a case, the take-up speed is lowered and the tension at the maximum take-up speed is set as MT. did. The unit is gram.

5) Paraxylene soluble component amount (CXS)
A 2 g sample was dissolved in 300 ml of p-xylene (containing 0.5 mg / ml BHT) at 130 ° C. to prepare a solution, and then left at 25 ° C. for 12 hours. Thereafter, the precipitated polymer was filtered off, p-xylene was evaporated from the filtrate, and further dried under reduced pressure at 100 ° C. for 12 hours to recover a room temperature xylene-soluble component. The ratio [wt%] of the weight of the recovered component to the charged sample weight was defined as CXS.

6) mm fraction
The detail of the measuring method of mm fraction of the propylene unit 3 chain | strand by ¹³ C-NMR is as follows.
A sample of 375 mg was completely dissolved in 2.5 ml of deuterated 1,1,2,2, -tetrachloroethane in an NMR sample tube (10φ), and then measured at 125 ° C. by a proton complete decoupling method. The chemical shift was set to 74.2 ppm in the middle of the three peaks of deuterated 1,1,2,2-tetrachloroethane. Other carbon peak chemical shifts were based on this.
Flip angle: 90 degrees Pulse interval: 10 seconds Resonance frequency: 100 MHz or more Integration frequency: 10,000 times or more Observation range: -20 ppm to 179 ppm
Number of data points: 32768
The analysis of the mm fraction was performed using a ¹³ C-NMR spectrum measured under the above conditions.
Spectral assignment is made with reference to Macromolecules, 8 pp. 687 (1975) and Polymer, 30 pages, 1350 (1989), and the determination of mm fraction is described in paragraphs of JP2009-275207A It was carried out according to the method described in [0053] to [0065].

7) Branching index g ′
The branching index (g ′) is determined according to the intrinsic viscosity ([η] br) obtained by measuring a sample of the polypropylene resin (X) having a long-chain branched structure with the following Viscometer according to the method described above, and linear It calculated as a ratio ([η] br / [η] lin) to the intrinsic viscosity ([η] lin) obtained by measuring a polymer (Novatech PP (registered trademark) grade name: FY6 manufactured by Nippon Polypro Co., Ltd.).
As a GPC device equipped with a differential refractometer (RI) and a viscosity detector (Viscometer), Waters Alliance GPCV2000 is used, and as a light scattering detector, a multi-angle laser light scattering detector (MALLS) manufactured by Wyatt Technology. DAWN-E was used. The detector is connected in the order of MALLS, RI, and Viscometer, and the mobile phase solvent is 1,2,4-trichlorobenzene (added with BASF Japan antioxidant Irganox 1076 at a concentration of 0.5 mg / mL). It was.
The flow rate was 1 mL / min, and the column was used by connecting two Tosoh Corporation GMHHR-H (S) HT, and the temperature of the column, the sample injection section and each detector was 140 ° C. The sample concentration was 1 mg / mL, and the injection volume (sample loop volume) was 0.2175 mL.

8) Degree of strain hardening in measurement of elongational viscosity (λmax (0.1))
The extensional viscosity was measured under the following conditions.
・ Device: Ares manufactured by Rheometrics
・ Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
・ Measurement temperature: 180 ℃
-Strain rate: 0.1 / sec
-Preparation of test piece: A sheet of 18 mm x 10 mm and a thickness of 0.7 mm was prepared by press molding (manufactured by masada seisakusyo, AH-200, heating temperature: 180 ° C, cooling temperature: 25 ° C), and a measurement sample piece It was.
9) Melting point Using a differential operation calorimeter (DSC, DSC6200 model, manufactured by Seiko Instruments Inc.), once the temperature was raised to 200 ° C. and the thermal history was erased at a rate of 10 ° C./min. The temperature was lowered to 40 ° C., and the temperature at the top of the endothermic peak when measured at a rate of temperature increase of 10 ° C./min was taken as the melting point.

9) Flexural modulus Measured at 23 ° C. according to JIS K7203. The dimension of the molded product was 90 × 10 × 4 mm. The unit is MPa.
10) Bending strength Measured at 23 ° C. according to JIS K7203. The dimension of the molded product was 90 × 10 × 4 mm. The unit is MPa.
11) Charpy impact strength (with notch)
It was measured at a measurement temperature of 23 ° C. in accordance with JIS K7111. The unit is kJ / m ² .

12) Formability Sheet test pieces (120 × 120 × 2 mmt) were molded under the following conditions using an injection molding machine [IS100 manufactured by Toshiba Corporation].
Cylinder temperature: 220 ° C
Mold cooling temperature: 40 ° C
Injection speed: 35mm / sec
Filling time: 15 sec
The molded specimen was visually observed and evaluated according to the following evaluation items.
○: Short shot (unfilled) does not occur, no sink marks are observed, and good △: Short shot (unfilled) does not occur, but some sink marks are observed ×: Short shot (unfilled) is observed Occurred

13) Discoloration test (burning characteristics during molding)
The burn characteristics during molding were evaluated by the following procedure.
(I) It is made to retain for 30 minutes in the cylinder of the injection molding machine (TOSHIBA IS100) whose molding temperature is 220 degreeC.
(Ii) Constant molding (IS100 manufactured by Toshiba, mold temperature: 40 ° C., injection speed: 35 mm / sec, filling time: 20 sec, cooling time: 30 sec), and a test piece is produced (1 cycle 1 min).
(Iii) Visually confirm the test piece.
(Criteria)
○: Almost no discoloration is observed.
Δ: Some discoloration is observed.
X: Discoloration is remarkably recognized.

2. Materials and Evaluation (1) Polypropylene resin (A)
(1-1) Polypropylene resin (Y)
(Y-1) manufactured by Nippon Polypro Co., Ltd., Novatec PP series (polypropylene homopolymer, MFR 40 g / 10 min, isotactic pentad fraction (mmmm fraction) 0.98)
(1-2) Polypropylene resin (X) having a long-chain branched structure
(X-1): The polypropylene resin (X-1) having a long chain branched structure produced in Production Example 1 below was used.

[Production Example 1]
<Synthesis example 1 of catalyst component (A)>
Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium: (component [A-1] ( Synthesis of complex 1):
(I) Synthesis of 4- (4-i-propylphenyl) indene To a 500 ml glass reaction vessel, 15 g (91 mmol) of 4-i-propylphenylboronic acid and 200 ml of dimethoxyethane (DME) were added, and 90 g of cesium carbonate ( 0.28 mol) and 100 ml of water were added, 13 g (67 mmol) of 4-bromoindene and 5 g (4 mmol) of tetrakistriphenylphosphinopalladium were added in this order, and the mixture was heated at 80 ° C. for 6 hours.
After allowing to cool, the reaction solution was poured into 500 ml of distilled water, transferred to a separatory funnel, and extracted with diisopropyl ether. The ether layer was washed with saturated brine and dried over sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 15.4 g (yield 99%) of 4- (4-i-propylphenyl) indene as a colorless liquid.

(Ii) Synthesis of 2-bromo-4- (4-i-propylphenyl) indene In a 500 ml glass reaction vessel, 15.4 g (67 mmol) of 4- (4-i-propylphenyl) indene, 7.2 ml of distilled water DMSO (200 ml) was added, and N-bromosuccinimide (17 g, 93 mmol) was gradually added thereto. The mixture was stirred at room temperature for 2 hours, poured into 500 ml of ice water, and extracted three times with 100 ml of toluene. The toluene layer was washed with saturated brine, 2 g (11 mmol) of p-toluenesulfonic acid was added, and the mixture was heated to reflux for 3 hours while removing moisture. The reaction mixture was allowed to cool, washed with saturated brine, and dried over sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to obtain 19.8 g (yield 96%) of 2-bromo-4- (4-i-propylphenyl) indene as a yellow liquid. .

(Iii) Synthesis of 2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indene In a 500 ml glass reaction vessel, 6.7 g (82 ml mol) of 2-methylfuran and 100 ml of DME were added. In addition, it was cooled to −70 ° C. in a dry ice-methanol bath. To this was added dropwise 51 ml (81 mmol) of a 1.59 mol / L n-butyllithium-n-hexane solution, and the mixture was stirred for 3 hours. The solution was cooled to −70 ° C., and a solution of 20 ml (87 mmol) of triisopropyl borate and 50 ml of DME was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
The reaction solution was hydrolyzed with 50 ml of distilled water, and then a solution of 223 g of potassium carbonate and 100 ml of water and 19.8 gg (63 mmol) of 2-bromo-4- (4-i-propylphenyl) indene were added in that order at 80 ° C. The mixture was heated and reacted for 3 hours while removing low-boiling components.
After allowing to cool, the reaction solution was poured into 300 ml of distilled water, transferred to a separatory funnel and extracted three times with diisopropyl ether. The ether layer was washed with saturated brine and dried over sodium sulfate. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to obtain 19.6 g of 2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indene as a colorless liquid ( Yield 99%).

(Iv) Synthesis of dimethylbis (2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl) silane In a 500 ml glass reaction vessel, 2- (5-methyl-2- Furyl) -4- (4-i-propylphenyl) indene (9.1 g, 29 mmol) and THF (200 ml) were added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. To this, 17 ml (28 mmol) of a 1.66 mol / L n-butyllithium-hexane solution was dropped, and the mixture was stirred as it was for 3 hours. The mixture was cooled to −70 ° C., 0.1 ml (2 mmol) of 1-methylimidazole and 1.8 g (14 mmol) of dimethyldichlorosilane were sequentially added, and the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, transferred to a separatory funnel and washed with brine until neutral, and sodium sulfate was added to dry the reaction solution. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column. 8.6 g (88% yield) of a yellow solid was obtained.

(V) Synthesis of dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium In a 500 ml glass reaction vessel, 8.6 g (13 mmol) of dimethylbis (2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl) silane and 300 ml of diethyl ether were added, and -70 ° C. in a dry ice-methanol bath. Until cooled. To this, 15 ml (25 mmol) of a 1.66 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred for 3 hours. The solvent of the reaction solution was distilled off under reduced pressure, 400 ml of toluene and 40 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 4.0 g (13 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure, recrystallized with dichloromethane-hexane, and dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl]. }] 7.6 g (yield 65%) of hafnium racemate as yellow crystals was obtained.
The identified value by ^{1 H-NMR} of the obtained racemates are described below.
¹ H-NMR (C6D6) identification results Racemate: δ0.95 (s, 6H), δ1.10 (d, 12H), δ2.08 (s, 6H), δ2.67 (m, 2H), δ5. 80 (d, 2H), δ 6.37 (d, 2H), δ 6.74 (dd, 2H), δ 7.07 (d, 2H), δ 7.13 (d, 4H), δ 7.28 (s, 2H ), Δ 7.30 (d, 2H), δ 7.83 (d, 4H).

<Synthesis example 2 of catalyst component (A)>
Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium: (synthesis of component [A-1] (complex 2)):
The synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium is carried out according to the method described in Example 1 of JP-A-11-240909. It carried out like.

<Catalyst synthesis example 1>
(I) Chemical treatment of ion-exchange layered silicate 96% sulfuric acid (668 g) was added to 2,264 g of distilled water in a separable flask, and then montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL: average particle size 19 μm) as a layered silicate. ) 4L was added. The slurry was heated at 90 ° C. for 210 minutes. When 4,000 g of distilled water was added to the reaction slurry and filtered, 810 g of a cake-like solid was obtained.
Next, 432 g of lithium sulfate and 1,924 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution. The slurry was reacted at room temperature for 120 minutes. 4 L of distilled water was added to this slurry, followed by filtration, further washing with distilled water to pH 5-6, and filtration. As a result, 760 g of a cake-like solid was obtained.
The obtained solid was preliminarily dried overnight at 100 ° C. under a nitrogen stream, and then coarse particles of 53 μm or more were removed, followed by drying under reduced pressure at 200 ° C. for 2 hours to obtain 220 g of chemically treated smectite.
The composition of this chemically treated smectite is Al: 6.45 wt%, Si: 38.30 wt%, Mg: 0.98 wt%, Fe: 1.88 wt%, Li: 0.16 wt%, Al / Si = 0.175 [mol / mol].

(Ii) Catalyst preparation and prepolymerization In a three-necked flask (volume: 1 L), 20 g of the chemically treated smectite obtained above was placed, and heptane (132 mL) was added to form a slurry, which was triisobutylaluminum (25 mmol: concentration) 143 mg / mL heptane solution (68.0 mL) was added, and the mixture was stirred for 1 hour, washed with heptane until the residual liquid ratio became 1/100, and heptane was added so that the total volume became 100 mL.
In another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl)-] prepared in Synthesis Example 1 of the catalyst component (A) was used. 4- (4-i-propylphenyl) indenyl}] hafnium (210 μmol) is dissolved in toluene (42 mL) (solution 1), and the catalyst component (A) is synthesized in another flask (volume 200 mL). Rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (90 μmol) prepared in Example 2 was dissolved in toluene (18 mL) (solution 2 ).
Triisobutylaluminum (0.84 mmol: 1.2 mL of a heptane solution with a concentration of 143 mg / mL) was added to a 1 L flask containing the chemically treated smectite, and then the above solution 1 was added and stirred at room temperature for 20 minutes. Thereafter, triisobutylaluminum (0.36 mmol: 0.50 mL of a heptane solution having a concentration of 143 mg / mL) was added, and then the above solution 2 was added and stirred at room temperature for 1 hour.
Thereafter, 338 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed while maintaining the temperature at 40 ° C. for 4 hours. Thereafter, propylene feed was stopped and residual polymerization was carried out for 1 hour. After removing the supernatant of the resulting catalyst slurry by decantation, triisobutylaluminum (6 mmol: 17.0 mL of a heptane solution having a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes.
This solid was dried under reduced pressure for 1 hour to obtain 52.8 g of a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.64.
Hereinafter, this is referred to as “preliminary polymerization catalyst 1”.

<Polymerization>
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 40 kg of sufficiently dehydrated liquefied propylene was introduced. To this was added 4.4 liters of hydrogen (as a standard volume) and 470 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution, and the internal temperature was raised to 70 ° C. Next, 2.4 g of the prepolymerized catalyst 1 (by weight excluding the prepolymerized polymer) was injected with argon to initiate polymerization, and the internal temperature was maintained at 70 ° C. After 2 hours, 100 ml of ethanol was injected, purged of unreacted propylene, and the inside of the autoclave was purged with nitrogen to terminate the polymerization.
The obtained polymer was dried under a nitrogen stream at 90 ° C. for 1 hour to obtain 16.5 kg of a polymer (hereinafter referred to as “XX”).
The catalytic activity was 6880 (g-XX / g-cat). The MFR was 1.0 g / 10 minutes.

[Production of X-1]
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl), which is a phenolic antioxidant, with respect to 100 parts by weight of the polypropylene resin (XX) having a long chain branched structure produced in Production Example 1. -4'-hydroxyphenyl) propionate] methane (trade name: IRGANOX 1010, manufactured by BASF Japan Ltd.) 0.125 parts by weight, tris (2,4-di-t-butylphenyl) which is a phosphite antioxidant ) Phosphite (trade name: IRGAFOS 168, manufactured by BASF Japan Ltd.) 0.125 parts by weight was mixed and mixed for 3 minutes at room temperature using a high-speed agitating mixer (Henschel mixer, trade name). Melt kneading was carried out with a shaft extruder to obtain a polypropylene resin (X-1) pellet having a long-chain branched structure.
About these pellets (X-1), melting point, MFR, paraxylene soluble component amount (CXS), ¹³ C-NMR, GPC (Mw / Mn and Mz / Mw), branching index (mm), melt tension (MT ), And the degree of strain hardening (λmax (0.1)) in the measurement of elongational viscosity was evaluated. The evaluation results are shown in Table 1.

(X-2): The polypropylene resin (X-2) having a long chain branched structure produced in Production Example 2 below was used.

[Production Example 2]
In the <polymerization> operation of the above [Production Example 1], 45 kg of sufficiently dehydrated liquefied propylene was introduced, 10.0 liters of hydrogen (as a standard state volume) was added thereto, and the prepolymerized catalyst 1 was added in 2. 04 g (by weight excluding the prepolymerized polymer) was injected to start the polymerization, and the same operation as in [Production Example 1] was performed, and the obtained polymer was dried for 1 hour under a nitrogen stream at 90 ° C. 18.0 kg of a polymer (hereinafter referred to as “XXX”) was obtained. The catalytic activity was 8800 (g-XXX / g-cat), and the MFR was 10.0 g / 10 minutes.
Additives were similarly added to the obtained polypropylene resin (XXX) having a long-chain branched structure, and the evaluation results of the obtained (X-2) are shown in Table 1.

(2) Fiber (B)
(B-1) manufactured by Nippon Electric Glass Co., Ltd., glass fiber: T480 (chopped strand, fiber diameter 13 μm, length 4 mm)

(3) Organic flame retardant (C)
(C-1) ADEKA, FP2200 [Phosphorus flame retardant]
(4) Polytetrafluoroethylene resin (D)
(D-1) Made by Daikin Industries, Ltd. PTFE: Polyflon FA500H (unmodified, PTFE content 100% by weight)
(5) Other additives (E)
As other additives (E), antioxidants (E-1: manufactured by BASF, Irganox 1010), (E-2: manufactured by ADEKA, PEP36, neutralizer (E-3: manufactured by NOF Corporation) , Calcium stearate) and an interfacial treating agent (E-4: manufactured by Mitsubishi Chemical Corporation, maleic acid-modified polypropylene: CMPP2).

[Examples 1-16, Comparative Examples 1-4]
Polytetrafluoroethylene resin for a total of 100 parts by weight of polypropylene resin (A) (polypropylene resin (Y), polypropylene resin (X) having a long-term branched structure), fiber (B), and organic flame retardant (C) (D) is blended in the proportions shown in Table 2, Table 3 and Table 4, and as additional additives, antioxidants (E-1: BASF, Irganox 1010), (E-2: ADEKA) Tables 2 and 3 show PEP36, neutralizer (E-3: manufactured by Nippon Oil & Fats Co., Ltd., calcium stearate), and surface treatment agent (E-4: manufactured by Mitsubishi Chemical Corporation, maleic acid-modified polypropylene: CMPP2). And blended at the ratios shown in Table 4 and mixed for 3 minutes at room temperature using a high-speed stirring mixer (Henschel mixer, trade name), then melt-kneaded and extruded with a twin-screw extruder, After passing through the tank, the strand was cut with a strand cutter to obtain pellets, where the composition ratios of the respective components shown in Tables 2, 3 and 4 are all expressed in parts by weight. The proportion of (Y) and the polypropylene resin (X) having a long-term branched structure (provided that the total of the polypropylene resin (Y) and the polypropylene resin (X) having a long-chain branched structure is 100% by weight) is polypropylene. In the column of the resin (Y) and the polypropylene resin (X) having a long chain branched structure, it is described in parentheses.
The obtained pellets were evaluated according to the evaluation method. The evaluation results are shown in Table 2, Table 3 and Table 4.

[Comparative Example 5]
In the above examples, polypropylene resin (A) (polypropylene resin (X) having a long-term branched structure, polypropylene resin (Y)), fiber (B), organic flame retardant (C), polytetrafluoroethylene resin In place of (D), antioxidants (E-1), (E-2), neutralizing agent (E-3) and interfacial treating agent (E-4), commercially available flame-retardant ABS resin (technopolymer) The product was evaluated in the same manner as in the above example except that F5450, a flame retardant and various additives were used) were used. In the melt flow rate evaluation method of the present application, the fluidity of the entire resin composition was poor, and the melt flow rate could not be measured.

[Comparative Example 6]
In Comparative Example 5, a commercially available flame retardant polycarbonate resin (PC resin) (made by Idemitsu Kosan Co., Ltd .: RY1900, containing flame retardant and various additives) was used instead of the flame retardant ABS resin. Others were evaluated in the same manner as in Comparative Example 5. In the melt flow rate evaluation method of the present application, since the entire resin composition does not melt, the fluidity is poor, and the melt flow rate cannot be measured.

[Comparative Example 7]
In the comparative example 5, in place of the flame retardant ABS resin, a commercially available glass fiber-containing flame retardant ABS resin (manufactured by Toray Industries, Inc .: 855VG20, containing 20% by weight glass fiber, flame retardant and various additives). The operation was performed in the same manner as in Comparative Example 5 except that the above was used. In the melt flow rate evaluation method of the present application, the fluidity of the entire resin composition was poor, and the melt flow rate could not be measured.

3. Evaluation results From the results shown in Table 2, Table 3 and Table 4, tetrafluoroethylene resin (D) was used as the polypropylene resin composition of the present invention, polypropylene resin (A), fiber (B) and organic flame retardant ( It can be seen that by combining a specific amount with C), extremely good flame retardancy is exhibited. That is, in order to achieve “evaluation 5VA of UL94-5V” which is an evaluation index of flame retardancy, it is necessary to satisfy both self-extinguishing property and drip resistance. Has achieved a sex assessment. Further, by blending the fiber (B) within the range specified in the present invention, the mechanical properties are also improved. Further, in the examples, there are no defects such as moldability due to compounding and poor appearance due to molding.
Compared with Examples 1 and 2, since Comparative Examples 1 and 4 do not use tetrafluoroethylene resin (D), the drip property during combustion cannot be suppressed and satisfactory flame retardancy is not obtained. . On the other hand, in Comparative Example 2, since the amount of tetrafluoroethylene resin (D) used was too large, it was actually impossible to produce. This is presumably because the amount of the tetrafluoroethylene resin (D) used is too large, so that the melt tension increases, but the melt ductility deteriorates.

  On the other hand, since the fiber (B) has better heat conduction than polypropylene, if there is no fiber (B), the heat generated during combustion is stored inside the resin, and the viscosity of the resin part is rapidly reduced. Comparing Examples 7 and 8 with Comparative Example 3, even when the fiber (B) is not used, the drip property is suppressed by using the tetrafluoroethylene resin (D) as long as the heat amount is about the UL94-V test. However, when exposed to the heat of UL94-5V test, it is difficult to suppress dripping during combustion without using fiber (B) even if tetrafluoroethylene resin (D) is used. It can be seen that it is. Also, in other examples, it is clear that extremely good flame retardancy is exhibited by satisfying the provisions of the present application.

  Moreover, in Comparative Examples 5 to 7 using resins other than polypropylene, in Comparative Examples 5 and 7 using ABS resin, the flame retardancy is relatively good, but the flowability is poor, so the moldability is improved. The result was inferior and molding discoloration was insufficient. On the other hand, in Comparative Example 6 using a polycarbonate resin, the flame retardancy, moldability and molding discoloration were all insufficient.

  From these examples and comparative examples, in order to satisfy both high flame retardancy and mechanical properties satisfying UL94-5V required in the present application, a predetermined amount of tetrafluoroethylene resin (D) is added to the polypropylene resin (A). ), Fiber (B) and organic flame retardant (C) are essential.

  The polypropylene resin composition of the present invention has excellent flame resistance in addition to excellent mechanical properties, moldability, and weather resistance, and in particular, by combining both self-extinguishing property and drip resistance, “UL94-5V By being able to achieve “evaluation 5VA”, it can be suitably used for automobile parts, electrical parts, container packaging members, building members, large members, and the like.

Claims (5)

A polypropylene resin (A) that satisfies the following conditions (A-1) and (A-2), a fiber (B) that satisfies the following condition (B-1), and an organic flame retardant (C): And a polytetrafluoroethylene resin (D), and satisfy the following condition (a).
Condition (A-1)
The polypropylene resin (A) contains a polypropylene resin (Y) having the following properties (Yi) to (Y-ii).
Characteristic (Yi): at least one polypropylene resin selected from the group consisting of a propylene homopolymer, a propylene-α-olefin block copolymer and a propylene-α-olefin random copolymer, and the following long-chain branch It does not correspond to the polypropylene resin (X) having a structure.
Characteristic (Y-ii): The polypropylene resin (Y) has a melt flow rate (MFR) (230 ° C., 2.16 kg load) of 1.0 to 200 g / 10 min.
Condition (A-2)
The polypropylene resin (A) is at least selected from the group consisting of the polypropylene resin (Y) and a polypropylene resin (X) having a long chain branched structure having the following properties (Xi) to (X-iv): Contains one kind of polypropylene resin.
Characteristic (X-i): Melt flow rate (MFR) (230 ° C., 2.16 kg load) is 0.1 to 30.0 g / 10 min.
Characteristic (X-ii): GPC molecular weight distribution Mw / Mn is 3.0 to 10.0 and Mz / Mw is 2.5 to 10.0.
Characteristic (X-iii): Melt tension (MT) (unit: g) is
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy one of the following.
Characteristic (X-iv): 25 degreeC paraxylene soluble component amount (CXS) is less than 5.0 weight% with respect to polypropylene resin (X) whole quantity.
Condition (B-1)
The fiber (B) is at least one selected from the group consisting of glass fiber and carbon fiber.
Condition (A)
The content of each component is in the range of 20 to 77 parts by weight of polypropylene resin (A), 5 to 40 parts by weight of fiber (B) and 18 to 40 parts by weight of organic flame retardant (C) (provided that polypropylene resin ( A), fiber (B), and organic flame retardant (C) are 100 parts by weight), and polypropylene resin (A), fiber (B), and organic flame retardant (C) The polytetrafluoroethylene resin (D) is in the range of 0.01 to 1.5 parts by weight with respect to 100 parts by weight of the total amount. The polypropylene resin composition according to claim 1, wherein the polypropylene resin (A) satisfies the following condition (A-3).
Condition (A-3)
The polypropylene resin (A) contains a polypropylene resin (Y) and a polypropylene resin (X) having a long chain branched structure, and the proportion thereof has a long chain branched structure of 70 to 99% by weight of the polypropylene resin (Y). 1 to 30% by weight of the polypropylene resin (X) (provided that the total of the polypropylene resin (Y) and the polypropylene resin (X) having a long chain branched structure is 100% by weight).   The polypropylene resin composition according to claim 1 or 2, wherein the organic flame retardant (C) is a phosphorus flame retardant.   The polypropylene resin composition according to any one of claims 1 to 3, wherein the fiber (B) is a glass fiber.   The molded object formed by shape | molding the polypropylene resin composition of any one of Claims 1 thru | or 4.