JP6291778B2 - Polypropylene flame retardant resin composition - Google Patents

Description

  The present invention relates to a flame retardant polypropylene resin composition containing a filler, and more specifically, a specific amount of a polypropylene resin having a specific long chain branched structure, a halogen flame retardant and a filler is blended, preferably further The present invention relates to a flame retardant polypropylene resin composition comprising a specific amount of other polypropylene resin.

In order to obtain a flame retardant polypropylene resin, it is widely practiced to blend a flame retardant composition comprising a halogen flame retardant and an antimony compound with various polypropylene resins. This is because these flame retardant compositions can exhibit flame retardancy in a relatively small amount.
However, when these flame retardant compositions are used, since the drip property of the resin generated at the time of combustion cannot be suppressed, it is necessary to impart flame retardant performance only by the self-extinguishing effect. For this reason, the flame retardancy depends on the addition amount of the halogen-based flame retardant, and it is necessary to add a large amount of the flame retardant composition in order to develop higher flame retardancy. And with the addition of a large amount of the flame retardant composition, there is concern that the mechanical properties will deteriorate and the appearance will be poor at the time of molding, so in order to obtain higher flame retardant performance, the self-extinguishing effect A technique for imparting flame retardancy by a method other than the above is required.

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

  Patent Document 1 discloses a flame retardant resin composition that exhibits a drip resistance prevention effect (drip resistance) during combustion by using a polypropylene resin having a specific long chain branched structure, and has improved flame retardancy. However, it is still insufficient for the higher flame retardancy demanded in recent years, and the mechanical properties are not sufficient for practical use.

  In Patent Documents 2 and 3, a flame retardant resin in which tetrafluoroethylene (PTFE) is added to add an organic flame retardant (particularly, a phosphate flame retardant) to a thermoplastic resin and impart a drip suppression effect. A composition is described. However, PTFE aggregates due to the shear stress during kneading, and there is a concern that the mechanical properties and flame retardancy will decrease. In order to suppress aggregation to such an extent that the mechanical properties are not affected, it is necessary to make the addition amount of PTFE as small as possible. For this reason, a decrease in flame retardancy associated with a decrease in the amount of PTFE added is unavoidable, and it is difficult to maintain the flame retardancy without deteriorating mechanical properties.

  Patent Document 4 describes a technology in which a halogen flame retardant having a melting point of 300 ° C. or higher is used to impart extremely high flame retardancy. However, the above-mentioned flame retardant is added to the thermosetting resin, and the property that the thermosetting resin is cured by heat is applied to the effect of suppressing the drip property at the time of combustion. It is extremely difficult to develop this into a thermoplastic resin whose viscosity is lowered by heat.

JP 2009-275117 A JP 2005-60603 A Japanese Patent Laid-Open No. 10-30046 JP 2011-74210 A

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

  As a result of intensive studies to solve the above problems, the present inventors have determined that a specific amount of a halogen-based flame retardant, a flame retardant aid and a filler is added to a polypropylene resin containing a polypropylene resin having a specific long-chain branched structure. Blended, flame retardant polypropylene that has both self-extinguishing properties and drip resistance during combustion, exhibits extremely high flame resistance (5VA in UL94-5V), and has mechanical properties (especially rigidity) and molding processability The inventors have found that a resin composition can be obtained, and have completed the present invention.

That is, according to the first invention of the present invention, the polypropylene resin (A) that satisfies the following conditions (A-1) and (A-2) and the filler that satisfies the following conditions (B-1): It contains (B), a halogenated flame retardant (C) and a flame retardant aid (E), and has a melt flow rate (MFR) (230 ° C., 2.16 kg load) of 1.0 to 20 g / 10 min. and the polypropylene resin composition characterized by satisfying the following condition (a) is provided.
Condition (A-1)
The polypropylene resin (A) contains the polypropylene resin (X) having the following characteristics (Xi) to (X-iv) and having a long-chain branched structure.
Characteristic (X-i): Melt flow rate (MFR) (230 ° C., 2.16 kg load) is 0.1 to 30.0 g / 10 min.
Characteristic (X-ii): GPC molecular weight distribution Mw / Mn is 3.0 to 10.0 and Mz / Mw is 2.5 to 10.0.
Characteristic (X-iii): Melt tension (MT) (unit: g) is
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy one of the following.
Characteristic (X-iv): 25 degreeC paraxylene soluble component amount (CXS) is less than 5.0 weight% with respect to polypropylene resin (X) whole quantity.
Condition (A-2)
The polypropylene resin (A) is at least selected from the group consisting of the polypropylene resin (X) having the long-chain branched structure and the polypropylene resin (Y) having the following properties (Yi) to (Y-ii): Contains one type of polypropylene resin.
Characteristic (Yi): at least one polypropylene resin selected from the group consisting of a propylene homopolymer and a propylene-α-olefin block copolymer, corresponding to the polypropylene resin (X) having the long-chain branched structure do not do.
Characteristic (Y-ii): The polypropylene resin (Y) has a melt flow rate (MFR) (230 ° C., 2.16 kg load) of 1.0 to 100 g / 10 min.
Condition (B-1)
The filler (B) is at least one selected from the group consisting of glass fiber and talc.
Condition (A)
The content of each component is 13 to 75 parts by weight of polypropylene resin (A), 5 to 40 parts by weight of filler (B) and 15 to 35 parts by weight of halogenated flame retardant (C), flame retardant aid (E) 5 The total amount of polypropylene resin (A), filler (B), halogen flame retardant (C) and flame retardant aid (E) is 100 parts by weight.

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

  According to the third invention of the present invention, there is provided a polypropylene resin composition in the first or second invention, wherein the halogen flame retardant (C) is a bromine flame retardant.

  According to a fourth aspect of the present invention, in any one of the first to third aspects, the filler (B) is at least one selected from the group consisting of glass fiber and talc. A composition is provided.

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

  The polypropylene resin composition of the present invention is preferably further blended with another polypropylene resin by blending a specific amount of a polypropylene resin having a specific long chain branched structure, a halogen flame retardant, a flame retardant aid and a filler. By doing so, in addition to excellent mechanical properties (particularly rigidity) and molding processability, both self-extinguishing property during combustion and drip resistance are achieved, and extremely high flame retardancy is achieved.

  The present invention contains a polypropylene resin (X) having a specific long-chain branched structure (hereinafter, also simply referred to as component (X)) and satisfies the following conditions (A-1) and (A-2). Resin (A) (hereinafter also simply referred to as component (A)) 13 to 75 parts by weight, specific filler (B) (hereinafter also simply referred to as component (B)) 5 to 40 parts by weight, halogen 15 to 35 parts by weight of a flame retardant (C) (hereinafter also simply referred to as component (C)) and 5 to 12 parts by weight of a flame retardant aid (E) (hereinafter also simply referred to as component (E)) The total amount of component (A), component (B), component (C) and component (E) is 100 parts by weight), and component (A) is preferably a polypropylene resin ( Y) (hereinafter also simply referred to as component (Y)), the proportion of which is component (X) 1 99% by weight and component (Y) 1 to 99% by weight (provided that the total amount of component (X) and component (Y) is 100% by weight) and a molded resin composition It relates to a molded body.

  The polypropylene resin composition of the present invention and a molded product formed from the same eliminate the problems of the conventional polypropylene resin composition and the molded product formed from the same, and include various molded products, especially fillers. In addition to excellent mechanical properties, weather resistance, and moldability, it has extremely high flame retardancy, so that it can be suitably used for automobile parts, electrical parts, container packaging members, building members, large members, and the like.

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

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

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

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

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

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

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

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

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

1) -4. Characteristic (X-iv): 25 ° C. Paraxylene soluble component amount (CXS)
The polypropylene resin (X) having a long-chain branched structure used in the present invention is more sticky when the stereoregularity becomes the polypropylene-based resin composition of the present invention and a molded product formed by molding the same. And low crystalline components that cause bleed-out, and high rigidity can be maintained, which is preferable. This low crystallinity component is evaluated by the amount of xylene soluble component (CXS) at 25 ° C., and it must be less than 5.0% by weight, preferably 3. It is 0 weight% or less, More preferably, it is 1.0 weight% or less, More preferably, it is 0.5 weight% or less. The lower limit is not particularly limited, but is usually 0.01% by weight or more, preferably 0.03% by weight or more. By setting CXS in such a range, as described above, the rigidity of the polypropylene resin composition of the present invention and a molded product formed from the same can be increased, and at the same time, stickiness and bleed-out can be suppressed. Is possible.

The details of the CXS measurement method are as follows.
A 2 g sample is dissolved in 300 ml of p-xylene (containing 0.5 mg / ml BHT) at 130 ° C. to make a solution, and then left at 25 ° C. for 12 hours. Thereafter, the precipitated polymer is separated by filtration, p-xylene is evaporated from the filtrate, and further dried under reduced pressure at 100 ° C. for 12 hours to recover room temperature xylene-soluble components. The ratio [wt%] of the weight of the recovered component to the charged sample weight is defined as CXS.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

2). Polypropylene resin (Y)
Below, the detail of the polypropylene resin (Y) used for this invention is demonstrated.
2) -1. Characteristic (Yi): Polypropylene resin (Y) The polypropylene resin (Y) used in the present invention is at least one polypropylene selected from the group consisting of a propylene homopolymer and a propylene-α-olefin block copolymer. It is a resin and does not correspond to the polypropylene resin (X) having the long-chain branched structure.
The propylene-α-olefin block copolymer preferably used is a block copolymer having a C 2-8 α-olefin excluding propylene and propylene as a comonomer, and a propylene content of 70 to 99% by weight (that is, the comonomer content is 0.01 to 30% by weight), more preferably a block copolymer of propylene and an α-olefin having a propylene content of 90% by weight or more.

Moreover, the comonomer which is a C2-C8 alpha olefin except the propylene copolymerized with a propylene may be used 1 type, and may be used in combination of 2 or more type.
Specific examples of the propylene-α-olefin block copolymer include a propylene-ethylene block copolymer, a propylene-butene-1 block copolymer, a propylene-pentene-1 block copolymer, and a propylene-hexene-1 block. Copolymer, binary copolymer such as propylene-octene-1 block copolymer, ternary copolymer such as propylene-ethylene-butene-1 block copolymer, propylene-ethylene-hexene-1 block copolymer Examples thereof include propylene-ethylene block copolymers and propylene-ethylene-butene-1 block copolymers. The content of the α-olefin monomer in the propylene-α-olefin block copolymer is usually about 0.01 to 30% by weight, preferably 1 to 30% by weight, more preferably about 1 to 10% by weight. Can be included.

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

  From the viewpoint of moldability, the polypropylene resin (Y) preferably has a melting point of 100 to 170 ° C, more preferably 150 to 165 ° C. The melting point of the polypropylene resin can be appropriately controlled mainly by the type of propylene used as a raw material and the α-olefin other than propylene, the copolymerization ratio, MFR, and the like. The “melting point” in the present specification is a melting peak temperature measured by a differential scanning calorimeter (DSC).

2) -2. Characteristic (Y-ii): Melt flow rate of polypropylene resin (Y) The polypropylene resin (Y) used in the present invention is a melt flow rate (hereinafter also referred to as MFR) according to JIS K7210 [measurement temperature 230 ° C. , Load 2.16 kg (21.18 N)] is 1.0 to 150 g / 10 minutes. It is preferably 5.0 to 80 g / 10 minutes, more preferably 10 to 60 g / 10 minutes. By setting the MFR within such a range, the polypropylene resin composition of the present invention and a molded product obtained by molding the same can maintain good moldability and exhibit high drip resistance and high flame resistance. Can be achieved. That is, when the MFR is less than 1 g / 10 min, the load when molding the polypropylene resin composition of the present invention increases, the moldability deteriorates, and the molded article may be discolored and the appearance may deteriorate. On the other hand, if it exceeds 150 g / 10 minutes, appropriate drip resistance cannot be exhibited and flame retardancy may be deteriorated.

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

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

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

3). Compounding conditions (A-1)
It is essential that the polypropylene resin (A) contains a polypropylene resin (X) having a long-chain branched structure. By using the polypropylene resin (X) having a long-chain branched structure as an essential component in the polypropylene resin composition of the present invention and a molded product formed by molding the same, it is possible to maintain high rigidity and at the same time have appropriate fluidity. In addition to exhibiting good moldability, it has an appropriate melt tension, so that it has the effect of having good drip resistance and high flame retardancy.

Condition (A-2)
Furthermore, the polypropylene resin (A) is characterized by containing at least one polypropylene resin selected from the group consisting of the polypropylene resin (X) having a long chain branched structure and the polypropylene resin (Y). In particular, in the polypropylene resin composition of the present invention and a molded product formed by molding the same, the characteristics of the polypropylene resin (X) having a long-chain branched structure are further enhanced or another characteristic is newly added. In some cases, the use of polypropylene resin (Y) is effective.

Condition (A-3)
When the polypropylene resin (Y) is used in the present invention, the polypropylene resin usually has a long chain branched structure with respect to a total of 100% by weight of the polypropylene resin (X) having a long chain branched structure and the polypropylene resin (Y). (X) 1 to 99% by weight and polypropylene resin (Y) 1 to 99% by weight, polypropylene resin (X) 5 to 95% by weight and polypropylene resin (Y) 5 to 95% by weight having a long-chain branched structure Preferably there is. The polypropylene resin (X) having a long-chain branched structure is more preferably 10 to 70% by weight, more preferably 15 to 60% by weight, and particularly preferably 20 to 50% by weight. On the other hand, the polypropylene resin (Y) is more preferably 30 to 90% by weight, more preferably 40 to 85% by weight, and still more preferably 50 to 80% by weight. By setting the blending amount of the polypropylene resin (X) and the polypropylene resin (Y) having a long-chain branched structure in such a range, it becomes possible to maintain good molding processability as well as high rigidity and impact resistance. In addition, since it is possible to develop a high flame resistance by maintaining a higher drip resistance, it is possible to provide a higher level flame retardant material.

2. Filler (B)
The filler (B) used in the present invention not only improves physical properties such as rigidity in the polypropylene resin composition of the present invention and a molded product formed by molding the same, but also has heat resistance and dimensional stability (linear expansion coefficient). For example) and low shrinkage, and contributes to the improvement of additional physical properties. The filler (B) used in the present invention is preferably at least one filler selected from the group consisting of glass fibers and talc.

(1) Kind, Production The filler (B) used in the present invention not only improves physical properties such as rigidity in the polypropylene resin composition of the present invention and a molded product obtained by molding the same, but also has heat resistance and dimensions. It is not particularly limited as long as it contributes to improvement of additional physical properties such as stability (reduction of linear expansion coefficient, etc.), low shrinkage, etc., such as glass fiber, talc, wollastonite, heavy calcium carbonate, Various inorganic or organic fillers such as light calcium carbonate, colloidal calcium carbonate, barium sulfate, mica, glass balloon, basic magnesium sulfate whisker, potassium titanate whisker, aluminum borate whisker, carbon fiber, clay, organic clay, etc. Can be mentioned. Among these, it is possible to sufficiently achieve the intended effect of the present invention, and it is easy to handle and obtain, and because it is available in an industrially usable amount at low cost, glass fiber, At least one filler selected from the group consisting of talc is preferred.
This filler (B) can be used in combination of two or more for the purpose of further improving the effects of the present invention, and is a so-called master previously contained in the polypropylene resin (A) at a relatively high concentration. It can also be used in batch form.

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

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

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

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

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

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

The glass fiber can also be used as a so-called chopped strand glass fiber obtained by cutting a fiber yarn into a desired length. It is preferable to use this chopped strand glass fiber in order to further enhance each effect of improving the rigidity and impact strength of the polypropylene resin composition of the present invention and a molded product formed by molding the same.
Specific examples of the glass fiber include Nippon Electric Glass Co., Ltd. (T480).

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

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

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

(Ii) Talc Talc preferably has an average particle size of 1.5 μm to 15 μm, particularly preferably 2 to 8 μm. When the average particle size of talc is less than 1.5 μm, the appearance of the molded body (silver strake) tends to be reduced, and when it exceeds 15 μm, the impact strength may be lowered. The talc is produced, for example, by pulverizing raw talc with an impact pulverizer or a micron mill type pulverizer, or further pulverizing with a jet mill or the like and then adjusting the classification with a cyclone or micron separator. .

Talc may be chemically or physically surface-treated with various metal soaps or surfactants, and so-called compressed talc having an apparent specific volume of 2.50 ml / g or less may be used. The average particle diameter of the talc is a value measured using a laser diffraction / scattering particle size distribution analyzer, and as a measuring device, for example, Horiba LA-920 type is preferable because of its excellent measurement accuracy.
Talc preferably has an average aspect ratio of 4 or more, particularly 5 or more. Measurement of the aspect ratio of the talc is obtained from a value measured with a microscope or the like.

3. Halogen flame retardant (C)
The halogen-based flame retardant (C) used in the present invention must satisfy the following conditions.
Condition (C-1)
The melting point of the halogen flame retardant (C) is 250 ° C. or higher.

As the halogen-based flame retardant (C) used in the present invention, it is important to use a halogen-based flame retardant having a melting point of 250 ° C. or higher. If the melting point is 250 ° C. or higher, it is generally used as a flame retardant for polyolefins. What is used can be used. By using a halogen flame retardant having a melting point of 250 ° C. or higher as the halogen flame retardant (C), it is possible to prevent deterioration of the polypropylene resin composition due to decomposition of the halogen flame retardant and to obtain good drip resistance. Is possible.
Examples of the halogen flame retardant include organic halogenated aromatic compounds such as halogenated diphenyl compounds, halogenated bisphenol compounds, halogenated bisphenol-bis (alkyl ether) compounds, and halogenated phthalimide compounds. it can.

  Examples of the halogen flame retardant having a melting point of 250 ° C. include ethylene bispentabromophenyl, ethylene bistetrabromophthalimide, decabromodiphenyl oxide, and tetradecabromodiphenoxybenzene.

  Various flame retardants are known to have different melting points depending on their purity. In addition to the halogen-based flame retardant, any one having a high purity and a melting point of 250 ° C. or higher can be used. For example, (3,5-dibromo-4-2,3-dibromopropoxyphenyl)-(3-bromo-4-2,3-dibromopropoxyphenyl) methane, 1- (3,5-dibromo-4-2, 3-dibromopropoxyphenyl) -2- (3-bromo-4-2,3-dibromopropoxyphenyl) ethane, 1- (3,5-dibromo-4-2,3-dibromopropoxyphenyl) -3- (3 -Bromo-4-2,3-dibromopropoxyphenyl) propane, 2,2-bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) propane, (3,5-dichloro-4-2, 3-Dibromopropoxyphenyl)-(3-chloro-4-2,3-dibromopropoxyphenyl) methane, 1- (3,5-dichloro-4-2,3-dibromopropoxyphenyl) 2- (3-Chloro-4-2,3-dibromopropoxyphenyl) ethane, 1- (3,5-dichloro-4-2,3-dibromopropoxyphenyl) -3- (3-chloro-4-2 , 3-Dibromopropoxyphenyl) propane, bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) methane, 1,2-bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) ) Ethane, 1,3-bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) propane, bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) methane, 1,2 -Bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) ethane, 1,3-bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) pro 2-bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) propane, (3,5-dibromo-4-2,3-dibromopropoxyphenyl)-(3-bromo-4-2 , 3-Dibromopropoxyphenyl) ketone, (3,5-dichloro-4-2,3-dibromopropoxyphenyl)-(3-chloro-4-2,3-dibromopropoxyphenyl) ketone, bis (3,5- Dibromo-4-2,3-dibromopropoxyphenyl) ketone, bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) ketone, (3,5-dibromo-4-2,3-dibromopropoxyphenyl) )-(3-bromo-4-2,3-dibromopropoxyphenyl) ether, (3,5-dichloro-4-2,3-dibromopropoxyphenyl)-(3 -Chloro-4-2,3-dibromopropoxyphenyl) ether, bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) ether, bis (3,5-dichloro-4-2,3-dibromo Propoxyphenyl) ether, (3,5-dibromo-4-2,3-dibromopropoxyphenyl)-(3-bromo-4-2,3-dibromopropoxyphenyl) thioether, (3,5-dichloro-4-2) , 3-Dibromopropoxyphenyl)-(3-chloro-4-2,3-dibromopropoxyphenyl) thioether, bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) thioether, bis (3,5 -Dichloro-4-2,3-dibromopropoxyphenyl) thioether, (3,5-dibromo-4-2,3-dibromopropyl) Poxyphenyl)-(3-bromo-4-2,3-dibromopropoxyphenyl) sulfone, (3,5-dichloro-4-2,3-dibromopropoxyphenyl)-(3-chloro-4-2,3- Among dibromopropoxyphenyl) sulfone, bis (3,5-dibromo-4-2,3-dibromopropoxyphenyl) sulfone, bis (3,5-dichloro-4-2,3-dibromopropoxyphenyl) sulfone, etc. Those having a high melting point of 250 ° C. or higher can be used.

  Further, among the halogen-based flame retardants (C), bromine-based flame retardants are preferable because a higher flame retardant effect can be obtained in the present invention even if the amount used is smaller. Examples of these brominated flame retardants include the brominated flame retardants described above.

  These halogen flame retardants may be used alone or in combination of two or more. In addition to halogen-based flame retardants, other organic flame retardants (phosphorous flame retardants, magnesium hydroxide, etc.) that do not fall under the halogen-based flame retardants as long as the characteristics are not impaired can also be used.

3. Flame retardant aid (E)
The flame retardant aid (E) used in the present invention is not particularly limited, and various compounds can be used. Among them, the antimony compound reacts with the halogen flame retardant (C) to produce a halogen flame retardant. Even when the amount of (C) used is small, it is preferable because a higher flame retardant effect can be exhibited. An antimony compound is used in order to increase a flame-retardant effect by mix | blending with a polypropylene resin (A) with a halogenated flame retardant (C).
Specific examples of antimony compounds include antimony halides such as antimony trioxide, antimony pentoxide, antimony trichloride, and antimony pentachloride, antimony trisulfide, antimony pentasulfide, sodium antimonate, and antimony tartrate. Can be mentioned.
In the present invention, the antimony compound includes metal antimony. As the antimony compound used in the present invention, antimony trioxide is preferable.
Moreover, these flame retardant adjuvants (E) may be used independently and may use 2 or more types together.

4). Compounding amount of each component The polypropylene resin composition of the present invention must satisfy the following conditions.
Condition (A)
The content of each component is 13 to 75 parts by weight of polypropylene resin (A), 5 to 40 parts by weight of filler (B), 15 to 35 parts by weight of halogenated flame retardant (C) and flame retardant aid (E) 5 -12 parts by weight (however, the total amount of polypropylene resin (A), filler (B), halogen flame retardant (C) and flame retardant aid (E) is 100 parts by weight).
By setting the blending amount of each component in such a range, the polypropylene resin composition of the present invention and the molded product obtained by molding the polypropylene resin composition of the present invention have a self-extinguishing property and a drip resistance that have been difficult with conventional techniques. By achieving both, it is possible to express extremely high flame retardancy, achieve 5VA in UL94-5V, and impart mechanical properties (particularly rigidity) and molding processability.

  Polypropylene resin (A) is 13 to 75 parts by weight, preferably 21 to 69 parts by weight, particularly preferably 30 to 63 parts by weight.

The filler (B) is 5 to 40 parts by weight, preferably 8 to 35 parts by weight, particularly preferably 10 to 30 parts by weight. By setting the content of the filler (B) in such a range, the rigidity and moldability of the polypropylene resin composition of the present invention and the molded body thereof can be improved. That is, when the blending amount of the filler (B) falls below the range specified in the present application, the mechanical properties (particularly rigidity) of the polypropylene resin composition of the present invention and a molded product formed from the polypropylene resin composition may be lowered. . On the other hand, if the range specified in the present application is exceeded, moldability (fluidity) and the like may be reduced.
In addition, the compounding quantity of a filler (B) is a real quantity here, For example, when using the said filler containing pellet, it calculates based on the real content of the filler (B) contained in this pellet.

  The halogen-based flame retardant (C) is 15 to 35 parts by weight, preferably 17 to 33 parts by weight, particularly preferably 20 to 30 parts by weight. By making content of a halogen-type flame retardant (C) into such a range, the flame retardance and moldability of the polypropylene resin composition of this invention and its molded object can be made favorable. That is, when the blending amount of the halogen-based flame retardant (C) is below the range specified in the present application, sufficient flame retardancy cannot be obtained. In some cases, the improvement in flame retardancy commensurate with the above is not observed, which is economically disadvantageous.

The flame retardant aid (E) is 5 to 12 parts by weight, preferably 6 to 11 parts by weight, particularly preferably 7 to 10 parts by weight. By setting the content of the flame retardant auxiliary (E) in such a range, the flame retardancy and mechanical properties of the polypropylene resin composition of the present invention and the molded product thereof can be improved. That is, if the blending amount of the flame retardant auxiliary (E) is below the range specified in the present application, sufficient flame retardancy cannot be obtained. Deterioration and economic disadvantages.
In addition, the compounding quantity of each component of a polypropylene resin (A), a filler (B), a halogenated flame retardant (C), and a flame retardant adjuvant (E) is a polypropylene resin (A), a filler (B), and a halogen. It can select from the range of this application regulation of each component so that the total amount of a system flame retardant (C) and a flame retardant adjuvant (E) may be 100 weight part.

5. Optional additive component (D)
In the present invention, in addition to the polypropylene resin (A), the filler (B), the halogen flame retardant (C), and the flame retardant aid (E), the effect of the present invention is not significantly impaired as necessary. For example, an optional additive component (D) that is usually used can be blended to further improve the effects of the invention or to impart other effects.
Specifically, molecular weight depressants such as peroxides, colorants such as pigments, modified polyolefins, antioxidants such as phenols, phosphorus and sulfur, light stabilizers such as hindered amines, benzotriazoles, etc. UV absorbers, sorbitol-based nucleating agents, non-ionic antistatic agents, organometallic salt-based dispersants, nitrogen compounds and other metal deactivators, thiazole-based antibacterial and antifungal agents, Plasticizer, neutralizer, lubricant, elastomer (rubber component), polyolefin resin other than polypropylene resin (A) (polyolefin resin not corresponding to polypropylene resin (X) and polypropylene resin (Y)), polyamide resin and polyester Thermoplastic resins such as resins, phosphorus flame retardants other than halogen flame retardants (C), metal oxides and hydrated metal compounds Retardants, interface treatment agent (modified polyolefin), and the like.

  These optional addition components may be used in combination of two or more thereof, may be added to the polypropylene resin composition of the present invention, or the above components, polypropylene resin (A), filler (B), halogen type. It may be mixed and added to each component of the flame retardant (C) and the flame retardant aid (E), and two or more of these components may be used in combination. In the present invention, the blending amount of the optional additive component (D) is not particularly limited. Usually, however, with the polypropylene resin (A), filler (B), halogen flame retardant (C), and flame retardant aid (E). The total amount is about 0 to 4.0 parts by weight with respect to 100 parts by weight.

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

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

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

Examples of the antioxidant that can be used in the polypropylene resin composition of the present invention include phenol-based, phosphorus-based and sulfur-based antioxidants, and these include the polypropylene-based resin composition of the present invention and It is effective for imparting and improving the heat stability, processing stability, heat aging resistance, etc. of the molded product formed by molding it.
Examples of the antistatic agent that can be used in the polypropylene resin composition of the present invention include nonionic and cationic antistatic agents. These include the polypropylene resin composition of the present invention and the antistatic agent. This is effective for imparting and improving the antistatic property of a molded product.

  Examples of the metal oxide (a flame retardant not corresponding to the halogen flame retardant (C)) that can be used in the polypropylene resin composition of the present invention include zinc oxide, iron oxide, aluminum oxide, molybdenum oxide, and the like. More preferable metal oxides are zinc oxide and iron oxide, and those having an average particle size of 30 μm or less, preferably 10 μm or less, and more preferably 1 μm or less are suitable. When the average particle diameter of the metal oxide is larger than 30 μm, dispersibility with respect to the polypropylene resin composition is deteriorated, and high flame retardance cannot be obtained. The compounding amount in the case of using a metal oxide is 0.05 to 100 parts by weight with respect to 100 parts by weight of the polypropylene resin (A), the filler (B), the halogen flame retardant (C), and the flame retardant aid (E). 5 parts by weight is preferable, and 0.1 to 3 parts by weight is more preferable. By setting the blending amount of the metal oxide in such a range, it becomes possible to exhibit good flame retardancy due to a synergistic effect with the halogen-based flame retardant (C) and the flame retardant auxiliary (E). That is, if the blending amount is less than 0.05 parts by weight, there may be a case where a sufficient synergistic flame retardant effect cannot be obtained. On the other hand, if the blending amount exceeds 5 parts by weight, an effect commensurate with the addition amount is not seen. This is not preferable because it may be economically disadvantageous.

  A typical example of the surface treating agent that can be used in the polypropylene resin composition of the present invention is a modified polyolefin. Examples of these modified polyolefins include acid-modified polyolefins and / or hydroxy-modified polyolefins, and these have the characteristics of imparting higher functions such as mechanical properties (particularly rigidity and impact strength) in the present invention. .

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

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

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

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

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

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

  The amount of the modified polyolefin used as the interfacial treating agent is 100 parts by weight in total of the polypropylene resin (A), filler (B), halogen flame retardant (C), and flame retardant aid (E). 0 to 10 parts by weight, preferably 0.01 to 7 parts by weight, more preferably 0.5 to 5 parts by weight, and still more preferably 1 to 3 parts by weight. By setting the blending amount of the modified polyolefin within such a range, it is possible to maintain good impact strength. When the blending amount of the modified polyolefin exceeds 10 parts by weight, there is a possibility that the impact strength is lowered or the economy is lowered.

  Examples of the neutralizing agent that can be used in the polypropylene resin composition of the present invention include stearic acid metal salts (calcium salts, magnesium salts, aluminum salts, zinc salts), and behenic acid metal salts (calcium salts, zinc salts). And hydrotalcite, etc., among these, without impairing the intended effect of the present invention, and easy to handle and obtain, for the reason that the industrially usable amount can be obtained inexpensively The calcium salt of stearic acid is preferred, and calcium stearate (calcium stearate) is particularly preferred because it is easy to handle and obtain and is available in industrially inexpensive quantities. These neutralizing agents neutralize the residue of the catalyst used for polymerization (especially chloride ions) remaining in various polypropylene resins, thereby preventing the corrosion and deterioration of the mold due to the catalyst residue. It has the effect of preventing.

  The blending amount of the neutralizing agent used in the present invention is 100 parts by weight in total of polypropylene resin (A), filler (B), halogen flame retardant (C), and flame retardant aid (E). It is 0.01-1.0 weight part with respect to it, Preferably it is 0.02-0.5 weight part, More preferably, it is 0.05-0.3 weight part. By setting the blending amount in such a range, it becomes possible to obtain a good corrosion prevention effect according to the blending amount. That is, when the blending amount is less than 0.05 parts by weight, neutralization of the catalyst residue becomes insufficient, and a good corrosion prevention effect may not be obtained. On the other hand, when the blending amount exceeds 1.0 part by weight, the neutralization effect is not increased due to the increase in the blending amount, which may lead to excessive use of the neutralizing agent and the economical efficiency.

II. 1. Production method of polypropylene resin composition, production method of molded article and application Method for Producing Polypropylene Resin Composition The polypropylene resin composition of the present invention can be arbitrarily selected as necessary from polypropylene resin (A), filler (B), halogen flame retardant (C), flame retardant aid (E). It can be produced by adding the additive component (D), mixing at the above-mentioned mixing ratio by a conventionally known method, and passing through a kneading step of melt-kneading.

  Mixing is usually performed using a mixing device such as a tumbler, V blender, or ribbon blender, and melt kneading is usually performed by a single screw extruder, twin screw extruder, Banbury mixer, roll mixer, Brabender plastograph, kneader, stirring. Using a kneading machine such as a granulator (semi) melt kneading and granulating. When manufacturing by (semi) melt kneading and granulating, the blend of the above components may be kneaded at the same time, and each component is divided and kneaded to improve performance. That is, for example, first, a part or all of the polypropylene resin (A), the halogen-based flame retardant (C), and the flame retardant aid (E) and a part of the filler (B) are kneaded, and then the remaining A method of kneading and granulating the components can also be employed.

When using a fiber that is broken as a filler (B) in the polypropylene resin composition of the present invention, such as carbon fiber or glass fiber, when using glass fiber that is preferably used in the present invention, it is melted. The average length of the glass fibers present in the resin composition pellets obtained through the kneading step of kneading or in the molded body is usually 0.3 mm or more, preferably 0.4 mm or more, usually 2.5 mm or less, preferably It is preferable to manufacture by a compounding method so as to be 2.0 mm or less.
In addition, in this specification, the average length of the glass fiber which exists in a resin composition pellet or a molded object means the value which computed the average using the value measured with the digital microscope. Specifically, for example, the resin composition pellet or molded body of the present invention is burned, the ashed glass fiber is mixed with the surfactant-containing water, and the mixed water solution is dropped and diffused onto the thin glass plate. Thereafter, the glass fiber length is measured using a digital microscope (VHX-900, manufactured by Keyence Corporation), and the average value is calculated.
Further, as a preferable production method for bringing the glass fiber into such a range, for example, in melt kneading with a twin screw extruder, for example, a polypropylene resin (A), a halogen flame retardant (C), a flame retardant aid ( After sufficiently melt-kneading E), glass fibers are fed by a side feed method or the like, and the bundled fibers are dispersed while minimizing breakage of the glass fibers.

  In addition, for example, polypropylene resin (A), filler (B), halogen flame retardant (C), and flame retardant aid (E) are stirred in a Henschel mixer at high speed to bring them into a semi-molten state. The so-called agitation granulation method in which the filler (B) is kneaded is also one of the preferable production methods because the fibers can be easily dispersed while minimizing fiber breakage. This method is an effective production method because talc can be well dispersed even when talc is used as the filler (B).

Furthermore, a polypropylene resin (A) excluding the filler (B), a halogen flame retardant (C), and a flame retardant aid (E) are melt-kneaded with an extruder or the like to form pellets, and the pellets and glass fibers A production method for producing a fiber reinforced composition by mixing so-called “filler (B) -containing pellets” such as a pellet containing carbon or a pellet containing carbon fiber is one of the preferable methods for the same reason as described above.
As described above, as a preferred method for producing the polypropylene resin composition of the present invention, a method of adding the filler (B) after kneading components other than the filler (B) in the kneading step can be easily performed. The polypropylene resin composition of the present invention can be produced by the production method.

2. Manufacturing method, characteristic and use of molded product The molded product of the present invention is obtained by, for example, injection molding (gas injection molding, two-color injection molding, core back injection molding, sandwich injection) of the polypropylene resin composition manufactured by the above method. Including molding), injection compression molding (press injection), extrusion molding, sheet molding, and hollow molding. Among these, it is preferable to obtain by injection molding or injection compression molding.

The polypropylene resin composition of the present invention exhibits flame retardancy and drip resistance superior to conventionally known flame retardant polyolefin resins, and is excellent in mechanical properties, weather resistance, and moldability.
Although the expression mechanism of the action is not clear, the present inventors consider as follows.
That is, since the polypropylene resin (X) has a long-chain branched structure, the polypropylene resin composition of the present invention and a molded product obtained by molding the polypropylene resin composition (X) have a significantly improved melt tension. The effect is expressed.
In addition, since the halogen-based flame retardant (C) having a melting point of 250 ° C. or higher is used, the flame retardant mechanism of the halogen-based flame retardant (C) is exhibited without causing an extreme decrease in melt viscosity during combustion. . This makes it possible to develop a drip-proof effect and an excellent self-extinguishing effect.

  In the polypropylene resin composition of the present invention, the melt flow rate is preferably 1.0 to 30 g / 10 min, and more preferably 1.5 to 20 g / min. By setting the melt flow rate in such a range, it is possible to achieve good moldability and to obtain good flame resistance (drip resistance) and appearance. That is, if it is less than 1.0 g / 10 min, problems such as short shots and poor appearance (Tracima) may occur in injection molding. On the other hand, if it exceeds 30 g / 10 min, it becomes difficult to maintain the melt viscosity, the drip resistance is impaired, and there is a tendency to cause appearance defects (silver strake) due to gas during injection molding.

  In the polypropylene resin composition of the present invention, the deflection temperature under load (HDT) is preferably 120 ° C. or higher. The upper limit is not particularly limited, but is usually 200 ° C. By setting the deflection temperature under such a range, the polypropylene resin composition of the present invention can be applied to a high-temperature member, and the use is further expanded. That is, when the deflection temperature under load is lower than 120 ° C., it becomes difficult to use the high temperature member (engine member, heater peripheral device, etc.).

  In the polypropylene resin composition of the present invention, the flexural modulus is preferably 2000 MPa or more. The upper limit is not particularly limited, but is usually 15000 MPa. When the flexural modulus is in such a range, sufficient rigidity can be obtained and usually sufficient bending strength can be obtained, and the polypropylene resin of the present invention is also used for applications that require high rigidity such as automobile members. Can be used. That is, when the flexural modulus is less than 2000 MPa, sufficient rigidity cannot be maintained, and it becomes difficult to apply to automobile members from the viewpoint of safety and productivity.

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

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

1. Evaluation method 1) Flame retardancy 1) -1 UL94-5V (bar test)
Test pieces (length × width × thickness = 123 × 12 × 2 mm) were produced at an injection temperature of 200 to 230 ° C. and a mold temperature of 40 ° C. using an injection molding machine [IS100 manufactured by Toshiba Machine Co., Ltd.]. Evaluation was performed according to UL94-5V which is UL standard. Evaluation results were evaluated by the following methods.
5V: meets the standard of 5V in UL94-5V NG: does not meet the standard of 5V in UL94-5V 1) -2 UL94-5V (flat plate test)
A test piece (150 × 150 × 2 mm) was produced by a press molding machine [manufactured by Shinfuji Metal Industry Co., Ltd.] at a molding temperature of 230 ° C. under conditions of a press time of 7 minutes and a cooling time of 5 minutes. Evaluation was performed according to UL94-5V which is UL standard. The evaluation method was evaluated by the following method.
5V: No hole is formed in the flat plate. NG: A hole is formed in the flat plate.
1) -3 Drip suppression effect The presence or absence of drip was confirmed in the UL94-5V bar test. Judgment criteria are as follows.
○: There is no molten resin that drip during the combustion test ×: There is a molten resin that drip during the combustion test 1) -4 UL94-V
A test piece for flame retardancy evaluation (thickness 1.5 mmt or 3.0 mmt) was molded and evaluated by an injection molding machine [IS100 manufactured by Toshiba Corporation] according to the UL94-V standard. When the determination does not satisfy the UL94-V standard, “NG” is indicated.

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

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

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

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

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

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

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

9) Flexural modulus Measured at 23 ° C. according to JIS K7203. The dimension of the molded product was 90 × 10 × 4 mm. The unit is MPa.
10) Bending strength It measured at 23 degreeC based on JISK7203. The dimension of the molded product was 90 × 10 × 4 mm. The unit is MPa.
11) Charpy impact strength (with notch)
It was measured at a measurement temperature of 23 ° C. in accordance with JIS K7111. The unit is kJ / m ² .

12) Deflection temperature under load (HDT)
Measurement was performed at a load of 0.45 MPa in accordance with JIS K7191-1 and JIS2. The test piece used the test piece based on JISK7152-1.

13) Formability The formability was evaluated from the melt flow rate. The evaluation criteria are shown below.
×: Melt flow rate is less than 1.0 g / 10 min Δ: Melt flow rate is 1.0 g / 10 min or more and less than 4.0 g / 10 min ○: Melt flow rate is 4.0 g / 10 min or more

14) Silver Stroke Using an injection molding machine (IS100 manufactured by Toshiba Corporation) with a molding temperature of 200 to 230 ° C., a mold temperature of 40 ° C., an injection speed of 30, 50, 80 mm / sec, and a cooling time of 20 sec. A sheet test piece (2 × 120 × 120 mmt) having a pin gate of 1 mm was prepared and the appearance was observed. The evaluation criteria are as follows.
(Criteria)
○: Silver strake is not seen at any injection speed.
Δ: Silver strake can be confirmed at any injection speed ×: Silver strake can be confirmed at all injection speeds

2. Materials and Evaluation (1) Polypropylene resin (A)
(1-1) Polypropylene resin (X) having a long-chain branched structure
(X-1): The polypropylene resin (X-1) having a long chain branched structure produced in Production Example 1 below was used.

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

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

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

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

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

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

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

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

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

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

(1-2) Polypropylene resin (Y)
(Y-1) manufactured by Nippon Polypro, Novatec PP series (polypropylene homopolymer, MFR 0.5 g / 10 min, isotactic pentad fraction (mmmm fraction) 0.98)
(Y-2) manufactured by Nippon Polypro, Novatec PP series (polypropylene homopolymer, MFR 20.0 g / 10 min, isotactic pentad fraction (mmmm fraction) 0.98)
(Y-3) manufactured by Nippon Polypro Co., Ltd., Novatec PP series (polypropylene homopolymer, MFR 40.0 g / 10 min, isotactic pentad fraction (mmmm fraction) 0.98)
(Y-4) manufactured by Nippon Polypro Co., Ltd., Novatec PP series (propylene-ethylene block copolymer, total MFR 130 g / 10 min, first stage MFR 350 g / 10 min, ethylene content of random copolymer portion 26. 3% by weight, 9% by weight of random copolymer part, Mw / Mn 12.6)
(Y-5) manufactured by Nippon Polypro, Novatec PP series (polypropylene homopolymer, MFR 10.0 g / 10 min, isotactic pentad fraction (mmmm fraction) 0.98)

(2) Filler (B)
(B-1) manufactured by Nippon Electric Glass Co., Ltd., glass fiber: T480 (chopped strand, fiber diameter 13 μm, length 4 mm)
(B-2) Nippon Talc Co., Ltd., talc: 5000SMA (average particle size 5.0 μm)

(3) Halogen flame retardant (C)
(C-1) Albemarle SAYTEX8010 [ethylene bispentabromophenyl, melting point 350 ° C.]

(3) Flame retardant aid (E)
(E-1) PATOX-M [antimony trioxide, average particle size 0.5 μm] manufactured by Nippon Seikosho Co., Ltd.
(4) Other additives (D)
As other additives (D), antioxidants (D-1: manufactured by BASF, Irganox 1010), (D-2: manufactured by ADEKA, PEP36, neutralizer (D-3: manufactured by NOF Corporation) , Calcium stearate) and an interfacial treatment agent ((D-4: manufactured by Mitsubishi Chemical Corporation, maleic acid-modified polypropylene: CMPP2) were used.

[Examples 1-7, Comparative Examples 1-2]
Total 100 parts by weight of polypropylene resin (A) (polypropylene resin (X), polypropylene resin (Y) having a long-term branched structure), filler (B), halogen flame retardant (C), flame retardant aid (E) In addition, as additional additives, antioxidants (D-1: manufactured by BASF, Irganox 1010), (D-2: manufactured by ADEKA, PEP36, neutralizing agent (D-3: Japanese fats and oils) Co., Ltd., calcium stearate) and an interfacial treating agent (D-4: manufactured by Mitsubishi Chemical Corporation, maleic acid-modified polypropylene: CMPP2) were blended in the proportions shown in Table 2, respectively, and a high-speed stirring mixer (Henschel mixer- The product was mixed for 3 minutes at room temperature, then melt-kneaded and extruded with a twin screw extruder, passed through a cold water tank, and then cut with a strand cutter. In addition, the compounding quantity of each component described in Table 2 is part by weight, and the ratio of the polypropylene resin (X) and the polypropylene resin (Y) having a long-term branched structure (however, the long-chain branched structure) In the column of polypropylene resin (X) and polypropylene resin (Y) having a long chain branched structure, the total of the polypropylene resin (X) and polypropylene resin (Y) containing It was described in.
The obtained pellets were evaluated according to the evaluation method. The evaluation results are shown in Table 2.

3. Evaluation results From the results shown in Table 2, the use of the polypropylene resin (X) having a long-chain branched structure as the polypropylene resin (A) in the polypropylene resin composition of the present invention shows extremely good flame retardancy. Recognize. That is, in order to achieve “evaluation 5VA of UL94-5V” which is an evaluation index of flame retardancy, it is necessary to satisfy both self-extinguishing property and drip resistance. Has achieved a sex assessment. Further, by blending the filler (B) within the range specified in the present invention, the mechanical properties are also improved. Further, in the examples, there are no defects such as formability by compounding and poor appearance due to silver strake that occurs during molding.
For each example, since Comparative Example 1 does not use a polypropylene resin (X) having a long-chain branched structure, it is difficult to maintain drip properties and shape during combustion, and satisfactory flame retardancy Can't get. Moreover, the gas etc. which generate | occur | produce at the time of shaping | molding cannot be suppressed, but the malfunction of appearance defect, such as a silver stroke, has arisen.
On the other hand, in Comparative Example 2, polypropylene having low fluidity is added instead of polypropylene resin (X) having a long-chain branched structure, but it is found that it is difficult to maintain drip properties and shape during combustion. . It can be said that it is difficult to maintain the drip property and shape at the time of combustion only by adding a polypropylene resin having low fluidity, and the elasticity and viscosity of the polypropylene resin (X) having a long-chain branched structure. It can be seen that the effect is due to the balance.

  From these examples and comparative examples, a polypropylene resin (A) containing a polypropylene resin (X) having a long chain branched structure, a filler (B), a halogen flame retardant (C) and a flame retardant aid (E) are added. It can be seen that by using the essential component and the predetermined amount specified in the present application, both high flame retardancy and mechanical properties satisfying UL94-5V required in the present application can be satisfied.

Claims (5)

A polypropylene resin (A) that satisfies the following conditions (A-1) and (A-2), a filler (B), and a halogen flame retardant (C) that satisfies the following conditions (C-1): And a flame retardant aid (E), the melt flow rate (MFR) (230 ° C., 2.16 kg load) is 1.0 to 20 g / 10 min, and the following condition (a) is satisfied. A feature of a polypropylene resin composition.
Condition (A-1)
The polypropylene resin (A) contains a polypropylene resin (X) having a long-chain branched structure having the following properties (Xi) to (X-iv).
Characteristic (X-i): Melt flow rate (MFR) (230 ° C., 2.16 kg load) is 0.1 to 30.0 g / 10 min.
Characteristic (X-ii): GPC molecular weight distribution Mw / Mn is 3.0 to 10.0 and Mz / Mw is 2.5 to 10.0.
Characteristic (X-iii): Melt tension (MT) (unit: g) is
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy one of the following.
Characteristic (X-iv): 25 degreeC paraxylene soluble component amount (CXS) is less than 5.0 weight% with respect to polypropylene resin (X) whole quantity.
Condition (A-2)
The polypropylene resin (A) is at least selected from the group consisting of the polypropylene resin (X) having the long-chain branched structure and the polypropylene resin (Y) having the following properties (Yi) to (Y-ii): Contains one kind of polypropylene resin.
Characteristic (Yi): at least one polypropylene resin selected from the group consisting of a propylene homopolymer and a propylene-α-olefin block copolymer, corresponding to the polypropylene resin (X) having the long-chain branched structure do not do.
Characteristic (Y-ii): The polypropylene resin (Y) has a melt flow rate (MFR) (230 ° C., 2.16 kg load) of 1.0 to 150 g / 10 min.
Condition (C-1)
The melting point of the halogen flame retardant (C) is 250 ° C. or higher.
Condition (A)
The content of each component is 13 to 75 parts by weight of polypropylene resin (A), 5 to 40 parts by weight of filler (B), 15 to 35 parts by weight of halogenated flame retardant (C) and flame retardant aid (E) 5 -12 parts by weight (however, the total amount of polypropylene resin (A), filler (B), halogen flame retardant (C) and flame retardant aid (E) is 100 parts by weight). The polypropylene resin composition according to claim 1, wherein the polypropylene resin (A) further satisfies the following condition (A-3).
Condition (A-3)
The polypropylene resin (A) contains a polypropylene resin (Y) and a polypropylene resin (X) having a long chain branched structure, and the proportion thereof has 1 to 99% by weight of the polypropylene resin (Y) and a long chain branched structure. 1 to 99% by weight of the polypropylene resin (X) (provided that the total of the polypropylene resin (Y) and the polypropylene resin (X) having a long chain branched structure is 100% by weight).   The polypropylene resin composition according to claim 1 or 2, wherein the halogen flame retardant (C) is a bromine flame retardant.   The polypropylene resin composition according to any one of claims 1 to 3, wherein the filler (B) is at least one selected from the group consisting of glass fibers and talc.   The molded object formed by shape | molding the polypropylene resin composition of any one of Claims 1 thru | or 4.