JP2009275074A - Flame-retardant polypropylene resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant polypropylene resin composition having excellent drip preventing properties, appearance or the like upon burning even if a PTFE is not added and having excellent flame retardancy with a small compounding amount of flame retardant. <P>SOLUTION: The flame-retardant polypropylene resin composition contains 10 to 50 pts.wt. non-halogen-based flame retardant (C) to 100 pts.wt. polypropylene resin component including 60 to 99 wt.% crystalline polypropylene resin (A) having 0.1 to 80 g/10 min MFR and isotactic triad fraction (mm) of 0.95 or more and 1 to 40 wt.% propylene-based polymer (B) comprising an insoluble component (I) and a soluble component (S) in p-xylene at 25°C and having (i) a weight-average molecular weight (Mw) measured by GPC of 100,000 to 1,000,000, (ii) ≤0.3 wt.% insoluble component in heat p-xylene, and (iii) a degree (γmax) of strain hardening measured by elongational viscosity of 1.1 or more. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a flame retardant polypropylene resin composition, and more specifically, a propylene polymer composed of a polymer having a specific branched structure is combined with a non-halogen flame retardant such as a phosphate flame retardant. The present invention relates to a flame retardant polypropylene resin composition obtained by blending a specific amount with a resin.

Flame retardant polypropylene is widely used to blend a flame retardant composition composed of a halogenated flame retardant and an antimony compound because it can exhibit flame retardancy in a relatively small amount and does not easily impair the advantageous performance of the polypropylene resin. It has been broken.
However, since there is a problem that halogen gas is generated during combustion, 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, the flame retardancy evaluation standard requires a characteristic that the resin in a burned or molten state is difficult to drip and spread to other objects (so-called drip prevention effect). Yes.

It is known that tetrafluoroethylene resin (PTFE) has a large drip-preventing effect in making a thermoplastic resin flame-retardant when added in a small amount to the thermoplastic resin. In general, when PTFE is added to a thermoplastic resin, the melting point of PTFE is higher than the processing temperature of the thermoplastic resin, so that it is kneaded below the melting point of PTFE. PTFE is easily fibrillated or aggregated by receiving a shearing force, and PTFE kneaded and added to a thermoplastic resin is said to be fiberized in a network and exhibit effects such as drip prevention.
However, the ease of fiberizing and agglomerating PTFE is very troublesome in handling, and various techniques for improving the handling properties have been proposed. For example, a method of treating PTFE with a higher fatty acid dispersant in advance has been proposed (see Patent Document 1).

On the other hand, in order to improve the handleability, various granular compositions containing PTFE at a high concentration have been studied (for example, see Patent Documents 2 to 5).
However, the polyolefin resin has problems such as insufficient dispersibility of PTFE, flame retardancy, anti-drip property during combustion, and insufficient rigidity even in these technologies.

Moreover, in order to improve the flame retardance of polyolefin, the method of using a specific phosphate flame retardant and a drip inhibitor in combination has been proposed (see Patent Document 6).
However, even with these methods, a composition having both sufficient flame retardancy and rigidity has not been achieved.
Furthermore, in the above proposal, in view of practicality, the addition of PTFE is indispensable and does not satisfy the non-halogen requirement.

On the other hand, a technique for preventing the drip by increasing the melt tension of the polypropylene resin itself without adding PTFE has been proposed (see Patent Document 7). This technology meets the non-halogen requirements and is expected.
However, according to such a proposal, the polypropylene resin is (a) polyethylene 0 consisting of an ethylene homopolymer or an ethylene olefin copolymer containing 50% by weight or more of ethylene polymer units, and having an intrinsic viscosity of 15 to 100 dl / g. 0.01 to 5 parts by weight, and (b) a propylene homopolymer or 100 parts by weight of a propylene ethylene copolymer containing 50% by weight or more of a propylene polymer unit, and a melt tension at 230 ° C. is 1 to 20 cN, Although the present inventors have examined the MFR, the melting point, and the density, when the processing temperature during molding is increased, there is a problem that the drip prevention effect of the resin itself decreases.
Japanese Patent Laid-Open No. 10-30046 JP 09-324124 A JP 09-324071 A JP 09-324092 A JP 2001-2947 A JP-A-2003-26935 Japanese Patent Laid-Open No. 10-231397

  An object of the present invention is to solve the problem of rigidity reduction, which is a flame retardant characteristic and a basic physical property of polypropylene resin, in view of the current state of the prior art, and prevents dripping at the time of combustion without adding PTFE. Another object of the present invention is to provide a flame retardant polypropylene resin composition having an excellent appearance and the like, and having excellent flame retardancy with a small amount of flame retardant.

  As a result of intensive research to solve the above problems, the present inventors have determined that a propylene-based polymer composed of a polymer having a specific branched structure is a non-halogen-based difficulty such as a phosphate-based flame retardant. When a specific amount is blended with a polypropylene resin together with a flame retardant, it is possible to obtain a flame retardant polypropylene resin composition having excellent anti-drip property during combustion, appearance, etc. and having excellent flame retardancy with a small amount of flame retardant. The headline and the present invention were completed.

That is, according to the first aspect of the present invention, the crystallinity has an MFR (230 ° C., 2.16 kg load) of 0.1 to 80 g / 10 min and an isotactic triad fraction (mm) of 0.95 or more. The polypropylene resin (A) is composed of 60 to 99% by weight and the following component (I) that is insoluble in p-xylene at 25 ° C. and component (S) that is soluble in p-xylene at 25 ° C., and (i) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000, (ii) the component insoluble in hot p-xylene is 0.3% by weight or less, and (iii) strain hardening in the measurement of elongational viscosity. The halogen-free flame retardant (C) is contained in an amount of 10 to 50 parts by weight with respect to 100 parts by weight of the polypropylene resin component consisting of 1 to 40% by weight of the propylene polymer (B) having a degree (λmax) of 1.1 or more. Features Flame-retardant polypropylene resin composition is provided.
Component (I): Component (CXIS) that is insoluble in p-xylene at 25 ° C. having the requirements defined in the following (I1) to (I5).
(I1) 20 to 95% by weight based on the total amount of the polymer (B).
(I2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(I3) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 0.93 or more.
(I4) The degree of strain hardening (λmax) in the measurement of elongational viscosity is 2.0 or more.
(I5) A propylene unit and an ethylene unit or an α-olefin unit are contained.
Component (S): Component (CXS) that dissolves in p-xylene at 25 ° C. having the requirements defined in the following (S1) to (S3).
(S1) 5 to 80% by weight based on the total amount of the polymer (B).
(S2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(S3) Contains propylene units, ethylene units and / or α-olefin units.

According to the second invention of the present invention, in the first invention, the component (S) of the propylene-based polymer (B) further has (S4) a strain hardening degree (λmax) of 1. There is provided a flame retardant polypropylene resin composition characterized by having two or more requirements.
According to the third invention of the present invention, in the first invention, the propylene-based polymer (B) has a crystalline propylene polymer segment as a side chain and an amorphous propylene copolymer segment as a main chain. Provided is a flame retardant polypropylene resin composition comprising a polymer having a branched structure.
Furthermore, according to the fourth invention of the present invention, in the first invention, the component (I) of the propylene-based polymer (B) has a crystalline propylene polymer segment as a side chain, and an amorphous propylene copolymer segment. There is provided a flame retardant polypropylene resin composition comprising a polymer having a branched structure having a main chain as a main chain.

According to the fifth aspect of the present invention, in the first aspect, the component (I) of the propylene polymer (B) contains an ethylene unit and has an ethylene content of 0.1 to 10. There is provided a flame retardant polypropylene resin composition characterized by being in wt%.
Furthermore, according to the sixth invention of the present invention, in the first invention, the component (S) of the propylene-based polymer (B) contains an ethylene unit and has an ethylene content of 10 to 60% by weight. A flame retardant polypropylene resin composition is provided.

  According to a seventh invention of the present invention, in any one of the first to sixth inventions, the non-halogen flame retardant (C) is a phosphate flame retardant, a flame retardant polypropylene resin composition Things are provided.

  In the flame-retardant polypropylene resin composition of the present invention, a propylene polymer composed of a polymer having a specific branched structure is added to a polypropylene resin together with a non-halogen flame retardant such as a phosphate flame retardant. By blending, in addition to excellent mechanical strength and moldability, it has excellent flame retardancy, and is particularly excellent in drip prevention during combustion. Furthermore, since a halogen-free flame retardant such as a phosphate flame retardant is used as the flame retardant and no chlorine, fluorine and bromine-containing compounds are used, the environmental impact is small.

The flame-retardant polypropylene resin composition of the present invention is a crystalline polypropylene having an MFR (230 ° C., 2.16 kg load) of 0.1 to 80 g / 10 min and an isotactic triad fraction (mm) of 0.95 or more. The resin (A) is composed of 60 to 99% by weight and the following component (I) that is insoluble in p-xylene at 25 ° C. and component (S) that is soluble in p-xylene at 25 ° C., and (i) GPC The weight average molecular weight (Mw) measured in (100) is 100,000 to 1,000,000, (ii) the component insoluble in hot p-xylene is 0.3% by weight or less, and (iii) the strain hardening degree in the measurement of elongational viscosity. 10 to 50 parts by weight of the halogen-free flame retardant (C) is contained with respect to 100 parts by weight of the polypropylene resin component consisting of 1 to 40% by weight of the propylene polymer (B) having (λmax) of 1.1 or more. It is an butterfly.
Component (I): Component (CXIS) that is insoluble in p-xylene at 25 ° C. having the requirements defined in the following (I1) to (I5).
(I1) 20 to 95% by weight based on the total amount of the polymer (B).
(I2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(I3) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 0.93 or more.
(I4) The degree of strain hardening (λmax) in the measurement of elongational viscosity is 2.0 or more.
(I5) A propylene unit and an ethylene unit or an α-olefin unit are contained.
Component (S): Component (CXS) that dissolves in p-xylene at 25 ° C. having the requirements defined in the following (S1) to (S3).
(S1) 5 to 80% by weight based on the total amount of the polymer (B).
(S2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(S3) Contains propylene units, ethylene units and / or α-olefin units.

Hereinafter, the components of the flame retardant polypropylene resin composition, the adjustment of the flame retardant polypropylene resin composition, and the like will be described in detail.
I. 1. Components of flame retardant polypropylene resin composition Crystalline polypropylene resin (A)
The crystalline polypropylene resin (A) used in the flame retardant polypropylene resin composition of the present invention includes (i) a crystalline propylene homopolymer, (ii) propylene as a main component, and the propylene and ethylene or carbon number 4 Examples thereof include random copolymers with the above α-olefins, (iii) so-called block copolymers made of a crystalline polypropylene and a rubbery copolymer of propylene-ethylene, or (iv) a mixture of two or more of these. It is done.

  The melt flow rate (MFR, measurement conditions: 230 ° C., 2.16 kg load) of the crystalline polypropylene resin (A) according to the present invention is 0.1 to 80 g / 10 minutes, preferably 5 to 60 g / 10 minutes. And having a high degree of stereoregularity having an isotactic triad fraction (mm) of 0.95 or more, preferably 0.955 or more, and more preferably 0.96 or more.

The isotactic triad fraction (mm) in the present invention is the mm fraction of three propylene units obtained by ¹³ C-NMR.
The mm fraction is a ratio of three propylene unit chains in which the direction of methyl branching in each propylene unit is the same among arbitrary three propylene unit chains composed of head-to-tail bonds in the polymer chain. 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.
When the mm fraction of the crystalline polypropylene resin (A) is less than 0.95, when various flame retardants are blended, rigidity is lowered and sufficient mechanical properties cannot be maintained.

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 at the center of the three peaks of deuterated 1,1,2,2-tetrachloroethane. 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

The mm fraction is measured using a ¹³ C-NMR spectrum measured under the above conditions.
Spectra assignment is made according to the method described in detail in Japanese Patent Application No. 2006-311249, with reference to Macromolecules, (1975) 8 pp. 687, Polymer, 30 pages, 1350 (1989). Do.

The crystalline polypropylene resin (A) used in the present invention has a strain hardening degree (λmax) in the measurement of elongational viscosity of preferably less than 1.5, more preferably less than 1.1, still more preferably 1. .05 or less. By doing so, the appearance of the product is further improved.
Details of the method for measuring the strain hardening degree (λmax) in the measurement of the extensional viscosity will be described later.

  The polypropylene resin (A) according to the present invention is not particularly limited as long as the above MFR and mm fraction are satisfied. Usually, a Ziegler type highly active catalyst or a metallocene catalyst is used. Manufactured.

  As the Ziegler (ZN) catalyst, a highly active catalyst in which a solid catalyst component containing magnesium, titanium, halogen, and an electron donor as an essential component and an organoaluminum compound is combined is preferable.

  Examples of metallocene catalysts include organic compounds having a cyclopentadienyl skeleton and transition metal such as zirconium, hafnium, titanium, metallocene complexes coordinated with halogen atoms, alumoxane compounds, ion-exchange layered silicates, organoaluminum compounds, etc. A combination of these is effective.

  Examples of the comonomer copolymerized with propylene include ethylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1. These comonomer components are 0 to 15% by weight, preferably 0 to 10% by weight. Among these, a particularly preferable one is a random copolymer of propylene and ethylene and / or butene-1.

  The amount ratio of each monomer in the reaction system does not need to be constant over time, it is convenient to supply each monomer at a constant mixing ratio, and the mixing ratio of the supplied monomers can be changed over time. Is also possible. Also, any of the monomers can be added in portions in consideration of the copolymerization reaction ratio.

  As the polymerization method, any method can be adopted as long as the catalyst component and each monomer come into efficient contact. Specifically, a slurry method using an inert solvent, a bulk method using substantially no inert solvent as a solvent, a solution method, or a solution method, or substantially using each liquid without substantially using a liquid solvent. A gas phase method can be employed.

  Further, either continuous polymerization or batch polymerization may be used. In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene and toluene can be used alone or as a polymerization solvent.

  As polymerization conditions, the polymerization temperature is −78 to 160 ° C., preferably 0 to 150 ° C., and hydrogen can be used supplementarily as a molecular weight regulator at that time. The polymerization pressure is 0 to 9 MPa, preferably 0 to 6 MPa, particularly preferably 1 to 5 MPa.

2. Propylene polymer (B)
The propylene-based polymer (B) used in the flame-retardant polypropylene resin composition of the present invention is a component (I) that is insoluble in p-xylene at 25 ° C. and a component (S) that is soluble in p-xylene at 25 ° C. And (i) a weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000, and (ii) a component insoluble in hot p-xylene is 0.3% by weight or less ( iii) The strain hardening degree (λmax) in the measurement of elongational viscosity is 1.1 or more.

  The propylene polymer (B) includes a crystalline propylene polymer segment and a propylene-ethylene containing a copolymer in which a crystalline propylene polymer segment and a part of an amorphous propylene copolymer segment are chemically bonded. It is a propylene-ethylene copolymer component obtained by sequentially producing a random copolymer component by a multistage polymerization method.

The multistage polymerization is preferably a two-stage polymerization in which the crystalline propylene polymer component is polymerized in the first stage and the propylene-ethylene random copolymer component is polymerized in the second stage.
At this time, a part of the crystalline propylene polymer produced in the first stage is present in a state in which the reaction is terminated in the state of the terminal vinyl group. As a macromonomer, the crystalline propylene polymer is involved in the second stage polymerization, the non-crystalline propylene copolymer segment (propylene-ethylene random copolymer segment) is the main chain, and the crystalline propylene polymer segment is the side chain. A copolymer having a certain branched structure is formed.

The present inventors consider that the factor that the propylene-based copolymer (B) according to the present invention exhibits a good anti-drip effect can be attributed to the presence of this branched structure. A polymer having a portion composed of a chain of different monomers in one molecule, such as a real block copolymer or a graft copolymer, is called a microphase separation structure, which is much smaller than a normal phase separation structure. It is known to have an order phase separation structure, and such a fine phase separation structure is considered to significantly improve the drip prevention effect. Actually, in the electron micrographs (FIGS. 3 and 4) of the propylene-based polymer (B) (copolymer having a branched structure) according to the present invention, a normal propylene-based polymer (without a branched structure) (FIG. 3). Compared with 5)), a very fine dispersion structure of rubber domains is seen, which supports the above inference.
The propylene polymer (B) is a copolymer having a branched structure in which an amorphous propylene copolymer segment (propylene-ethylene random copolymer segment) is a main chain and a crystalline propylene polymer segment is a side chain. Is included. In addition to propylene and ethylene, the component constituting the main chain may contain other unsaturated compounds, for example, α-olefins such as 1-butene, as long as the essence of the present invention is not significantly impaired. The component constituting the side chain is mainly propylene, and may contain a small amount of other unsaturated compounds, for example, α-olefins such as ethylene and 1-butene, as long as the essence of the present invention is not significantly impaired. Good.

As one of the techniques for determining whether or not there is a graft copolymer in which the propylene-ethylene random copolymer component as described above is a main chain and the crystalline propylene polymer component is a side chain, It is effective to use the strain hardening degree (λmax) obtained from the measurement of the extensional viscosity.
The strain hardening degree (λmax) is an index representing the strength at the time of melting, and when this value is large, there is an effect of improving the melt tension.
The degree of strain hardening is an index representing the nonlinearity of elongational viscosity, and it is usually said that this value increases as the molecular entanglement increases. Molecular entanglement is affected by the amount of branching and the length of the branched chain. Therefore, the greater the amount of branching and the length of branching, the greater the degree of strain hardening.
In the propylene polymer (B) according to the present invention, a propylene polymer having a terminal vinyl group is involved in the polymerization as a macromonomer during the production of the first-stage crystalline propylene polymer, and a branched propylene polymer is obtained. Generate. Therefore, this degree of strain hardening is an index of the amount of terminal vinyl propylene polymer produced, and is preferably 1.1 or more.
Here, as to the method for measuring the strain hardening degree, the same value can be obtained in principle by any method as long as the uniaxial extensional viscosity can be measured. For example, details of the measuring method and the measuring instrument are disclosed in the publicly known document: Polymer. 42 (2001) 8663, and preferable measuring methods and measuring instruments include the following.

Measuring method 1:
Device: Ales manufactured by Rheometrics
Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Preparation of test piece: A sheet of 18 mm × 10 mm and a thickness of 0.7 mm is formed by press molding.

Measurement method 2:
Apparatus: Toyo Seiki Co., Ltd., Melten Rheometer
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Preparation of test piece: An extruded strand is prepared at a speed of 10 to 50 mm / min using an orifice having an inner diameter of 3 mm at 180 ° C. using a capillograph manufactured by Toyo Seiki Co., Ltd.

Calculation method:
The elongational viscosity at a strain rate of 0.1 / sec is plotted as a log-log graph of time t (second) on the horizontal axis and elongational viscosity ηE (Pa · second) on the vertical axis. On the logarithmic graph, the viscosity immediately before strain hardening is approximated by a straight line, the maximum value (ηmax) of the extensional viscosity ηE until the amount of strain becomes 4.0 is obtained, and on the approximate straight line up to that time Let ηlin be the viscosity.
FIG. 2 is an example of a plot of elongational viscosity. ηmax / ηlin is defined as λmax and is used as an index of strain hardening degree.
The elongational viscosity and strain hardening degree calculated from the measuring method 1 and the measuring method 2 are, in principle, for measuring the inherent extensional viscosity and strain hardening degree of the substance and exhibit the same value. Therefore, either measurement method 1 or measurement method 2 may be used.

However, measurement method 2 has a measurement restriction that a measurement sample hangs down when the molecular weight is relatively low (that is, when MFR> 2), and the measurement accuracy is lowered. In the measuring method 1, when measuring a relatively high molecular weight (MFR <1), the measurement sample is contracted and deformed non-uniformly, and distortion occurs at the time of measurement. There is a problem of measurement accuracy that is averaged and the strain hardening degree is estimated to be small.
Therefore, it is preferable for convenience to use the measuring method 1 for those having a low molecular weight and the measuring method 2 for those having a high molecular weight.
In general, in order to show a high degree of strain hardening, the length of branching is preferably entangled molecular weight (Me) of 7000 or more, and the degree of strain hardening is said to increase as the length of branching increases.

The propylene polymer (B) according to the present invention is fractionated into a crystalline component and an amorphous component, and the amount of the component (S) dissolved in paraxylene at 25 ° C. is based on the total amount of the propylene polymer (B). What is 5 to 80% by weight and the amount of component (I) insoluble in paraxylene is 20 to 95% by weight is used.
Here, a specific method for separating the crystalline component and the amorphous component is as follows.

Sorting method:
A sample of 2 g was dissolved in 300 ml of p-xylene (0.5 mg / ml BHT: 2,6-di-tert-butyl-4-methylphenol included) at 130 ° C. to obtain a solution, and then at 25 ° C. Leave for 48 hours. Thereafter, it is separated into a precipitated polymer and a filtrate. The p-xylene is evaporated from the filtrate and further dried under reduced pressure at 100 ° C. for 12 hours, and the component (CXS) dissolved in xylene at 25 ° C. is recovered. In addition, the precipitated polymer removes the remaining p-xylene in the same manner and makes it a component insoluble in xylene (CXIS) at 25 ° C.

As described above, the propylene polymer (B) is composed of a crystalline component (I) and an amorphous component (S), and a part of each component is a propylene-ethylene random copolymer segment. Includes a copolymer having a branched structure in which the crystalline propylene polymer segment is a side chain, and analytically, the following characteristics (i) to (iii), (I1) to (I5) ), (S1) to (S3).
(I): The weight average molecular weight (Mw) measured by GPC of the propylene-based polymer (B) is 100,000 to 1,000,000.
(Ii): The amount of components insoluble in hot paraxylene of the propylene polymer (B) is 0.3% by weight or less based on the total amount of the propylene polymer (B).
(Iii) The degree of strain hardening (λmax) in the measurement of the extensional viscosity of the propylene polymer (B) is 1.1 or more.
(I1): The amount of component (I) is 20 to 95% by weight based on the total amount of propylene polymer (B).
(I2): The weight average molecular weight (Mw) measured by GPC of component (I) is 100,000 to 1,000,000.
(I3): Isotactic triad fraction (mm) measured by ¹³ C-NMR of component (I) is 0.93 or more.
(I4): The strain hardening degree (λmax) in the measurement of the extensional viscosity of the component (I) is 2.0 or more.
(I5): Component (I) contains a propylene unit and an ethylene unit or an α-olefin unit.
(S1): The amount of component (S) is 5 to 80% by weight based on the total amount of propylene polymer (B).
(S2): The weight average molecular weight (Mw) measured by GPC of a component (S) is 100,000-1 million.
(S3) Component (S) contains a propylene unit, an ethylene unit and / or an α-olefin unit.

Hereinafter, each item will be described sequentially.
(I): The weight average molecular weight (Mw) measured by GPC of the propylene-based polymer (B) is 100,000 to 1,000,000.
As the propylene polymer (B), those having a weight average molecular weight in the range of 100,000 to 1,000,000 are used.
The weight average molecular weight (Mw) is measured by a GPC measuring apparatus and conditions described later, and it is necessary that the Mw of the propylene polymer (B) is in the range of 100,000 to 1,000,000. When this Mw is smaller than 100,000, the melt processability is inferior and the mechanical strength is insufficient. On the other hand, when the Mw exceeds 1 million, the melt viscosity is high and the melt processability is lowered. From the balance of melt processability and mechanical strength, the above range is preferable, and Mw is preferably 150,000 to 900,000, and more preferably 170,000 to 800,000.
The value of the weight average molecular weight (Mw) is obtained by gel permeation chromatography (GPC), and the details of the measuring method and measuring instrument are as follows.

Equipment: 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: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml

The sample is prepared by preparing a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolving it at 140 ° C. for about 1 hour. The baseline and section of the obtained chromatogram are performed as shown in FIG. Further, the conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a standard curve prepared in advance by standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
Brand: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
Inject 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL to create a calibration curve. The calibration curve uses a cubic equation obtained by approximation by the least square method. Viscosity formula used for conversion to molecular weight: [η] = K × M ^α uses the following numerical values.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

(Ii): The amount of components insoluble in hot paraxylene of the propylene-based polymer (B) is 0.3% by weight or less based on the total amount of the polymer (B). Preferably it is 0.2 weight% or less, More preferably, it is 0.1 weight% or less.
In the present invention, the component insoluble in hot p-xylene needs to be 0.3% by weight or less. A method for measuring a component insoluble in hot p-xylene is as follows.
In a separable flask made of glass with a stirrer, 500 mg of a polymer is placed in a bowl made of stainless steel 400 mesh (wire diameter 0.03 μm, aperture 0.034 mm, space ratio 27.8%). Fixed to. 700 ml of p-xylene containing 1 g of an antioxidant (BHT: 2,6-di-t-butyl-4-methylphenol) was added, and the polymer was dissolved while stirring at a temperature of 140 ° C. for 2 hours.
The soot containing the p-xylene insoluble part was collected, sufficiently dried and weighed to obtain a paraxylene insoluble part. The gel fraction (% by weight) defined as the hot p-xylene insoluble part was calculated by the following formula.
Gel fraction = [(residual amount in mesh g) / (prepared sample amount g)] × 100

Moreover, in order to have few gels or no gels as described above, it is important that there are no components having a very high molecular weight. Therefore, when the molecular weight distribution is measured by GPC, it is important that the molecular weight distribution does not spread to the high molecular weight side.
Therefore, the Q value (the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) measured by GPC is preferably 7 or less, more preferably 6 or less, and still more preferably 5 or less.
Moreover, in order not to extend extremely to the high molecular weight side, it is necessary that the molecular weight M (90) at which the integral value in the curve is 90% by GPC is 2,000,000 or less.
Here, M (90) is a molecular weight at which the integral value in the curve is 90% by GPC measured by the GPC measuring apparatus and conditions described above. In the present invention, M (90) is 2,000,000 or less. It is a feature. When M (90) exceeds 2,000,000, the high molecular weight component is excessively increased, gel is generated, and the appearance of the molded product is deteriorated. Therefore, M (90) is 2,000,000 or less, preferably 1,500,000 or less, and more preferably 1,000,000.

(Iii) The degree of strain hardening (λmax) in the measurement of the extensional viscosity of the propylene polymer (B) is 1.1 or more. Preferably it is 2.0 or more, More preferably, it is 3.0 or more, More preferably, it is 4.0 or more.
The physical significance of the strain hardening degree is as described above. When this value is less than 1.1, the drip prevention property is inferior.
The length of branching is preferably an entanglement molecular weight of 7000 or more of polypropylene. Strictly speaking, this molecular weight is different from the weight average (Mw) measured by GPC. Therefore, the weight average molecular weight (Mw) value measured by GPC is preferably 15000 or more, and more preferably 30000 or more.

(I1): The amount of component (I) is 20 to 95% by weight based on the total amount of propylene polymer (B). Preferably it is 30 to 93 weight%, More preferably, it is 40 to 90 weight%.
This rule is a range with respect to the total amount of the propylene polymer (B) of the component (I), and those in this range are used from the balance of rigidity and impact resistance.

(I2): The weight average molecular weight (Mw) measured by GPC of component (I) is 100,000 to 1,000,000.
Here, the weight average molecular weight (Mw) is measured by the GPC measuring apparatus and conditions described above, and the crystalline component (I) in the propylene polymer (B) has a weight average molecular weight of 100,000 to Those in the range of 1 million are used.
When this Mw is smaller than 100,000, the melt processability is inferior and the mechanical strength is insufficient. On the other hand, when the Mw exceeds 1 million, the melt viscosity is high and the melt processability is lowered. From the balance of melt processability and mechanical strength, the above range is preferable, and Mw is preferably 150,000 to 900,000, more preferably 160,000 to 500,000.

(I3): Isotactic triad fraction (mm) measured by ¹³ C-NMR of component (I) is 0.93 or more.
The crystalline component (I) of the propylene-based polymer (B) according to the present invention has a stereoregularity in which the mm fraction of three propylene units obtained by ¹³ C-NMR is 0.93 or more.
The mm fraction is a ratio of three propylene unit chains in which the direction of methyl branching in each propylene unit is the same among arbitrary three propylene unit chains composed of head-to-tail bonds in the polymer chain. 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. When the mm fraction of the crystalline component (I) is smaller than this value, the mechanical properties such as the elastic modulus, rigidity, heat resistance and strength of the product are lowered. Therefore, the mm fraction is preferably 0.95 or more, and more preferably 0.96 or more.
In addition, the detail of the measuring method of mm fraction of the propylene unit 3 chain | strand by < ¹³ > C-NMR is as having mentioned above.

(I4): The strain hardening degree (λmax) in the measurement of the extensional viscosity of the component (I) is 2.0 or more. Preferably it is 2.5 or more, More preferably, it is 3.0 or more.
The length of branching is preferably an entanglement molecular weight of 7000 or more of polypropylene. Moreover, as a weight average (Mw), it is 15000 or more, More preferably, it is 30000 or more.

The propylene polymer (B) according to the present invention satisfies (I5) in addition to the above (I1) to (I4).
(I5): Component (I) contains a propylene unit and an ethylene unit or an α-olefin unit.
As a unit constituting the crystalline component (I), it is necessary that propylene is arranged in an isotactic manner and has crystallinity. Further, ethylene or α-olefin may be contained as a comonomer unit within a range where crystallinity is exhibited. When α, ω-diene units are present, gelation due to crosslinking is a concern, so it is necessary that no α, ω-diene units be included.
As a kind of comonomer, ethylene or a linear alpha olefin is preferable, More preferably, it is ethylene.
Regarding comonomer content, it can contain arbitrary quantity in the range which crystallinity expresses.

The ethylene content of component (I) is preferably 0.1 to 10% by weight, more preferably 0.2 to 8% by weight, and still more preferably 0.3 to 7% by weight.
The ethylene unit is measured according to the method described in Macromolecules 1982 1150 using ¹³ C-NMR.
The melting point (Tm) measured by DSC, which is an index of crystallinity, is 120 ° C. or higher, preferably 150 ° C. or higher, more preferably 153 ° C. or higher. When the melting point (Tm) is 150 to 164 ° C, it has excellent heat resistance and rigidity, and can be used for industrial parts and members. When the melting point (Tm) is 120 to 150 ° C, it is excellent in flexibility and used for films and containers. it can.

(S1): The amount of component (S) is 5 to 80% by weight based on the total amount of polymer (B). Preferably it is 7 to 70 weight%, More preferably, it is 10 to 60 weight%.
This rule is a range with respect to the total amount of the propylene polymer (B) of the component (S), and those in this range are used from the balance of rigidity and impact resistance.

(S2): The weight average molecular weight (Mw) measured by GPC of a component (S) is 100,000-1 million.
Here, the weight average molecular weight (Mw) is measured by the GPC measuring apparatus and conditions described above, and the amorphous component (S) in the propylene polymer (B) has a weight average molecular weight of 100,000. Those in the range of ~ 1 million are used.
When this Mw is smaller than 100,000, the melt processability is inferior and the mechanical strength is insufficient. On the other hand, when the Mw exceeds 1 million, the melt viscosity is high and the melt processability is lowered. From the balance of melt processability and mechanical strength, it is in the above range, preferably Mw is 150,000 to 900,000, more preferably 200,000 to 800,000.

(S3): Component (S) contains a propylene unit, an ethylene unit and / or an α-olefin unit.
As a unit constituting the amorphous component (S), it is necessary that propylene and ethylene or α-olefin are copolymerized. Moreover, since there exists a concern about the gelatinization by bridge | crosslinking when there exists an alpha, omega-diene unit, it is preferable not to contain an alpha, omega-diene unit.
The kind of comonomer is preferably ethylene or a linear α-olefin, more preferably ethylene, and the ethylene content is usually 10 to 60% by weight. From the viewpoint of improving impact resistance at low temperatures, 40 to 60% by weight is preferable, and from the viewpoint of gloss and transparency, 10% by weight or more and less than 40% by weight is preferably used.

(S4): The strain hardening degree (λmax) in the measurement of the elongational viscosity of the component (S) is usually 1 to 20, preferably 1.2 or more.
As described above, when the value of strain hardening degree (λmax) is large, for example, the drip suppression effect during combustion is large. Therefore, 1.2 or more are preferable and 1.3-20 are still more preferable.

Regarding the method for producing the propylene polymer (B) according to the present invention, a macromer having a vinyl terminal can be produced, and a catalyst system capable of copolymerizing the macromer with propylene and ethylene may be used. It is a feature. Among them, by using a polymerization catalyst obtained by contacting the following catalyst components (a), (b) and (c),
(I) first step of polymerizing propylene alone or propylene with ethylene or α-olefin, and polymerizing ethylene or α-olefin with respect to all monomer components in an amount of 0 to 10% by weight; and (ii) propylene and ethylene. Or a second step of polymerizing α-olefin and polymerizing 10 to 70% by weight of ethylene with respect to the total monomer components;
The propylene-based polymer (B) according to the present invention can be produced with high productivity by the process having the above.

(1) Component (a):
The catalyst component (a) used for production of the propylene polymer (B) is a metallocene compound having hafnium as a central metal represented by the following general formula (1).

In general formula (1), each R ₁ is independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, a silicon-containing alkyl group having 1 to 6 carbon atoms, or carbon. An aryl group having 6 to 16 carbon atoms, a halogen-containing aryl group having 6 to 16 carbon atoms, a nitrogen or oxygen having 4 to 16 carbon atoms, and a heterocyclic group containing sulfur, and at least one of two R ₁ is carbon A heterocyclic group containing nitrogen, oxygen, or sulfur of several 4 to 16 is shown. Two R _{1 s} may be the same or different from each other. Each R ₂ is independently an alkyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, a silicon-containing alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms. , A halogen-containing aryl group having 6 to 16 carbon atoms, a silicon-containing aryl group having 6 to 16 carbon atoms, a nitrogen or oxygen having 6 to 16 carbon atoms, and a heterocyclic group containing sulfur. Two R ₂ may be the same as or different from each other.
X and Y are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Group, 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, Q is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom Represents a silylene group, an oligosilylene group, or a germylene group which may have ˜20 hydrocarbon groups.

The heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms of R ₁ is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, or a substituted 2 group. -Furfuryl group, 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.
Furthermore, R ₁ is particularly preferably a 2- (5-methyl) -furyl group. Moreover, it is preferable that two R ₁ are mutually the same.

R ₂ is preferably an aryl group having 6 to 16 carbon atoms, a halogen-containing aryl group having 6 to 16 carbon atoms, or a silicon-containing aryl group having 6 to 16 carbon atoms. Such an aryl group has 6 to 16 carbon atoms. 1 or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, and halogen-containing hydrocarbon groups having 1 to 6 carbon atoms on the aryl cyclic skeleton. You may have as a substituent.
R ₂ is preferably at least one of phenyl group, 4-t-butylphenyl group, 2,3-dimethylphenyl group, 3,5-dit-butylphenyl group, 4-phenyl-phenyl group, chlorophenyl group. , A naphthyl group, or a phenanthryl group, more preferably a phenyl group, a 4-t-butylphenyl group, or a 4-chlorophenyl group. Moreover, the case where two R < ₂ > is mutually the same is preferable.

In general formula (1), X and Y are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a carbon number of 1 to 20 A silicon-containing hydrocarbon group, 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. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and s-butyl, vinyl, propenyl, Examples include alkenyl groups such as cyclohexenyl, arylalkyl groups such as benzyl, arylalkenyl groups such as trans-styryl, and aryl groups such as phenyl, tolyl, 1-naphthyl, and 2-naphthyl.
Specific examples of the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms include alkoxy groups such as methoxy, ethoxy, propoxy and butoxy, allyloxy groups such as phenoxy and naphthoxy, arylalkoxy groups such as phenylmethoxy, and furyl groups. And oxygen-containing heterocyclic groups.
Specific examples of the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms include alkylamino groups such as methylamino, dimethylamino, ethylamino and diethylamino, arylamino groups such as phenylamino and diphenylamino, (methyl) ( (Alkyl) (aryl) amino groups such as phenyl) amino, and nitrogen-containing heterocyclic groups such as pyrazolyl and indolyl.

In the halogenated hydrocarbon group having 1 to 20 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenated hydrocarbon group is a compound in which, when the halogen atom is, for example, a fluorine atom, the fluorine atom is substituted at an arbitrary position of the hydrocarbon group. Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, and trichloromethyl groups.
Specific examples of the silicon-containing hydrocarbon group having 1 to 20 carbon atoms include trialkylsilylmethyl groups such as trimethylsilylmethyl and triethylsilylmethyl, dialkyl such as dimethylphenylsilylmethyl, diethylphenylsilylmethyl, and dimethyltolylsilylmethyl. (Alkyl) (aryl) silylmethyl group and the like can be mentioned.

In general formula (1), Q 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, which bonds two five-membered rings. , An oligosilylene group or a germylene group. When two hydrocarbon groups are present on the above-mentioned silylene group, oligosilylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 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; tetra An alkyl oligosilylene group such as methyldisilylene; a germylene group; an alkylgermylene group in which the silicon of the above-mentioned divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) germylene Group; arylgermylene group It can be mentioned. 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 (1), preferred compounds are specifically exemplified below.
Dimethylsilylenebis (2- (2-furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2-thienyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2 -(5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, diphenylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylgermylenebis (2- (2- (5-Methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylgermylenebis (2- (2- (5-methyl) -thienyl) -4-phenyl-indenyl) hafnium Dichloride, dimethylsilylenebis (2- (2- (5-t Butyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2 -(5-phenyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (4,5-dimethyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylene Bis (2- (2-benzofuryl) -4-phenyl-indenyl) hafnium dichloride, diphenylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis ( 2- (2- (5-Methyl -Furyl) -4-methyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-isopropyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2-furfuryl) ) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4- (4-chlorophenyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2 -(5-Methyl) -furyl) -4- (4-fluorophenyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4- (4-trifluoromethyl) Phenyl) -indenyl) hafnium dichloride, dimethylsilylenebi (2- (2- (5-methyl) -furyl) -4- (4-t-butylphenyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2-furyl) -4- (1-naphthyl) ) -Indenyl) hafnium dichloride, dimethylsilylenebis (2- (2-furyl) -4- (2-naphthyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2-furyl) -4- (2-phenanthryl) ) -Indenyl) hafnium dichloride, dimethylsilylenebis (2- (2-furyl) -4- (9-phenanthryl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl)- 4- (1-naphthyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2 (5-Methyl) -furyl) -4- (2-naphthyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4- (2-phenanthryl) -indenyl) Hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4- (9-phenanthryl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -Furyl) -4- (1-naphthyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -furyl) -4- (2-naphthyl) -indenyl) hafnium dichloride, Dimethylsilylenebis (2- (2- (5-t-butyl) -furyl) -4- (2-phenanthryl) -indene ) Hafnium dichloride, dimethylsilylene bis (2- (2- (5-t-butyl) -furyl) -4- (9-phenanthryl) -indenyl) hafnium dichloride, dimethylsilylene (2-methyl-4-phenyl-indenyl) ) (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylene (2-methyl-4-phenyl-indenyl) (2- (2- (5-methyl)- Thienyl) -4-phenyl-indenyl) hafnium dichloride, and the like.

  Of these, more preferred are dimethylsilylene bis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylgermylene bis (2- (2- (5-methyl). ) -Thienyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4- (4-chlorophenyl) -indenyl) hafnium dichloride, dimethylsilylenebis (2 -(2- (5-methyl) -furyl) -4-naphthyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4- (4-t-butylphenyl) -Indenyl) hafnium dichloride, dimethylsilylene (2-methyl-4-phenyl-indenyl) ( - (2- (5-methyl) - furyl) -4-phenyl - indenyl) hafnium dichloride.

  Also particularly preferred are dimethylsilylene bis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride, dimethylsilylene bis (2- (2- (5-methyl) -furyl). ) -4-naphthyl-indenyl) hafnium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4- (4-t-butylphenyl) -indenyl) hafnium dichloride.

(2) Component (b):
Next, the catalyst component (b) is an ion-exchange layered silicate.
In the present invention, an ion-exchange layered silicate (hereinafter sometimes simply referred to as a silicate) has a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other by a binding force, and , Refers to a silicate compound in which the contained ions are exchangeable. Most silicates are naturally produced mainly as the main component of clay minerals, and are generally dispersed / swelled in water and purified by differences in sedimentation rate, etc., but they can be completely removed. Although it may be difficult and contains impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicate, they may be included. 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 component (b).
In addition, the raw material of this invention refers to the silicate of the previous stage which performs the chemical treatment of this invention mentioned later. Further, the silicate used in the present invention is not limited to a natural product, and may be an artificial synthetic product.
In addition, in the present invention, if there is ion exchange properties before chemical treatment, the physical and chemical properties are changed by the treatment, and silicates having no ion exchange properties or layer structures are also included. Treated as an ion-exchanged layered silicate.

Specific examples of ion-exchanged layered silicates include layered silicates having a 1: 1 type structure or a 2: 1 type structure described in, for example, Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1988). Can be mentioned.
The 1: 1 type structure is basically a stack of 1: 1 layer structure in which a single-layer tetrahedral sheet and a single-layer octahedral sheet are combined as described in “Clay Mineralogy” and the like. The 2: 1 type structure is a structure based on a stack of 2: 1 layer structures in which two layers of tetrahedral sheets sandwich one layer of octahedral sheets.

  Specific examples of ion-exchangeable layered silicates in which the 1: 1 layer is the main constituent layer include kaolin group silicates such as dickite, nacrite, kaolinite, metahalloysite, halloysite, chrysotile, risardite, antigolite, etc. Examples include serpentine silicates.

Specific examples of ion-exchangeable layered silicates with 2: 1 layers as main constituent layers include smectite group silicates such as montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, and vermiculite groups such as vermiculite. Examples thereof include mica group silicates such as silicate, mica, illite, sericite, sea chlorite, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group and the like. These may form a mixed layer.
Among these, the main component is preferably an ion-exchange layered silicate having a 2: 1 type structure. More preferably, the main component is a smectite group silicate, and still more preferably, the main component is montmorillonite.

  The type of interlayer cations (cations contained between the layers of the ion-exchange layered silicate) is not particularly limited, but as a main component, alkali metals of the first group of the periodic table such as lithium and sodium, calcium and magnesium Alkali earth metals of Group 2 of the periodic table, etc., or transition metals such as iron, cobalt, copper, nickel, zinc, ruthenium, rhodium, palladium, silver, iridium, platinum, gold, etc. are relatively It is preferable in that it can be easily obtained.

  The ion-exchange layered silicate may be used in a dry state or in a slurry state in a liquid. In addition, the shape of the ion-exchange layered silicate is not particularly limited, and may be a naturally produced shape, a shape when artificially synthesized, or a shape by operations such as pulverization, granulation, and classification. You may use the processed ion exchange layered silicate. Of these, the granulated ion-exchange layered silicate is particularly preferable because it gives good polymer particle properties when the ion-exchange layered silicate is used as a catalyst component.

Processing of the shape of the ion-exchange layered silicate such as granulation, pulverization, and classification may be performed before the chemical treatment (that is, the following chemical treatment is performed on the ion-exchange layered silicate that has been processed in advance). The shape may be processed after chemical treatment.
Examples of the granulation method used here include, for example, stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, fluidized bed granulation method, emulsion granulation method , Submerged granulation method, compression molding granulation method, and the like, but are not particularly limited. Preferably, agitation granulation method, spray granulation method, rolling granulation method and fluidized granulation method are mentioned, and particularly preferably, agitation granulation method and spray granulation method are mentioned.
When spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene is used as a dispersion medium for the raw slurry. Preferably, water is used as a dispersion medium. The concentration of the component (b) in the raw slurry liquid for spray granulation from which spherical particles are obtained is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight. . The inlet temperature of the hot air for spray granulation from which spherical particles are obtained varies depending on the dispersion medium, but is 80 to 260 ° C, preferably 100 to 220 ° C when water is taken as an example.

  In granulation, in order to obtain a carrier having high particle strength and to improve propylene polymerization activity, the silicate is refined as necessary. The silicate may be refined by any method. As a method for miniaturization, either dry pulverization or wet pulverization is possible. Preferably, wet pulverization using water as a dispersion medium and utilizing the swellability of silicate, for example, a method using forced stirring using polytron or the like, a method using dyno mill, pearl mill, or the like. The average particle size before granulation is 0.01 to 3 μm, preferably 0.05 to 1 μm.

  Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation. Examples of the binder used include magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycols and the like.

  The spherical particles obtained as described above preferably have a compression fracture strength of 0.2 MPa or more in order to suppress crushing and fine powder generation in the polymerization step. The particle size of the granulated ion-exchange layered silicate is in the range of 0.1 to 1000 μm, preferably 1 to 500 μm. There is no particular limitation on the pulverization method, and either dry pulverization or wet pulverization may be used.

  The ion-exchange layered silicate of the catalyst component (b) can be used as it is without any particular treatment, but it is desirable to perform a chemical treatment. It means contacting an alkali, organic matter, etc. with an ion-exchange layered silicate.

  A common effect of chemical treatment is to exchange interlayer cations. In addition, various chemical treatments have the following various effects. For example, according to the acid treatment with acids, impurities on the silicate surface can be removed and the surface area can be increased by eluting cations such as Al, Fe, and Mg in the crystal structure. This contributes to increasing the acid strength of the silicate and increasing the amount of acid sites per unit weight.

  In alkali treatment with alkalis, the crystal structure of the clay mineral is destroyed, resulting in a change in the structure of the clay mineral.

  After carrying out the chemical treatment, it is possible to remove excess treatment agent and ions eluted by the treatment, which is preferable. At this time, generally, a liquid such as water or an organic solvent is used. After the dehydration, drying is performed. In general, the drying temperature can be 100 to 800 ° C, preferably 150 to 600 ° C. Exceeding 800 ° C. is not preferable because it may cause structural destruction of the silicate.

  Since these ion-exchange layered silicates have different characteristics depending on the drying temperature even if they are not structurally destroyed, it is preferable to change the drying temperature depending on the application. The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours, and the atmosphere is preferably dry air, dry nitrogen, dry argon, or under reduced pressure. It does not specifically limit regarding a drying method, It can implement by various methods.

As the catalyst component (b) according to the present invention, the chemically-exchanged ion-exchange layered silicate has an Al / Si atomic ratio of 0.01 to 0.25, preferably 0.03 to 0.24. And more preferably in the range of 0.05 to 0.23. The Al / Si atomic ratio is considered to be an index of the acid treatment strength of the clay portion. Moreover, as a method of controlling Al / Si atomic ratio in said range, the method of using a montmorillonite and performing a chemical process as an ion-exchange layered silicate before a chemical process is mentioned.
Aluminum and silicon in the ion-exchange layered silicate are measured by a method of preparing a calibration curve by a chemical analysis method by JIS method and quantifying with a fluorescent X-ray.

(3) Component (c):
The catalyst component (c) is an organoaluminum compound, and preferably an organoaluminum compound represented by the general formula: (AlR _n X _3-n ) _m is used. In formula, R represents a C1-C20 alkyl group, X represents a halogen, hydrogen, an alkoxy group, or an amino group, n represents 1-3, m represents the integer of 1-2, respectively. The organoaluminum compounds can be used alone or in combination.

  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 with m = 1 and n = 3 are preferable. More preferably, R is a trialkylaluminum having 1 to 8 carbon atoms.

(4) Catalyst adjustment:
The catalyst for olefin polymerization according to the present invention comprises the above component (a), component (b) and component (c). These may be contacted in the polymerization tank or outside the polymerization tank and preliminarily polymerized in the presence of olefin.
The olefin refers to a hydrocarbon containing at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, divinylbenzene, and the like. There is no restriction | limiting, You may use the mixture of these and another olefin. An olefin having 3 or more carbon atoms is preferable.

The amount of catalyst component (a), catalyst component (b) and catalyst component (c) used is arbitrary, but the ratio of the transition metal in component (b) to aluminum in component (c) is (A) It is preferable to make it contact so that it may become 0.1-1000 (micromol): 0-100,000 (micromol) per 1g. In addition to the component (a), other types of complexes may be used for the purpose of more efficiently producing the propylene polymer (B) according to the present invention.
In this case, it is preferable to combine a metallocene compound capable of copolymerizing the terminal vinyl macromer produced by the catalyst component (a) and producing a high molecular weight polymer compared to the catalyst component (a).
As a particularly preferred metallocene compound, a catalyst component (a-2) represented by the following general formula (2) can be mentioned.

The compound represented by the general formula (2) is a metallocene compound, and in the general formula (2), Q ²¹ is a binding group that bridges two conjugated five-membered ring ligands, and has a carbon number. A divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted silylene group or a substituted germylene group It is. 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.
Me is zirconium or hafnium, preferably hafnium.
Further, X ²¹ and Y ²¹ are auxiliary ligands, and react with the cocatalyst of component [b] to generate active metallocene having olefin polymerization ability. Therefore, as long as this purpose is achieved, X ²¹ and Y ²¹ are not limited to the type of ligand, and are independently hydrogen, halogen groups, hydrocarbon groups having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms is shown. .

In general formula (2), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms. is there. 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.
R ²³ and R ²⁴ each independently contains a halogen having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, or a plurality of hetero elements selected from these. A good aryl group. Preferable examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluorobiphenylyl), 4- (2-chlorobiphenylyl), 1-naphthyl, 2-naphthyl, 3,5-dimethyl-4-tert-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl Etc.

Non-limiting examples of the metallocene compound include the following.
For example, dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazulenyl)} hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylene Bis {2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazulenyl}] 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- (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-methyl-4- (4-chloro-2-naphthyl) -4-hydroazulenyl }] 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}] hafnium, dic B [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2 -Methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazulenyl}] 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}] hafnium, and the like.

  In addition to the catalyst component (a), when other types of catalyst component (a-2) are used, the catalyst component (a-2) relative to the total amount of the catalyst component (a) and the catalyst component (a-2) is used. The ratio of the amount of) is arbitrary as long as it satisfies the characteristics of the propylene-based polymer (B), but is preferably 0.01 to 0.6. By changing this ratio, it is possible to adjust the balance between the melt physical properties and the catalyst activity, and it is particularly preferably 0 for the production of a propylene-based polymer for uses requiring higher melt properties and high catalyst activities. The range is 0.03 to 0.40, and more preferably 0.07 to 0.2.

  The order in which the catalyst component (a), the catalyst component (b), and the catalyst component (c) are brought into contact is arbitrary, and after contacting two of these components, the remaining one component may be brought into contact. Three components may be contacted simultaneously. In these contacts, a solvent may be used for sufficient contact. Examples of the solvent include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons, halides thereof, and prepolymerized monomers. Specific examples of the aliphatic saturated hydrocarbon and the aromatic hydrocarbon include hexane, heptane, toluene and the like. Further, as a prepolymerized monomer, propylene can be used as a solvent.

[Prepolymerization]:
As described above, the catalyst according to the present invention is preferably subjected to a pre-polymerization treatment consisting of a small amount of polymerization by bringing an olefin into contact therewith. The olefin used is not particularly limited, but as described above, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcyclohexane. Examples include alkanes and styrene. 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. Further, the prepolymerization amount is preferably 0.01 to 100, more preferably 0.1 to 50, by weight ratio of the prepolymerized polymer to the component (b). Further, the component (c) can be added or added during the prepolymerization.
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 the contact of the above components is also possible.
The catalyst may be dried after the prepolymerization. The drying method is not particularly limited, and examples thereof include reduced-pressure drying, heat drying, and drying by circulating a drying gas. These methods may be used alone or in combination of two or more methods. May be. In the drying step, the catalyst may be stirred, vibrated, fluidized, or allowed to stand.

[Detailed description of polymerization method]:
As the polymerization mode, any mode can be adopted as long as the olefin polymerization catalyst comprising the catalyst component (a), the catalyst component (b) and the catalyst component (c) and the monomer come into efficient contact. Specifically, a slurry method using an inert solvent, a bulk polymerization method using propylene as a solvent without substantially using an inert solvent, or a gas phase polymerization method for maintaining each monomer in a gaseous state without using a liquid solvent. Etc. can be adopted.
As the polymerization method, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied.
Further, the number of polymerization stages is not particularly limited as long as the substance of the present invention can be produced. However, it is possible to employ a mode such as two stages of bulk polymerization, gas phase polymerization after bulk polymerization, and two stages of gas phase polymerization, and more. It is possible to produce with the number of polymerization stages.
However, in order to obtain the compound having the molecular weight and molecular weight distribution disclosed in the present invention, the first step is carried out by bulk polymerization and the second step is carried out by gas phase polymerization, or both the first step and the second step are carried out. It is preferable to carry out by phase polymerization.

[First step]:
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 to 150 ° C., and hydrogen can be used supplementarily as a molecular weight regulator. The polymerization pressure is 0-3 MPa, preferably 0-2 MPa.
In the case of the bulk polymerization method, the polymerization temperature is 0 to 80 ° C, preferably 60 to 90 ° C, and more preferably 70 to 80 ° C. The polymerization pressure is 0 to 5 MPa, preferably 0 to 4 MPa.
In the case of gas phase polymerization, the polymerization temperature is 0 to 200 ° C, preferably 60 to 120 ° C, more preferably 70 to 100 ° C. The polymerization pressure is 0 to 4 MPa, preferably 0 to 3 MPa.

[Second step]:
In the case of gas phase polymerization, the polymerization temperature is 0 to 200 ° C, preferably 20 to 90 ° C, more preferably 30 to 80 ° C. In addition, hydrogen can be used as a molecular weight regulator. The polymerization pressure is 0 to 4 MPa, preferably 0 to 3 MPa.
Here, the ethylene content of the propylene-ethylene (or α-olefin) copolymer to be polymerized is usually 10% by weight to 60% by weight. For example, the gas composition for producing it by gas phase polymerization is ethylene. When used, the lower limit is 10 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more, and the upper limit is 90 mol% or less, preferably 87 mol% or less, more preferably 85 mol% or less. is there.
This propylene-ethylene (or α-olefin) copolymer is partially copolymerized with a low vinyl terminal content, and both the main chain and side chain have (non-crystalline) propylene-ethylene random copolymer segments. It is considered that a polymer having a branched structure is formed. In this case, the lower the ethylene content in the amorphous propylene-ethylene random copolymer, the higher the vinyl terminal content. That is, by reducing the ethylene content in the amorphous propylene-ethylene random copolymer, it is possible to increase the λmax of the CXS component of the propylene polymer according to the present invention. Accordingly, the gas composition of ethylene can be controlled by further lowering the upper limit value.

  The propylene polymer (B) according to the present invention thus obtained has (i) a weight average molecular weight (Mw) measured by GPC of 100,000 to 1,000,000, and (ii) a component insoluble in hot p-xylene. (Iii) The strain hardening degree (λmax) in the measurement of elongational viscosity is 1.1 or more, and the crystalline segment is grafted as a side chain to the amorphous segment. Including polymers. In particular, such graft copolymers are present in the CXIS component (I). Polymerization mechanism in which the crystalline segment becomes a side chain and the non-crystalline segment becomes the main chain, in which the macromer of the crystalline component is produced in the first stage and copolymerized with the amorphous component in the second stage. From the point of view, it is natural.

3. Non-halogen flame retardant (C)
As the non-halogen flame retardant (C) used in the flame retardant polypropylene resin composition of the present invention, any non-halogen flame retardant can be used as long as it is generally used as a flame retardant for polyolefins. it can.
Specifically, hydrated metal compounds such as aluminum hydroxide, magnesium hydroxide and calcium aluminate, organophosphoric acids such as triphenyl phosphate, tricresyl phosphate, bisphenol-A-bisdiphenyl phosphate, resorcinol-bisdiphenyl phosphate Ester compounds, ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, piperazine orthophosphate, melamine pyrophosphate, piperazine pyrophosphate, melamine polyphosphate, melamine orthophosphate, calcium phosphate, magnesium phosphate, etc. Examples thereof include a phosphate compound or a mixture thereof. Of these, phosphate compounds are preferred.

  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). Composition ratio of components of flame retardant polypropylene resin composition In the flame retardant polypropylene resin composition of the present invention, crystalline polypropylene resin (A) 60 to 99 wt% and propylene polymer (B) 1 to 40 wt% It is important to contain 10 to 50 parts by weight of the halogen-free flame retardant (C) with respect to 100 parts by weight of the polypropylene resin component, and the halogen-free flame retardant (C) is preferably 16 to 45 parts by weight. Preferably it is 22-40 weight part. If the ratio of (C) is less than 10 parts by weight, sufficient flame retardancy cannot be obtained. On the other hand, if it exceeds 50 parts by weight, strength properties are deteriorated and economical disadvantages are not preferable.
The composition of the crystalline polypropylene resin (A) and the propylene polymer (B) is such that (A) is 60 to 99% by weight, preferably 65 to 95% by weight, more preferably 70 to 90% by weight, ( B) is 1 to 40% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight. When the propylene-based polymer (B) is less than 1% by weight, the drip prevention property is inferior. On the other hand, when it exceeds 40% by weight, not only the mechanical properties are deteriorated but the appearance is deteriorated, but it is economically disadvantageous.

5. Metal oxide (D)
The flame retardant polypropylene resin composition of the present invention desirably contains a metal oxide (D) in addition to the above-described components (A), (B), and (C).
Examples of the metal oxide (D) 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, the dispersibility with respect to the polypropylene resin component is deteriorated, and there is a possibility that high flame retardancy cannot be obtained.

  In this invention, the compounding quantity in the case of using a metal oxide (D) is 0.05-100 with respect to 100 weight part of polypropylene resin components which consist of crystalline polypropylene resin (A) and a propylene-type polymer (B). 5 parts by weight is preferable, and 0.1 to 3 parts by weight is more preferable. If the amount is less than 0.05 part by weight, the synergistic flame retardant effect due to sufficient addition cannot be obtained.

6). Other optional ingredients (E)
The flame-retardant polypropylene resin composition of the present invention can be blended with any known additive that is usually used for polyolefins, in order to impart other characteristics within a range that does not impair the effects of the present invention. . For example, antioxidants, processing stabilizers, ultraviolet absorbers, light stabilizers, antistatic agents, crystallization nucleating agents, lubricants, anti-drip agents, metal deactivators, color pigments, various inorganic fillers, glass fibers, etc. Can be added.
Also, high density polyethylene (HDPE), high pressure method low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene / propylene rubber (EPR), ethylene butene rubber (EBR), C2 / C6 copolymer, C2 / C8 copolymer, polystyrene, ethylene / acrylic acid copolymer, ethylene / vinyl acetate copolymer (EVA), styrene / butadiene copolymer hydrogenated product (SEBS), etc. can be combined. It is. Furthermore, it is also possible to combine a modified polyolefin containing a polar group such as a maleic anhydride modified product of polypropylene and a maleic anhydride modified product of ethylene / propylene copolymer.

  Among the above optional components, various stabilizers and the like are usually 0 to 5 parts by weight with respect to 100 parts by weight of the polypropylene resin component comprising the crystalline polypropylene resin (A) and the propylene-based polymer (B), and an inorganic filler. The polymer system compounding agent is used in the range of 0 to 30 parts by weight.

II. Method for preparing flame retardant polypropylene resin composition The method for preparing the flame retardant polypropylene resin composition of the present invention is not particularly limited. For example, a predetermined amount of a non-halogen flame retardant (C) is mixed with 100 parts by weight of a polypropylene resin component composed of a crystalline polypropylene resin (A) and a propylene polymer (B), and other additives are added as necessary. A predetermined amount of the agent is mixed. For example, each component is put into a mixing apparatus such as a super mixer and a tumbler mixer, and after mixing for 1 to 5 minutes, the resulting mixture is melt-kneaded at a kneading temperature of 170 to 230 ° C. with an extruder, a heating roll, a kneader, The method of pelletizing can be mentioned. Among them, the extruder kneading with two axes is preferable in terms of productivity and flame retardancy.
Further, the non-halogen flame retardant (C) may be previously mixed with the crystalline polypropylene resin (A) and then mixed with the propylene polymer (B). (A), (B), and (C) may be mixed simultaneously, and various additives may be mixed simultaneously.

III. Features, Actions, and Uses of Flame Retardant Polypropylene Resin Composition The flame retardant polypropylene resin composition of the present invention exhibits flame retardancy and drip resistance superior to those of conventionally known flame retardant polyolefin resins, and mechanically. Excellent strength.
The action is not clear, but the present inventors consider as follows.
That is, when various compounding components are melted and kneaded with the polypropylene resin, the crystalline polypropylene resin (A) melts, but the propylene polymer (B) also melts, and a specific branched structure of the propylene polymer (B). By the effect of the copolymer having, the melt tension of the molten resin is improved, and the effect of preventing drip is exhibited.
Moreover, since non-halogen flame retardants (C) such as phosphate flame retardants are used as flame retardants, the environmental impact is small compared to halogen flame retardants. For example, phosphate flame retardants are: During combustion, it is thermally decomposed into polymetaphosphoric acid. As a result of the formation of a protective layer by the generated phosphoric acid layer and the dehydration action by polymetaphosphoric acid, the flame retardant effect is exhibited by blocking oxygen by forming a carbon film to be formed.

  Furthermore, the flame-retardant polypropylene resin composition of the present invention has excellent flame resistance in addition to excellent mechanical strength and moldability, and particularly excellent drip prevention during combustion. It can be suitably used for parts, container packaging members, building 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, the physical properties of the flame retardant polypropylene resin composition or its constituent components were measured and evaluated according to the following evaluation methods, and the following resins were used. Further, unless otherwise specified, the parts shown in the examples are parts by weight.

1. Evaluation method (1) Melt flow rate (MFR) [unit: g / 10 min]:
The propylene-based resin conforms to JIS K7210: 1999 “Method for testing plastics-thermoplastic melt mass flow rate (MFR) and melt volume flow rate (MVR)”, condition M (230 ° C., 2.16 kg load). Measured in conformity.
(2) Weight average molecular weight (Mw), molecular weight distribution:
It was measured by the method described in the present specification by gel permeation chromatography (GPC).
(3) mm fraction:
The measurement was carried out by the method described in the present specification using GSX-400 and FT-NMR manufactured by JEOL.
(4) Elongation viscosity:
Using a rheometer, measurement was performed by the method described in the present specification.

(5) Melting temperature (Tm):
Measurements were made using a Seiko DSC.
After taking 5.0 mg of sample and holding it at 200 ° C. for 5 minutes, it is crystallized at a rate of 10 ° C./min. The peak temperature of the melting curve is taken as the melting point. When a plurality of melting points are observed in the resin, the one observed at the highest temperature is taken as the melting point of the resin.
(6) Determination of ethylene content:
It is measured by ¹³ C-NMR under the same conditions as the mm measurement described above. The analysis method is calculated according to the method described in Macromolecules 1982 1150.

(7) Flame retardancy:
Using an injection-molded sheet molded at a resin temperature of 220 ° C., the vertical combustion test method defined in the UL94V test (Underwriters Laboratories) “Plastic material combustion test for equipment parts” was used.
(8) Dripping property (drip property):
Compliant with the vertical combustion test method specified in “Plastic material combustion test for equipment parts” of UL94V test (Underwriter Laboratories Corp.) using injection molded sheets molded at resin temperatures of 200 ° C and 220 ° C And evaluated according to the following criteria.
◎: No dripping ○: Dropping, but cotton is not ignited ×: Massive dripping that ignites cotton

(9) Appearance evaluation:
Foreign matters on an injection molded sheet of 120 mm × 120 mm × 2 mm molded at a resin temperature of 200 ° C. were visually observed and evaluated according to the following criteria.
○: No gel-like foreign matters Δ: One to 10 gel-like foreign matters 0.2 mm or more could be observed ×: 11 or more gel-like foreign matters 0.2 mm or more could be observed

(10) Flexural modulus Measured at 23 ° C. according to JIS K7203. The dimension of the molded product was 90 × 10 × 4 mm. Unit: MPa.

2. Materials used (I) Crystalline polypropylene resin (A)
The crystalline polypropylene resin (A1) produced in Production Example 1 below was used.

<Production of crystalline polypropylene resin (A)>
[Production Example A1]:
(Manufacture of Ziegler catalysts)
To a 500-ml glass three-necked flask (with a thermometer, a dropping funnel and a stirring rod) purged with nitrogen, 144 ml of purified heptane and 58 ml of titanium tetrachloride were added. The dropping funnel was charged with 120 ml of heptane and 66 ml of diethylaluminum chloride. The flask is cooled to −10 ° C., and diethylaluminum chloride is added dropwise over 3 hours under stirring at 120 rpm. Furthermore, after reacting at -10 ° C for 1 hour, the temperature of the system was slowly raised to 65 ° C in 1 hour. After reacting at 65 ° C. for 1 hour, the supernatant was separated by decantation and washed 5 times with 200 ml of fresh purified heptane. Next, 250 ml of heptane and 99 ml of diisoamyl ether were added and reacted at 35 ° C. for 1 hour. After completion of the reaction, it was washed 5 times with 200 ml of purified heptane in the same manner as in the previous reduction of titanium tetrachloride. Next, 150 ml of heptane and 116 ml of titanium tetrachloride were added and reacted at 65 ° C. for 2 hours. After completion of the reaction, washing was performed 5 times with 200 ml of purified heptane. Finally, 150 ml of heptane and 2.3 ml of n-butanol were added, reacted at room temperature for 1 hour, washed 3 times with 200 ml of heptane to obtain a solid catalyst component.

(Propylene polymerization)
After thoroughly replacing the 200-liter stirred autoclave with propylene, introduce 63 liters of fully dehydrated and deoxygenated n-heptane, mix diethylaluminum monochloride and ethylaluminum dichloride, and stir at room temperature for 2 hours. Then, 50 g of ethylaluminum chloride prepared by homogenization and 10 g of the titanium trichloride composition were introduced at 65 ° C. in a propylene atmosphere. The first stage polymerization was started by heating the autoclave to 70 ° C. and then introducing propylene at a flow rate of 9 kg / hr while adjusting the hydrogen concentration to 5 vol%. After 202 minutes, the introduction of propylene was stopped, and the polymerization was further continued at 70 ° C. for 90 minutes. Vapor phase propylene was purged to 0.2 kg / cm ² G. The second stage polymerization was carried out for 60 minutes by lowering the temperature of the autoclave to 65 ° C., and then introducing propylene at 4.6 kg / hr and ethylene at 3 kg / hr.

  The slurry thus obtained was filtered and dried to obtain a powdery propylene / ethylene block copolymer (A1). [Mm] of the copolymer was 0.96, and MFR was 30 g / 10 min. The copolymer did not undergo strain hardening in the measurement of uniaxial elongational viscosity (λmax: 1.0).

(II) Propylene polymer (B)
The propylene resin (B1) to propylene resin (B4) produced in the following production examples B1 to B4 were used.

[Production Example B1]:
(1) [Synthesis of rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride]:
Synthesis of (1-a) dimethylbis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) silane:
Synthesis was performed according to the method described in Example 1 of JP-A No. 2004-124044.

Synthesis of (1-b) rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride:
To a 100 ml glass reaction vessel, 5.3 g (8.8 mmol) of dimethylbis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) silane and 150 ml of diethyl ether were added, and dry ice was added. -It cooled to -70 degreeC with the methanol bath. To this, 12 ml (18 mmol) of a 1.50 mol / liter n-butyllithium-hexane solution was added dropwise. After dropping, the temperature was returned to room temperature and stirred for 16 hours. The solvent of the reaction solution was concentrated under reduced pressure to about 20 ml, 200 ml of toluene was added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 2.8 g (8.7 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred for 3 days while gradually returning to room temperature.
The solvent was distilled off under reduced pressure, recrystallized from dichloromethane / hexane, and racemic dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride (purity 99% or more). ) Was obtained as yellow-orange crystals (2.9 g, yield 39%).
The resulting proton nuclear magnetic resonance method for racemate identified value according to ^{(1 H-NMR)} are shown below.
_{^{[1 H-NMR (CDCl 3}} ) Identification Results
Racemate: δ 1.12 (s, 6H), δ 2.42 (s, 6H), δ 6.06 (d, 2H), δ 6.24 (d, 2H), δ 6.78 (dd, 2H), δ 6. 97 (d, 2H), δ 6.96 (s, 2H), δ 7.25 to δ 7.64 (m, 12H).

(2) [Catalyst synthesis]:
(2-1) Chemical treatment of ion-exchangeable layered silicate 96% sulfuric acid (1044 g) was added to 3456 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. ) 600 g was added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, added with 2400 g of distilled water and then filtered to obtain 1230 g of a cake-like solid.
Next, 648 g of lithium sulfate and 1800 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution, and the entire amount of the above-mentioned cake solid was added, and further 522 g of distilled water was added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, filtered after adding 1980 g of distilled water, further washed with distilled water to pH 3, and filtered to obtain 1150 g of cake-like solid.
The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed, and further, rotary kiln drying was performed under a condition of 215 ° C. under a nitrogen stream for a residence time of 10 minutes. 340 g was obtained.
The composition of this chemically treated smectite is Al: 7.81 wt%, Si: 36.63 wt%, Mg: 1.27 wt%, Fe: 1.82 wt%, Li: 0.20 wt%, Al / Si = 0.222 [mol / mol].

(2-2) Catalyst Preparation and Prepolymerization In a three-necked flask (volume: 1 L), 20 g of the chemically treated smectite obtained above was added, and heptane (114 mL) was added to form a slurry, to which triethylaluminum (50 mmol: 81 mL) of a heptane solution having a concentration of 71 mg / mL was added and stirred for 1 hour, then washed to 1/1000 with heptane, and heptane was added so that the total volume became 200 mL.
In another flask (volume 200 mL), heptane (85 mL) was added to rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride (0.3 mmol). Then, triisobutylaluminum (0.6 mmol: 0.85 mL of a heptane solution with a concentration of 140 mg / mL) was added and stirred for 45 minutes at room temperature to cause a reaction. This solution was added to a 3 L flask containing chemically treated smectite and stirred at room temperature for 45 minutes. Thereafter, 214 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 20 g / hour and prepolymerization was performed while maintaining the temperature at 40 ° C. for 2 hours. Thereafter, propylene feed was stopped, and residual polymerization was performed at 50 ° C. for 0.5 hour. After removing the supernatant of the resulting catalyst slurry by decantation, the prepolymerized catalyst was washed by adding decantation again with heptane. Triisobutylaluminum (12 mmol: 17 mL of a heptane solution having a concentration of 140 mg / mL) was added to the portion remaining after the decantation, and the mixture was stirred for 10 minutes. This solid was dried under reduced pressure for 2 hours to obtain 47.6 g of a dry prepolymerized catalyst. The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.38.

(3) [Polymerization]
First step polymerization:
The 3 L autoclave was thoroughly dried in advance by circulating nitrogen under heating, and then the interior of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL) and introducing 750 g of liquid propylene, the temperature was raised to 70 ° C. Thereafter, 200 mg of the above prepolymerized catalyst in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 70 ° C. for 1 hour, unreacted propylene was quickly purged, and the inside of the autoclave was purged with nitrogen to stop the polymerization in the first step. Using a Teflon (registered trademark) tube from the nitrogen-substituted autoclave, 7 g of the polymer after the first step was collected and analyzed.

Second step polymerization:
After maintaining the nitrogen-substituted autoclave at 50 ° C. and atmospheric pressure, propylene was added at a partial pressure of 1.0 MPa, and ethylene was then added at a partial pressure of 1.0 MPa to start polymerization in the second step. During the polymerization, a mixed gas of ethylene / propylene, which had been adjusted in advance so as to have a constant composition, was introduced to keep the total pressure at 2.0 MPa and maintained at 50 ° C. The average gas composition of the polymerization in the second step was C2: 53.4%. After 2 hours, the polymerization was stopped by purging an unreacted ethylene / propylene mixed gas. As a result, 275 g of the polymer (B1) was obtained.

[Production Example B2]
(1) [Polymerization]
First step polymerization:
The 3 L autoclave was thoroughly dried beforehand by circulating nitrogen under heating, and then the inside of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL) and introducing 16 g of ethylene and 750 g of liquid propylene, the temperature was raised to 70 ° C.
Thereafter, 100 mg of the prepolymerized catalyst prepared in Production Example B1 in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 70 ° C. for 1 hour, unreacted propylene was quickly purged, and the inside of the autoclave was purged with nitrogen to stop the polymerization in the first step.
From the nitrogen-substituted autoclave, 15.6 g of the polymer after the first step was collected and analyzed using a Teflon (registered trademark) tube.

Second step polymerization:
After maintaining the above nitrogen-substituted autoclave at 50 ° C. and atmospheric pressure, the second polymerization was started by quickly adding 1.0 MPa and then ethylene at a partial pressure of 1.0 MPa. During the polymerization, a mixed gas of ethylene / propylene, which had been adjusted in advance so as to have a constant composition, was introduced to keep the total pressure at 2.0 MPa and maintained at 50 ° C.
The average gas composition of the polymerization in the second step was C2: 57.6%. After 2 hours, the polymerization was stopped by purging an unreacted ethylene / propylene mixed gas. As a result, 445 g of the polymer (B2) was obtained.

[Production Example B3]
(1) [Synthesis of rac-dichloro (1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl)) hafnium dichloride]:
The synthesis of rac-dichloro (1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl)) hafnium dichloride was carried out in the same manner as in Example 1 of JP-A-11-240909. Carried out.

(2) Catalyst preparation and prepolymerization:
In a three-necked flask (volume: 1 L), 10 g of chemically treated smectite obtained by chemical treatment of (2-1) ion-exchange layered silicate of Production Example B1 was added, and heptane (66 mL) was added to form a slurry. Triisobutylaluminum (24 mmol: 34 mL of a 140 mg / mL heptane solution) was added thereto and stirred for 1 hour, then washed with heptane to a residual liquid ratio of 1/100, and heptane was added so that the total volume became 100 mL. .
In another flask (volume 200 mL), rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) hafnium dichloride (0.135 mmol) synthesized in Example 1 was used. ) Was dissolved in toluene (38 mL) (complex solution 1).
In another flask (volume 200 mL), rac- (1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl)) hafnium dichloride (0. 015 mmol) was dissolved in toluene (5 mL) (complex solution 2).

To a 1 L flask containing chemically treated smectite, triisobutylaluminum (0.6 mmol: 0.85 mL of a heptane solution having a concentration of 140 mg / mL) was added, and the complex solution 1 was added, followed by the addition of the complex solution 2. Stir at room temperature for 60 minutes. Thereafter, 356 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 40 ° C. for 2 hours. Thereafter, propylene feed was stopped, and residual polymerization was performed at 50 ° C. for 0.5 hour. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (12 mmol: 8.5 mL of a heptane solution having a concentration of 140 mg / mL) was added and stirred for 10 minutes. This solid was dried under reduced pressure for 2 hours to obtain 26.1 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 1.84.

(2) [Polymerization]
First step polymerization:
The 3 L autoclave was thoroughly dried in advance by circulating nitrogen under heating, and then the interior of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL) and introducing 300 Nml of hydrogen and 750 g of liquid propylene, the temperature was raised to 75 ° C.
Thereafter, 150 mg of the above prepolymerized catalyst in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 75 ° C. for 1 hour, unreacted propylene was quickly purged, and the inside of the autoclave was purged with nitrogen to stop the polymerization in the first step.
Using a Teflon (registered trademark) tube from the nitrogen-substituted autoclave, 22 g of the polymer after the first step was collected and analyzed.

Second step polymerization:
After maintaining the above nitrogen-substituted autoclave at 60 ° C. and atmospheric pressure, propylene was added at a partial pressure of 0.5 MPa, and then ethylene was added at a partial pressure of 1.5 MPa to start polymerization in the second step. During the polymerization, a mixed gas of ethylene / propylene, which had been adjusted in advance so as to have a constant composition, was introduced to maintain the total pressure at 2.0 MPa and maintained at 60 ° C.
The average gas composition of the polymerization in the second step was C2: 81.7%. After 50 minutes, polymerization was stopped by purging an unreacted ethylene / propylene mixed gas. As a result, 330 g of the polymer (B3) was obtained.

[Production Example B4]
(1) Preparation of transition metal compound catalyst component:
In a stainless steel reactor equipped with a stirrer, 0.3 l of decane, 48 g of anhydrous magnesium chloride, 170 g of orthotitanate-n-butyl and 195 g of 2-ethyl-1-hexanol were mixed and stirred at 130 ° C. for 1 hour. It was dissolved by heating to obtain a uniform solution. This homogeneous solution was heated to 70 ° C., 18 g of di-i-butyl phthalate was added with stirring, and after 1 hour, 520 g of silicon tetrachloride was added over 2.5 hours to precipitate a solid. For 1 hour. The solid was separated from the solution and washed with hexane to give a solid product.
The total amount of the solid product is mixed with 1.5 liters of titanium tetrachloride dissolved in 1.5 liters of 1,2-dichloroethane, then 36 g of di-i-butyl phthalate is added and allowed to react at 100 ° C. for 2 hours with stirring. After that, the liquid phase part was removed by decantation at the same temperature, 1.5 liters of 1,2-dichloroethane and 1.5 liters of titanium tetrachloride were added again, and the mixture was stirred and held at 100 ° C. for 2 hours, and washed with hexane. Dried to obtain a titanium-containing supported catalyst component containing 2.8% by weight of titanium.

(2) Preparation of preactivated catalyst:
After replacing the stainless steel reactor with inclined blades having an inner volume of 5 liters with nitrogen gas, 2.8 liters of n-hexane, 4 mmoles of triethylaluminum and 9.0 g of titanium-containing supported catalyst component (5 in terms of titanium atoms) Then, 20 g of propylene was supplied, and prepolymerization was performed at −2 ° C. for 10 minutes.
When the polymer produced by the prepolymerization was analyzed, 2 g of propylene became polypropylene (B) per 1 g of the titanium-containing supported catalyst component.
After completion of the reaction time, unreacted propylene is discharged out of the reactor, the gas phase portion of the reactor is purged with nitrogen once, and then the pressure in the reactor is maintained while maintaining the temperature in the reactor at -1 ° C. Was maintained at 0.59 MPa by continuously supplying ethylene to the reactor for 2 hours for preactivation. As a result of analyzing the polymer produced by the preactivation polymerization, 22 g of polyethylene was present per 1 g of the titanium-containing supported catalyst component, and the intrinsic viscosity of the polymer measured in tetralin at 135 ° C. was 34.0 dl / g. .
After completion of the reaction time, unreacted ethylene was discharged out of the reactor, the gas phase portion of the reactor was purged with nitrogen once, 1.6 mmol of diisopropyldimethoxysilane was added to the reactor, and then 20 g of propylene was added. And kept at 1 ° C. for 10 minutes to carry out addition polymerization after the preactivation treatment.
As a result of analyzing the polymer produced by addition polymerization, the amount of polypropylene produced by addition polymerization was 2.0 g per 1 g of the titanium-containing supported catalyst component. After completion of the reaction time, unreacted propylene was discharged out of the reactor, and the gas phase portion of the reactor was purged with nitrogen once to obtain a preactivated catalyst slurry for the present (co) polymerization.

(3) Production of polypropylene composition (book (co) polymerization of propylene):
A stainless steel polymerization vessel equipped with a stirrer with an internal volume of 500 liters was purged with nitrogen, and at 20 ° C., 240 liters of n-hexane, 780 mmol of triethylaluminum, 78 mmol of diisopropyldimethoxysilane, and 1 of the preactivated catalyst slurry obtained above / 2 amount was charged into the polymerization vessel. Subsequently, after introducing 100 liters of hydrogen into the polymerization vessel and raising the temperature to 70 ° C., propylene was continuously added under the condition of the polymerization temperature of 70 ° C. while maintaining the gas phase pressure in the polymerization vessel at 0.79 MPa. The mixture was fed into the polymerization vessel for 90 minutes to carry out the first step polymerization. After the polymerization was completed, the supply of propylene was stopped, the internal temperature was cooled to 30 ° C., and hydrogen and unreacted propylene were released. Subsequently, a part of the polymerization slurry was extracted and MFR was measured and found to be 7.5.

  After raising the internal temperature to 60 ° C., 25 liters of hydrogen was introduced into the polymerization reactor, and ethylene and propylene were continuously supplied for 2 hours so that the supply ratio of ethylene was 35% by weight. The total ethylene supply was 7.5 kg. After the polymerization time has elapsed, 1 liter of methanol is introduced into the polymerization vessel, the catalyst deactivation reaction is carried out at 70 ° C. for 15 minutes, the unreacted gas is subsequently discharged, the solvent is separated, and the polymer is dried. 40.5 kg (B4) of 1.95 dl / g of polymer was obtained.

  Table 1 shows the physical properties of the raw materials (B1) to (B4).

(III) Non-halogen flame retardant (C)
The following phosphorous flame retardant (C1) was used as the non-halogen flame retardant (C).
(C1) “ADK STAB FP2000” manufactured by Asahi Denka Co., Ltd. was used as a phosphate flame retardant. As physical properties of the flame retardant, there is no melting point (decomposes at 250 ° C. or higher), a nitrogen content of 20 to 23% by weight, and a phosphorus content of 18 to 21% by weight.

[Example 1]
For 100 parts by weight of a polymer mixture of 90% by weight of (A1) obtained above as a polypropylene resin and 10% by weight of (B1) obtained above as a specific propylene polymer component (B), 30 parts by weight of the above (C1) as a phosphate flame retardant and pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Ciba) as other additives・ 0.2 parts by weight of antioxidant irganox 1010 manufactured by Specialty Chemicals, Inc., tris (2,4-di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals, processing stabilizer irgaphos 168) ) 0.2 parts by weight and calcium stearate 0.05 parts by weight were each placed in a Henschel mixer and stirred and mixed for 3 minutes. The obtained mixture was melt-kneaded and extruded at 200 ° C. using a biaxial extruder having a diameter of 30 mm, and pelletized. After drying the obtained pellets at 80 ° C. for 4 hours, using an injection molding machine with a clamping pressure of 100 t, the molding temperature (resin temperature) is 200 ° C. and 220 ° C., and the mold cooling temperature is 40 ° C. A test piece for UL94V having a thickness of 5 mm was prepared. Further, an injection molded sheet of 120 mm × 120 mm × 2 mm was molded under the same conditions and used for appearance evaluation.

  Table 2 shows the formulation of the flame retardant polypropylene resin composition and the results of flame retardant evaluation of the composition.

[Examples 2 to 7]
Using the blending raw materials shown in Table 1, according to the blending recipe shown in Table 2, other additives were blended in the same manner as in Example 1, and the mixture was stirred, mixed and melt-kneaded to form pellets. Table 2 shows the results of flame retardant evaluation performed by preparing test pieces from the obtained pellets.

[Comparative Examples 1-3]
Using the blending raw materials shown in Table 1, according to the blending recipe shown in Table 2, other additives were blended in the same manner as in Example 1, and the mixture was stirred, mixed and melt-kneaded to form pellets. Table 2 shows the results of flame retardant evaluation performed by preparing test pieces from the obtained pellets.

The evaluation results in Table 2 revealed the following.
(1) Unless the propylene polymer (B) is blended, excellent flame retardancy and anti-drip properties are not achieved (Comparative Example 1).
(2) When the amount of the propylene polymer (B) is too large, the appearance evaluation is slightly poor (Comparative Example 2).
(3) When blended with (B4) which does not satisfy the standard of the propylene polymer (B) according to the present invention instead of the propylene polymer (B), excellent flame retardancy and drip at the time of high temperature molding Preventability is not achieved (Comparative Example 3). Further, when the blending amount of (B4) is increased, the appearance evaluation is poor (comparative example 4), although the flame retardancy and the drip prevention property are good.

  In addition to excellent mechanical strength and moldability, the flame-retardant polypropylene resin composition of the present invention has excellent flame retardancy, and particularly excellent drip prevention during combustion. It can utilize suitably for a container packaging member, a building member, etc.

It is a figure of explanation of the base line and section of a chromatogram in GPC It is a plot figure which shows an example of the extensional viscosity measured with the uniaxial extensional viscometer. It is a figure which shows an example of the TEM observation result of the propylene polymer (B) which concerns on this invention. It is a figure which shows an example of the TEM observation result of the propylene polymer (B) which concerns on this invention. It is a figure which shows an example of the TEM observation result of a normal propylene polymer.

Claims (7)

Crystalline polypropylene resin (A) having an MFR (230 ° C., 2.16 kg load) of 0.1 to 80 g / 10 min, an isotactic triad fraction (mm) of 0.95 or more and 60 to 99% by weight and It is composed of a component (I) that is insoluble in p-xylene at 25 ° C. and a component (S) that is soluble in p-xylene at 25 ° C., and (i) a weight average molecular weight (Mw) measured by GPC is 100,000 1 million, (ii) a component insoluble in hot p-xylene is 0.3% by weight or less, and (iii) a strain hardening degree (λmax) in the measurement of elongational viscosity is 1.1 or more. A flame retardant polypropylene resin composition comprising 10 to 50 parts by weight of a halogen-free flame retardant (C) with respect to 100 parts by weight of a polypropylene resin component comprising 1 to 40% by weight of the polymer (B).
Component (I): Component (CXIS) that is insoluble in p-xylene at 25 ° C. having the requirements defined in the following (I1) to (I5).
(I1) 20 to 95% by weight based on the total amount of the polymer (B).
(I2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(I3) The isotactic triad fraction (mm) measured by ¹³ C-NMR is 0.93 or more.
(I4) The degree of strain hardening (λmax) in the measurement of elongational viscosity is 2.0 or more.
(I5) A propylene unit and an ethylene unit or an α-olefin unit are contained.
Component (S): Component (CXS) that dissolves in p-xylene at 25 ° C. having the requirements defined in the following (S1) to (S3).
(S1) 5 to 80% by weight based on the total amount of the polymer (B).
(S2) The weight average molecular weight (Mw) measured by GPC is 100,000 to 1,000,000.
(S3) Contains propylene units, ethylene units and / or α-olefin units.   The component (S) of the propylene-based polymer (B) further has a requirement that the strain hardening degree (λmax) in the measurement of the elongational viscosity (S4) is 1.2 or more. Flame retardant polypropylene resin composition.   2. The propylene polymer (B) is composed of a polymer having a branched structure in which a crystalline propylene polymer segment is a side chain and an amorphous propylene copolymer segment is a main chain. The flame-retardant polypropylene resin composition described in 1.   Component (I) of the propylene polymer (B) is composed of a polymer having a branched structure in which a crystalline propylene polymer segment is a side chain and an amorphous propylene copolymer segment is a main chain. The flame-retardant polypropylene resin composition according to claim 1.   The flame-retardant polypropylene according to claim 1, wherein component (I) of the propylene-based polymer (B) contains an ethylene unit and has an ethylene content of 0.1 to 10% by weight. Resin composition.   The flame retardant polypropylene resin composition according to claim 1, wherein the component (S) of the propylene-based polymer (B) contains an ethylene unit and has an ethylene content of 10 to 60% by weight. object.   The flame retardant polypropylene resin composition according to any one of claims 1 to 6, wherein the non-halogen flame retardant (C) is a phosphate flame retardant.

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