JP6831218B2 - Masterbatch composition and polypropylene resin composition containing it - Google Patents

Description

The present invention relates to a masterbatch composition and a polypropylene resin composition containing the same.

Polypropylene is widely used in automobile applications because it is inexpensive and has excellent physical properties. However, since polypropylene has an amorphous component, it is known to have a large coefficient of linear expansion. Therefore, in automobile parts, there is a problem that a gap is formed at a joint portion between the polypropylene resin and another material. Further, attempts have been made to add a large amount of an inorganic filler such as talc for the purpose of reducing the coefficient of linear expansion, but this leads to an increase in weight and is not preferable from the viewpoint of improving fuel efficiency by reducing the weight of the automobile.

To solve this problem, Patent Document 1, between the intrinsic viscosity of the portion soluble polyolefin composition in xylene (IV _s) at room temperature, and the intrinsic viscosity (IV _A) of component (A) Wide molecular weight distribution with IV _s / IV _A ratio of 2 to 2.5, (A) 5 to 15 polydispersity index, and melting flow of 80 to 200 g / 10 minutes (ASTM-D1238, according to condition L). A polyolefin composition comprising 40-60% propylene polymer (component A) and 40-60% (B) a partially xylene-insoluble olefin polymer rubber (component B) containing at least 65% by weight ethylene. Proposed. The composition is said to have a low coefficient of linear expansion.

Special Table 2002-528621

In automobile parts, high elastic modulus, high impact strength at low temperature, and low linear expansion coefficient are required, and these are generally in a trade-off relationship, and it is difficult to satisfy all of them in a well-balanced manner. The composition described in Patent Document 1 is said to have high impact strength at low temperature and a low coefficient of linear expansion, but its elastic modulus is not at a sufficient level. In view of such circumstances, it is an object of the present invention to provide a composition having a high elastic modulus, a high impact strength at a low temperature, and a low linear expansion coefficient.

The problem is solved by the following invention.
[1] (A) A solid catalyst containing an electron donor compound selected from magnesium, titanium, halogen, and a succinate compound as an essential component;
A masterbatch composition obtained by polymerizing propylene and ethylene using a catalyst containing (B) an organoaluminum compound and (C) an external electron donor compound.
The component (1) contains a propylene homopolymer, and the component (2) contains a propylene-ethylene copolymer containing 55 to 80% by weight of ethylene-derived units.
The weight ratio of the components (1): (2) is 85-60: 15-40.
The following requirements:
1) Mw / Mn of the xylene-insoluble component of the composition measured by GPC is 6 to 20. 2) The ultimate viscosity of the xylene-soluble component of the composition is 1 to 3 dl / g. 3) The composition. A masterbatch composition that satisfies a melt flow rate (230 ° C., load 21.18 N) of 1 to 50 g / 10 min.
[2] The masterbatch composition according to claim 1, wherein the ethylene-derived unit of the propylene-ethylene copolymer in the component (2) is 60 to 75% by weight.
[3] The masterbatch composition according to [1] or [2], wherein the weight ratio of the components (1): (2) is 75 to 60:25 to 40.
[4] The masterbatch composition according to any one of [1] to [3], wherein the melt flow rate is 10 to 35 g / 10 minutes.
[5] The masterbatch composition according to any one of [1] to [4], which contains 0.01 to 5 parts by weight of a crystal nucleating agent with respect to 100 parts by weight of the composition.
[6] In the masterbatch composition according to any one of [1] to [5], an elastomer different from the component (2) of the masterbatch composition or a polypropylene resin different from the masterbatch composition is added. A polypropylene resin composition obtained by mixing at least one of them.
[7] A polypropylene resin composition containing a filler of more than 5% by weight and 40% by weight or less in the composition according to the above [6].
[8] An injection-molded product obtained by injection-molding the polypropylene resin composition according to the above [6] or [7].

It is possible to provide a composition having a high elastic modulus, a high impact strength at a low temperature, and a low linear expansion coefficient.

In the present invention, a composition containing the components (1) and (2) as essential components and optionally containing known additives is referred to as a "masterbatch composition". The masterbatch composition can be used by mixing with other resins, but can also be used alone. A resin composition containing at least one of a "masterbatch composition" and an elastomer or polypropylene-based resin different from the masterbatch composition, and optionally a filler, is referred to as a "polypropylene resin composition". Hereinafter, the present invention will be described in detail. In the present invention, "X to Y" includes the fractional values X and Y. "X or Y" means either one or both of X and Y.

1. 1. Masterbatch Composition The masterbatch composition of the present invention contains the following components.
Component (1): Propylene homopolymer Component (2): Propylene-ethylene copolymer containing 55-80% by weight of ethylene-derived units

(1) Component (1): Propylene homopolymer As the component (1) of the present invention, a propylene homopolymer (homopolypropylene) is used in order to satisfy the requirements for rigidity and heat resistance in the final product. The propylene homopolymer of the present invention contains 2.0% by weight or less, preferably 1.0% by weight or less so as not to impair the gist of the invention due to the presence of recycled monomers in the production process, mixing of transitional products, or the like. It may contain a small amount of ethylene or one or more C4-C10-α-olefin-derived units.

(2) Component (2): Propylene-Ethylene Copolymer The propylene-ethylene copolymer used in the present invention contains 55 to 80% by weight of ethylene-derived units. If the content of ethylene-derived units is less than the lower limit, the coefficient of linear expansion increases. Further, when the upper limit is exceeded, the coefficient of linear expansion increases and the impact strength also decreases. Further, in the production, especially when the content of the ethylene-derived unit is about 55% by weight, if the ratio of the component (2) is set to 25 parts by weight or more, the polymerized particles are easily adhered to each other and the line is blocked. .. From this viewpoint, the content of ethylene-derived units is preferably 60 to 75% by weight.

(3) Composition ratio The weight ratio of the components (1) and (2) is (1) :( 2) = 85-60: 15-40. If the amount of the component (2) exceeds this upper limit, the rigidity is significantly reduced, and if it is less than the lower limit, the impact resistance is significantly reduced. From this point of view, the ratio is preferably 75-60: 25-40.

(4) Other components In addition, the masterbatch composition includes antioxidants, chlorine absorbers, heat-resistant stabilizers, light stabilizers, ultraviolet absorbers, internal lubricants, external lubricants, antiblocking agents, antistatic agents, and antifogging agents. Olefin polymers such as agents, crystal nucleating agents, flame retardants, dispersants, copper damage inhibitors, neutralizing agents, plasticizers, bubble inhibitors, cross-linking agents, peroxides, oil spreads and other organic and inorganic pigments. May be added with commonly used additives. The amount of each additive added may be a known amount.

The masterbatch composition of the present invention particularly preferably contains a crystal nucleating agent. As the crystal nucleating agent, those known in the art can be used. Examples of the crystal nucleating agent include an inorganic filler having a crystal nucleating action such as talc, and an organic crystal nucleating agent such as eltel phosphate, a metal carboxylic acid salt, benzylidene sorbitol, and a triaminobenzene derivative. The amount of the crystal nucleating agent is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the composition.

(5) Characteristics 1) XI Mw / Mn
The Mw / Mn of the xylene insoluble matter (XI) of the composition measured by GPC is 6 to 20. The xylene insoluble component is a crystalline component in the composition. In the present invention, Mw / Mn, which is an index of molecular weight distribution, is in a wide range. That is, there are many high molecular weight components, and the components promote the orientation of the polymer chains during molding. Therefore, a low coefficient of linear expansion can be achieved. Furthermore, the high molecular weight component improves impact resistance, especially at low temperatures. From this viewpoint, Mw / Mn is preferably 7 to 20. Mw / Mn of XI can be obtained by obtaining a component insoluble in xylene at 25 ° C. and measuring the component by a GPC (gel permeation chromatography) method.

3) XSIV
The ultimate viscosity (XSIV) of the xylene-soluble component (XS) of the composition is also an index of the molecular weight of the non-crystalline component in the composition. XSIV is obtained by obtaining a component soluble in xylene at 25 ° C. and measuring the ultimate viscosity of the component by a conventional method. In the present invention, XSIV is relatively low at 1 to 3 dl / g. A low XSIV is advantageous in achieving a low coefficient of linear expansion because the component (2) is easily stretched in an injection-molded product, but if it is too low, the impact resistance deteriorates. Therefore, it is considered that when XSIV is in this range, both low coefficient of linear expansion and high impact resistance can be achieved. From this point of view, the ultimate viscosity is preferably 1.5 to 2.5 dl / g.

4) Melt flow rate The melt flow rate (hereinafter, also referred to as “MFR”) of the masterbatch composition at 230 ° C. and a load of 21.18 N is 1 to 50 g / 10 minutes. When the MFR is in this range, excellent moldability can be achieved. When the MFR exceeds the upper limit value, the MFR of the component (1) becomes very high (the molecular weight is low), and as a result, the impact resistance is lowered and the production becomes difficult. If the MFR value is less than the lower limit, the MFR of the polypropylene resin composition using the masterbatch composition will decrease, making molding such as injection molding difficult. From this point of view, the melt flow rate is preferably 5 to 35 g / 10 minutes.

4) Elastic modulus The masterbatch composition of the present invention preferably has a flexural modulus of 1000 to 1500 MPa, more preferably 1100 to 1300 MPa.

5) Coefficient of linear expansion The masterbatch composition of the present invention preferably has a coefficient of linear expansion in the MD direction at -30 to 80 ° C. of 60 to 80 × 10 ^-6 / K, preferably 65 to 78 × 10 ^-6. It is preferably / K. The coefficient of linear expansion can be measured by performing thermomechanical analysis (TMA) after annealing the molded product.

6) The master batch composition of the impact strength present invention is preferably Charpy impact strength at room temperature is 20~50kJ / ^{m 2,} Charpy impact strength at low temperature (-30 ° C.) is 3~6kJ / ^{m 2} Is preferable.

(6) Production Method The master batch composition of the present invention contains the raw material monomer of the component (1) and the raw material monomer of the component (2), (A) magnesium, titanium, halogen, and a succinate-based compound as an internal electron donor. It is produced by a method including a step of polymerizing using a catalyst containing a solid catalyst (B), an organoaluminum compound, and (C) an external electron donor compound.

The polymer polymerized using a catalyst containing a succinate compound as an internal electron donor has a wide molecular weight distribution, and the high molecular weight component and the low molecular weight component are uniformly dispersed. The molecular weight distribution is a physical quantity and can be determined by measurement. However, this measured value cannot represent the degree of dispersion of the high molecular weight component and the low molecular weight component. For example, by blending a high molecular weight component and a low molecular weight component by powder blending or pellet blending, or by increasing the number of steps in multi-step polymerization, a polymer having a molecular weight distribution (measured value) similar to that of the present invention can be obtained. It is also possible to obtain. However, the degree of dispersion of the high molecular weight component and the low molecular weight component is different between the polymer thus obtained and the polymer of the present invention, and a uniform degree of dispersion is achieved in the present invention. The difference is remarkable in performance such as low coefficient of linear expansion and high impact resistance.
Therefore, since there is a limit to specifying the performance of a polymer obtained by a catalyst using succinate as an internal electron donor compound by a physical quantity such as a measured value, it is not realistic to specify the property in words in the claims. Absent.

1) Solid catalyst (component A)
The component (A) can be prepared by a known method, for example, by bringing the magnesium compound, the titanium compound and the electron donor compound into mutual contact.

As the titanium compound used for the preparation of the component (A), a tetravalent titanium compound represented by the general formula: Ti (OR) _g X _4-g is suitable. In the formula, R is a hydrocarbon group, X is a halogen, and 0 ≦ g ≦ 4. As titanium compounds, TiCl ₄ and more specifically, TiBr _4, titanium tetrahalides such as _{TiI 4; Ti (OCH 3)} Cl 3, Ti (OC 2 H 5) Cl 3, Ti (O n -C 4 H ₉ ) Trihalogenated alkoxytitanium such as Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OisoC ₄ H ₉ ) Br ₃ ; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl _{2, Ti (O n -C 4} H 9) 2 Cl 2, Ti (OC 2 H 5) 2 dihalogenated alkoxy titanium such as _{Br 2; Ti (OCH 3)} 3 Cl, Ti (OC 2 H 5) 3 Cl _{, Ti (O n -C 4 H} 9) 3 Cl, Ti (OC 2 H 5) monohalide trialkoxy titanium such as _{3 Br; Ti (OCH 3)} 4, Ti (OC 2 H 5) 4, Ti ( such as O _n -C ₄ tetraalkoxy titanium such as H _{9) 4} and the like. Among these, a halogen-containing titanium compound, particularly titanium tetrahalogenate, is preferable, and a more particularly preferable one is titanium tetrachloride.

Examples of the magnesium compound used for preparing the component (A) include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamilmagnesium, dihexylmagnesium, and dihexylmagnesium. Examples thereof include decylmagnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxymagnesium, ethyl butyl magnesium, and butyl magnesium hydride. These magnesium compounds can be used in the form of a complex compound with, for example, organoaluminum, and may be in a liquid state or a solid state. More suitable magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; magnesium methoxychloride, magnesium ethoxychloride, magnesium isopropoxychloride, magnesium butoxychloride, magnesium octoxychloride. Alkoxymagnesium halide; Allyloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium; phenoxy Alyloxymagnesium such as magnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate can be mentioned.

The electron donor compound used for the preparation of the component (A) is generally referred to as an "internal electron donor". In the present invention, it is preferable to use an internal electron donor that gives a wide molecular weight distribution. Generally, it is known that the molecular weight distribution can be increased by carrying out polymerization in multiple steps, but it is difficult to increase the molecular weight distribution when the molecular weight of XI is low. However, by using a specific internal electron donor, it is possible to increase the molecular weight distribution even when the molecular weight of XI is low. The composition polymerized using the catalyst is a composition having the same molecular weight distribution obtained by pelleting or powder blending a polymer polymerized using another catalyst, and a composition having the same molecular weight distribution by further polymerizing in multiple stages. It shows excellent fluidity and large swell compared to the thing. This is because the composition produced by using the catalyst is integrated with the high molecular weight component and the low molecular weight component in a state close to the molecular level, but the latter resin composition is not mixed in a state close to the molecular level. It is considered that this is because they seem to show the same molecular weight distribution. However, it is not realistic to express this in words in the claims. The preferred internal electron donor will be described below.

The preferred internal electron donor in the present invention is a succinate compound. In the present invention, the succinate compound refers to a succinic acid diester or a substituted succinic acid diester. Hereinafter, the succinate compound will be described in detail. The succinate-based compound preferably used in the present invention is represented by the following formula (I).

In the formula, the groups R ₁ and R ₂ are linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkyl from C _{1 to} C ₂₀ , which are the same or different from each other and may contain heteroatoms. Aryl groups; groups R _{3 to} R ₆ are linear or branched alkyl, alkenyl, cycloalkyl, aryl, of C _{1 to} C ₂₀ , which are the same or different from each other and contain hydrogen or, in some cases, heteroatoms. Groups R _{3 to} R ₆ , which are arylalkyl or alkylaryl groups and are bonded to the same or different carbon atoms, may be bonded together to form a ring.

R ₁ and R ₂ are preferably C _1- C ₈ alkyl, cycloalkyl, aryl, arylalkyl, and alkylaryl groups. Compounds in which R ₁ and R ₂ are selected from primary alkyls, particularly branched primary alkyls, are particularly preferred. Examples of suitable R ₁ and R ₂ groups are alkyl groups C _{1 to} C ₈ , such as methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Ethyl, isobutyl, and neopentyl are particularly preferred.

One of the preferred groups of compounds represented by formula (I) is branched alkyl, cycloalkyl, aryl, arylalkyl, where R _{3 to} R ₅ are hydrogen and R ₆ has 3 to 10 carbon atoms. , And an alkylaryl group. Preferred specific examples of such a monosubstituted succinate compound are diethyl-sec-butyl succinate, diethyl texyl succinate, diethyl cyclopropyl succinate, diethyl norbonyl succinate, diethyl perihydro succinate, diethyl. Trimethylsilyl succinate, diethyl methoxy succinate, diethyl-p-methoxyphenyl succinate, diethyl-p-chlorophenyl succinate, diethyl phenyl succinate, diethyl cyclohexyl succinate, diethyl benzyl succinate, diethyl cyclohexyl Methyl succinate, diethyl-t-butyl succinate, diethyl isobutyl succinate, diethyl isopropyl succinate, diethyl neopentyl succinate, diethyl isopentyl succinate, diethyl (1-trifluoromethyl ethyl) succinate , Diethylfluorenyl succinate, 1-ethoxycarbodiisobutylphenyl succinate, diisobutyl-sec-butyl succinate, diisobutyltexyl succinate, diisobutylcyclopropyl succinate, diisobutylnorbonyl succinate, diisobutylperihydro Succinate, diisobutyltrimethylsilyl succinate, diisobutylmethoxysuccinate, diisobutyl-p-methoxyphenyl succinate, diisobutyl-p-chlorophenyl succinate, diisobutylcyclohexylsuccinate, diisobutylbenzyl succinate, diisobutylcyclohexylmethyl Succinate, diisobutyl-t-butyl succinate, diisobutylisobutyl succinate, diisobutylisopropyl succinate, diisobutylneopentyl succinate, diisobutylisopentyl succinate, diisobutyl (1-trifluoromethylethyl) succinate, Diisobutylfluorenyl succinate, dineopentyl-sec-butyl succinate, dineopentyltexyl succinate, geneopentylcyclopropyl succinate, dineopentyl norbonyl succinate, dineopentyl perihydrosuccinate , Dineopentyltrimethylsilyl succinate, dineopentylmethoxysuccinate, geneopentyl-p-methoxyphenyl succinate, geneopentyl-p-chlorophenyl succinate, geneopentylphenyl succinate, genine Opentyl Cyclohexyl succinate, Dineopentyl benzyl succinate, Dineopentyl cyclohexylmethyl succinate, Dineopentyl-t-butyl succinate, Dineopentyl isobutyl succinate, Dineopentyl isopropyl succinate, Di Neopentyl Neopentyl succinate, dineopentyl isopentyl succinate, dineopentyl (1-trifluoromethylethyl) succinate, dineopentyl fluorenyl succinate.

Another preferred group of compounds within the range of formula (I) is a linear C _{1 to} C ₂₀ in which at least two groups from R _{3 to} R ₆ differ from hydrogen and in some cases contain heteroatoms. Alternatively, it is selected from branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups. A compound in which two groups different from hydrogen are bonded to the same carbon atom is particularly preferable. Specifically, it is a compound in which R ₃ and R ₄ are different groups from hydrogen, and R ₅ and R ₆ are hydrogen atoms. Preferred specific examples of such disubstituted succinates are diethyl-2,2-dimethylsuccinate, diethyl-2-ethyl-2-methylsuccinate, diethyl-2-benzyl-2-isopropylsuccinate, diethyl. -2-Cyclohexylmethyl-2-isobutyl succinate, diethyl-2-cyclopentyl-2-n-butyl succinate, diethyl-2,2-diisobutyl succinate, diethyl-2-cyclohexyl-2-ethyl succinate Nate, diethyl-2-isopropyl-2-methylsuccinate, diethyl-2-tetradecyl-2-ethylsuccinate, diethyl-2-isobutyl-2-ethylsuccinate, diethyl-2- (1-trifluoro) Methylethyl) -2-methylsuccinate, diethyl-2-isopentyl-2-isobutylsuccinate, diethyl-2-phenyl-2-n-butylsuccinate, diisobutyl-2,2-dimethylsuccinate, Diisobutyl-2-ethyl-2-methylsuccinate, diisobutyl-2-benzyl-2-isopropylsuccinate, diisobutyl-2-cyclohexylmethyl-2-isobutylsuccinate, diisobutyl-2-cyclopentyl-2-n- Butyl succinate, diisobutyl-2,2-diisobutyl succinate, diisobutyl-2-cyclohexyl-2-ethyl succinate, diisobutyl-2-isopropyl-2-methylsuccinate, diisobutyl-2-tetradecyl-2- Ethyl succinate, diisobutyl-2-isobutyl-2-ethyl succinate, diisobutyl-2- (1-trifluoromethylethyl) -2-methyl succinate, diisobutyl-2-isopentyl-2-isobutyl succinate , Diisobutyl-2-phenyl-2-n-butyl succinate, dineopentyl-2,2-dimethylsuccinate, dineopentyl-2-ethyl-2-methylsuccinate, dineopentyl-2-benzyl-2-isopropyls Xinate, Dineopentyl-2-cyclohexylmethyl-2-isobutyl succinate, Dineopentyl-2-cyclopentyl-2-n-butyl succinate, Dineopentyl-2,2-diisobutyl succinate, Dineopentyl-2-cyclohexyl-2 -Ethyl succinate, dineopentyl-2-isopropyl-2-methylsuccinate, dineopentyl-2-tetradecyl-2-ethylsuccine , Dineopentyl-2-isobutyl-2-ethyl succinate, dineopentyl-2- (1-trifluoromethylethyl) -2-methylsuccinate, dineopentyl-2-isopentyl-2-isobutyl succinate, dineopentyl It is -2-phenyl-2-n-butyl succinate.

Further, compounds in which at least two groups different from hydrogen are bonded to different carbon atoms are also particularly preferable. Specifically, it is a compound in which R ₃ and R ₅ are different groups from hydrogen. In this case, R ₄ and R ₆ may be hydrogen atoms or groups different from hydrogen, but it is preferable that one of them is a hydrogen atom (trisubstituted succinate). Preferred specific examples of such compounds are diethyl-2,3-bis (trimethylsilyl) succinate, diethyl-2,2-sec-butyl-3-methylsuccinate, diethyl-2- (3,3,3-). Trifluoropropyl) -3-methylsuccinate, diethyl-2,3-bis (2-ethylbutyl) succinate, diethyl-2,3-diethyl-2-isopropylsuccinate, diethyl-2,3-diisopropyl-2 -Methyl succinate, diethyl-2,3-dicyclohexyl-2-methyldiethyl-2,3-dibenzylsuccinate, diethyl-2,3-diisopropylsuccinate, diethyl-2,3-bis (cyclohexylmethyl) ) Succinate, diethyl-2,3-di-t-butyl succinate, diethyl-2,3-diisobutyl succinate, diethyl-2,3-dineopentyl succinate, diethyl-2,3-diiso Pentyl succinate, diethyl-2,3- (1-trifluoromethylethyl) succinate, diethyl-2,3-tetradecyl succinate, diethyl-2,3-fluorenyl succinate, diethyl-2-isopropyl -3-Isobutyl succinate, diethyl-2-tert-butyl-3-isopropyl succinate, diethyl-2-isopropyl-3-cyclohexyl succinate, diethyl-2-isopentyl-3-cyclohexyl succinate, diethyl -2-Tetradecyl-3-cyclohexylmethyl succinate, diethyl-2-cyclohexyl-3-cyclopentyl succinate, diisobutyl-2,3-diethyl-2-isopropylsuccinate, diisobutyl-2,3-diisopropyl-2 -Methyl succinate, diisobutyl-2,3-dicyclohexyl-2-methylsuccinate, diisobutyl-2,3-dibenzylsuccinate, diisobutyl-2,3-diisopropylsuccinate, diisobutyl-2,3- Bis (cyclohexylmethyl) succinate, diisobutyl-2,3-di-t-butyl succinate, diisobutyl-2,3-diisobutyl succinate, diisobutyl-2,3-dineopentyl succinate, diisobutyl-2, 3-Diisopentyl succinate, diisobutyl-2,3- (1-trifluoromethylethyl) succinate, diisobutyl-2,3-tetradecyl succinate, diisobutyl-2,3-fluorenyl succinate , Diisobutyl-2-isopropyl-3-isobutyl succinate, diisobutyl-2-tert-butyl-3-isopropyl succinate, diisobutyl-2-isopropyl-3-cyclohexyl succinate, diisobutyl-2-isopentyl-3-3 Cyclohexyl succinate, diisobutyl-2-tetradecyl-3-cyclohexylmethyl succinate, diisobutyl-2-cyclohexyl-3-cyclopentyl succinate, dineopentyl-2,3-bis (trimethylsilyl) succinate, dineopentyl-2,2- sec-Butyl-3-methylsuccinate, dineopentyl-2- (3,3,3-trifluoropropyl) -3-methylsuccinate, dineopentyl-2,3-bis (2-ethylbutyl) succinate, dineopentyl- 2,3-Diethyl-2-isopropyl succinate, dineopentyl-2,3-diisopropyl-2-methyl succinate, dineopentyl-2,3-dicyclohexyl-2-methyl succinate, dineopentyl-2,3-di Benzyl succinate, dineopentyl-2,3-diisopropyl succinate, dineopentyl-2,3-bis (cyclohexylmethyl) succinate, dineopentyl-2,3-di-t-butyl succinate, dineopentyl-2,3- Diisobutyl succinate, geneopentyl-2,3-dineopentyl succinate, dineopentyl-2,3-diisopentyl succinate, dineopentyl-2,3- (1-trifluoromethylethyl) succinate, dineopentyl-2 , 3-Tetradecyl succinate, Dineopentyl-2,3-Fluorenyl succinate, Dineopentyl-2-isopropyl-3-isobutyl succinate, Dineopentyl-2-tert-butyl-3-isopropyl succinate, Dineopentyl -2-Isopropyl-3-cyclohexyl succinate, dineopentyl-2-isopentyl-3-cyclohexyl succinate, dineopentyl-2-tetradecyl-3-cyclohexylmethyl succinate, dineopentyl-2-cyclohexyl-3-cyclopentyl succinate Nate.

Among the compounds of formula (I), a compound some are bonded to form a ring together of the radicals R ₃ to R ₆ may be also preferably used. As such compounds, the compounds listed in Special Table 2002-542347, for example, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2,6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1-( Ethoxyacetyl) -2,5-1 dimethylcyclopentane, 1- (ethoxycarbonyl) -1- (ethoxyacetylmethyl) -21methylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxy (cyclohexyl) acetyl) cyclohexane Can be mentioned. In addition, cyclic succinate compounds such as diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylic acid and diisobutyl cyclohexane-1,2-dicarboxylic acid as disclosed in International Publication No. 2009/069483 are also preferable. Can be used. As an example of other cyclic succinate compounds, the compounds disclosed in WO 2009/0577747 are also preferred.

Among the compounds of the formula (I), when the groups R3 to R6 contain a heteroatom, the heteroatom is preferably a Group 15 atom containing a nitrogen and phosphorus atoms or a Group 16 atom containing an oxygen and sulfur atoms. Examples of the compound in which the groups R3 to R6 contain a Group 15 atom include compounds disclosed in JP-A-2005-306910. On the other hand, examples of the compound in which the groups R3 to R6 contain a Group 16 atom include compounds disclosed in JP-A-2004-131537.

In addition, an internal electron donor that gives a molecular weight distribution equivalent to that of the succinate compound may be used. Examples of such an internal electron donor include the diphenyldicarboxylic acid ester described in JP2013-288704, the cyclohexenedicarboxylic acid ester described in JP2014-2016002, and JP2013-28705. Dicycloalkyldicarboxylic acid ester, diol dibenzoate described in Patent No. 4959920, 1,2-phenylenedibenzoate described in International Publication No. 2010/078494.

2) Organoaluminium compound (component B)
Examples of the organoaluminum compound of the component (B) include the following.
Trialkylaluminum such as triethylaluminum and tributylaluminum;
Trialkenyl aluminum such as triisoprenyl aluminum:
Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide;
Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxydo and butylaluminum sesquibutoxide;

Partially halogenated alkylaluminum such as alkylaluminum dihalogenide such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromid;
Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;
Partially hydrogenated alkylaluminum such as alkylaluminum dihydrides such as ethylaluminum dihydrides and propylaluminum dihydrides;
Partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butokicyclolide, ethylaluminum ethoxybromid.

3) Electron donor compound (component C)
The electron donor compound of component (C) is generally referred to as an "external electron donor". As such an electron donor compound, an organosilicon compound is preferable. Preferred organosilicon compounds include:
Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyl Dimethoxysilane, diphenyldiethoxysilane, biso-tolyldimethoxysilane, bism-tolyldimethoxysilane, bisp-tolyldimethoxysilane, bisp-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane Silane, Cyclohexylmethyldimethoxysilane, Cyclohexylmethyldiethoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Vinyltrimethoxysilane, Methyltrimethoxysilane, n-propyltriethoxysilane, Decyltrimethoxysilane, Decyltriethoxysilane, Phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, texyltrimethoxysilane, n-butyltriethoxysilane, iso- Butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornantrimethoxysilane , 2-Norbornan triethoxysilane, 2-Norbornan methyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyl Tetraethoxydisiloxane.

Among them, ethyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, t-butyltriethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-butylethyldimethoxysilane, t-Butylpropyldimethoxysilane, t-butylt-butoxydimethoxysilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane, isobutylmethyldimethoxysilane, i-butylsec-butyldimethoxysilane, ethyl (perhydroisoquinolin 2- Il) dimethoxysilane, bis (decahydroisoquinolin-2-yl) dimethoxysilane, tri (isopropeniroxy) phenylsilane, texyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltri Butoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, i-butyl i-propyldimethoxysilane, cyclopentyl t-butoxydimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyl i-butyldimethoxysilane, cyclopentyl i -Butyldimethoxysilane, cyclopentylisopropyldimethoxysilane, di-sec-butyldimethoxysilane, diethylaminotriethoxysilane, tetraethoxysilane, tetramethoxysilane, isobutyltriethoxysilane, phenylmethyldimethoxysilane, phenyltriethoxylan, bisp-tolyl Dimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, 2-norbornantriethoxysilane, 2-norbornanmethyldimethoxysilane, diphenyldiethoxysilane, methyl (3,3,3-trifluoropropyl) Dimethoxysilane, ethyl silicate and the like are preferable.

4) Polymerization The raw material monomer is brought into contact with the catalyst prepared as described above to polymerize. At this time, it is preferable to first perform prepolymerization using the catalyst. The prepolymerization is a step of forming a polymer chain as a foothold for the subsequent main polymerization of the raw material monomer in the solid catalyst component. Prepolymerization can be carried out by a known method. Prepolymerization is usually carried out at 40 ° C. or lower, preferably 30 ° C. or lower, and more preferably 20 ° C. or lower.
Next, the prepolymerized catalyst is introduced into the polymerization reaction system to carry out the main polymerization of the raw material monomer. In this polymerization, it is preferable to polymerize the raw material monomer of the component (1) and the raw material monomer of the component (2) using two or more reactors. The polymerization may be carried out in a liquid phase, a gas phase or a liquid-gas phase. The polymerization temperature is preferably room temperature to 150 ° C., more preferably 40 ° C. to 100 ° C. The polymerization pressure is preferably in the range of 33 to 45 bar when carried out in the liquid phase and in the range of 5 to 30 bar when carried out in the gas phase. Conventional molecular weight modifiers known in the art, such as chain transfer agents (eg, hydrogen or ZnEt ₂ ), may be used.

Further, a polymerizer having a gradient of monomer concentration and polymerization conditions may be used. In such a polymerizer, for example, one in which at least two polymerization regions are connected can be used, and the monomer can be polymerized by vapor phase polymerization. Specifically, in the presence of a catalyst, a monomer is supplied and polymerized in a polymerization region consisting of an ascending tube, and a monomer is supplied and polymerized by a descending tube connected to the ascending tube. The polymer product is recovered while circulating. This method comprises means to prevent the gas mixture present in the ascending tube from entering the descending tube in whole or in part. Also, a gas and / or liquid mixture having a composition different from that of the gas mixture present in the ascending tube is introduced into the descending tube. As the above polymerization method, for example, the method described in JP-A-2002-520426 can be applied.

2. 2. Polypropylene resin composition In the polypropylene resin composition of the present invention, at least one of an elastomer different from the component (2) of the masterbatch composition or a polypropylene resin different from the masterbatch composition is added to the masterbatch composition. Obtained by mixing. The total amount of the elastomer and the polypropylene-based resin different from the masterbatch composition is preferably 5 to 40% by weight, more preferably 5 to 30% by weight in the polypropylene resin composition.

(1) Elastomer Elastomer is a polymer having elasticity, and is mainly added for the purpose of improving the impact resistance of the composition. Examples of the elastomer used in the present invention include a copolymer of ethylene and α-olefin. Examples of the α-olefin include α-olefins having 3 to 12 carbon atoms, and specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and the like are preferable. The elastomer preferably has a lower density than the polymers of component (1) and component (2). For example the density of the elastomer is preferably but not limited a 0.850~0.890g / cm ^3, more preferably 0.860~0.880g / cm ^3. Such an elastomer can be prepared, for example, by polymerizing a monomer using a homogeneous catalyst such as metallocene or half metallocene as described in Japanese Patent Application Laid-Open No. 2015-113363. The MFR of the elastomer is preferably 0.1 to 50 g / 10 min under a load of 190 ° C. and 21.6 N.

(2) Polypropylene resin different from the masterbatch composition A polypropylene resin different from the masterbatch composition is added for the purpose of improving the fluidity, rigidity, impact resistance and the like of the composition. Polypropylene-based resins different from the master batch composition include propylene homopolymers, ethylenes of more than 0% by weight and 5% by weight or less, or propylene random copolymers containing one or more types of C4-C10-α-olefins, propylene. Examples thereof include a polymerization mixture (also referred to as HECO) obtained by polymerizing ethylene with one or more kinds of C3 to C10-α olefins in the presence of a polymer. The masterbatch composition of the present invention is also a kind of HECO, and HECO added to the masterbatch composition can be produced by the same method as the masterbatch composition, but the two are different in composition.

(3) Filler The polypropylene resin composition of the present invention may contain a filler. The filler is added mainly for the purpose of improving the rigidity of the material. Examples of the filler include inorganic fillers such as talc, clay, calcium carbonate, magnesium hydroxide and glass fiber, and organic fillers such as carbon fiber and cellulose fiber. In order to improve the dispersibility of these fillers, surface treatment of the filler and preparation of a masterbatch of the filler and the resin may be performed, if necessary. Among the fillers, talc is preferable because it easily mixes with the propylene (co) polymer and the copolymer of ethylene and α-olefin and easily improves the rigidity of the molded product. The amount of the filler is preferably more than 5% by weight and 40% by weight or less, more preferably 10 to 35% by weight in the polypropylene resin composition.

(3) Other Ingredients The polypropylene resin composition of the present invention includes antioxidants, chlorine absorbers, heat stabilizers, light stabilizers, ultraviolet absorbers, internal lubricants, external lubricants, antiblocking agents, antistatic agents, etc. Olefin such as antifogging agents, crystal nucleating agents, flame retardants, dispersants, copper damage inhibitors, neutralizing agents, plasticizers, bubble inhibitors, cross-linking agents, peroxides, oil spreads and other organic and inorganic pigments. Conventional additives commonly used for the polymer may be added. The amount of each additive added may be a known amount.

(4) Production Method The polypropylene resin composition of the present invention can be produced by melt-kneading the above components. The kneading method is not limited, but a method using a kneader such as an extruder is preferable. The kneading conditions are not particularly limited, but the cylinder temperature is preferably 180 to 250 ° C. The polypropylene resin composition thus obtained is preferably in the form of pellets. Alternatively, a polypropylene resin composition can be produced as a molded product by weighing the dry blend of the above components in an injection molding machine and kneading it in a melt-kneading portion (cylinder). As described above, the polypropylene resin composition of the present invention is obtained by mixing the masterbatch composition with other components. The phase structure of the polypropylene resin composition consists of a propylene-ethylene copolymer component derived from the masterbatch composition and an elastomer (in some cases, the masterbatch composition) in a matrix containing a propylene homopolymer derived from the masterbatch composition as a main component. Is a copolymer of ethylene and α-olefin derived from different HECOs), and the effect of the present invention is exhibited by forming the phase structure. However, in the polypropylene resin composition, a dispersed phase derived from the masterbatch composition obtained by the polymerization blend and a dispersed phase such as a pellet-blended elastomer exist in a complicated manner, and which component is derived from these phases? There are circumstances in which it is difficult to pinpoint exactly.

(5) Injection Molding The masterbatch composition and polypropylene resin composition of the present invention are suitable for injection molding. The polypropylene resin composition of the present invention has high rigidity, high impact resistance, and a low coefficient of linear expansion, and is therefore suitable for automobile parts. General injection conditions are a cylinder temperature of 200 to 230 ° C., a mold temperature of 20 to 50 ° C., and an injection speed of 30 to 50 mm / sec.

1. 1. Masterbatch Composition [Example 1]
As described below, a master batch composition comprising 65.5% by weight of the polypropylene homopolymer as the component (1) and 34.5% by weight of the propylene-ethylene copolymer having 65.7% by weight of the ethylene-derived unit as the component (2). Manufactured a thing.
A solid catalyst component was prepared according to the preparation method described in Examples of JP-A-2011-500907. Specifically, it was prepared as follows.
250 mL of TiCl ₄ was introduced at 0 ° C. into a 500 mL four-necked round bottom flask purged with nitrogen. While stirring, according to the method described in Example 2 10.0g of the fine spherical _{MgCl 2 · 1.8C 2 H 5 OH} ( US Patent 4,399,054, however operating at 3000rpm instead of 10000rpm production And 9.1 mmol of diethyl-2,3- (diisopropyl) succinate were added. The temperature was raised to 100 ° C. and held for 120 minutes. The stirring was then stopped, the solid product was allowed to settle and the supernatant was sucked out. The following operation was then repeated twice: 250 mL of fresh TiCl ₄ was added, the mixture was reacted at 120 ° C. for 60 minutes and the supernatant was sucked out. The solid was washed 6 times with anhydrous hexane (6 x 100 mL) at 60 ° C.

The solid catalyst and triethylaluminium (TEAL) and dicyclopentyldimethoxysilane (DCPMS) are prepared in such an amount that the weight ratio of TEAL to the solid catalyst is 18 and the weight ratio of TEAL / DCPMS is 10 at room temperature. Contacted for minutes. Prepolymerization was carried out by holding the obtained catalyst system in a suspended state in liquid propylene at 20 ° C. for 5 minutes.
The obtained prepolymer was introduced into the first-stage liquid-phase polymerization reactor to obtain a propylene homopolymer, and then the obtained polymer was introduced into the second-stage gas-phase polymerization reactor to have a common weight. The coalescence (propylene-ethylene copolymer) was polymerized. During the polymerization, the temperature and pressure were adjusted, and hydrogen was used as a molecular weight modifier. The ratio of the polymerization temperature to the reactant was that the polymerization temperature and hydrogen concentration were 70 ° C. and 0.31 mol% in the first stage reactor, respectively, and the polymerization temperature, H2 / C2 and C2 / in the second stage reactor. (C2 + C3) was 80 ° C., 0.16 molar ratio, and 0.69 molar ratio, respectively. Further, the residence time distributions of the first and second stages were adjusted so that the amount of the copolymer component was 34.5 parts by weight out of 100 parts by weight of the polymer.

To 100 parts by weight of the obtained polypropylene polymer, 0.2 parts by weight of BASF B225 as an antioxidant and 0.05 parts by weight of calcium stearate manufactured by Tannan Chemical Co., Ltd. as a neutralizing agent were blended. After stirring and mixing with a Henschel mixer for 1 minute, the mixture was melt-kneaded and extruded at a cylinder temperature of 200 ° C. using a twin-screw extruder (manufactured by Technobel Co., Ltd., model number KZW15TW-30MG) having a screw diameter of 15 mm. After cooling the strands in water, they were cut with a pelletizer to obtain pellets. Next, the pellet was injection-molded into various test pieces using an injection molding machine (manufactured by FANUC, model number Roboshot S-2000i 100B). The molding conditions were a cylinder temperature of 200 ° C., a mold temperature of 40 ° C., and an injection speed of 200 mm / sec. Various physical properties were evaluated using the test piece. The evaluation method will be described later.

[Example 2]
The hydrogen concentration of the first-stage reactor was 0.28 mol%, and the H2 / C2 and C2 / (C2 + C3) of the second-stage reactor were 0.22 mol ratio and 0.59 mol ratio, respectively. A polypropylene polymer was produced in the same manner as in Example 1 except that the residence time distributions of the first and second stages were adjusted so that the amount of the components was 32.9 parts by weight in 100 parts by weight of the polymer. Using the polypropylene polymer, a masterbatch composition for this example was produced and evaluated in the same manner as in Example 1.

[Example 3]
Pellets were prepared and evaluated by melt-kneading in the same manner as in Example 1 except that talc was further added to the polypropylene polymer obtained in Example 2. The blending amount of talc (trade name: HTP05L, manufactured by IMI Fabi) was 1 part by weight with respect to 100 parts by weight of the polymer.

[Comparative Example 1]
A solid catalyst in which Ti and diisobutylphthalate as an internal donor were supported on MgCl ₂ was prepared by the method described in Example 5 of European Patent No. 728769. Next, using the solid catalyst, triethylaluminium (TEAL) as the organoaluminum compound, and dicyclopentyldimethoxysilane (DCPMS) as the external electron donor compound, the weight ratio of TEAL to the solid catalyst was 20, and the weight ratio of TEAL / DCPMS was 20. The contact was carried out at 12 ° C. for 24 minutes in an amount such that the value was 10. Prepolymerization was carried out by holding the obtained catalyst system in a suspended state in liquid propylene at 20 ° C. for 5 minutes.
Using the obtained prepolymer, a propylene homopolymer was produced by multistage polymerization using two liquid phase polymerization reactors. The hydrogen concentration of the first polymerization reactor was 0.16 mol%, the hydrogen concentration of the second polymerization reactor was 1.70 mol%, and the polymerization pressure was adjusted at a polymerization temperature of 70 ° C. The residence time distribution was adjusted so that was 50:50.
Subsequently, the obtained propylene homopolymer was introduced into a gas phase polymerization reactor to polymerize a copolymer (propylene / ethylene copolymer) in the same manner as in Example 1. During the polymerization, the temperature and pressure were adjusted, and hydrogen was used as a molecular weight modifier. In the second-stage reactor, the polymerization temperature, H2 / C2, and C2 / (C2 + C3) were 80 ° C., 0.12 molar ratio, and 0.68 molar ratio, respectively. Further, the residence time distributions of the first and second stages were adjusted so that the amount of the copolymer component was 30.0 parts by weight out of 100 parts by weight of the polymer.
Using the polypropylene polymer thus obtained, a comparative masterbatch composition was produced and evaluated in the same manner as in Example 1.

[Comparative Example 2]
Pellets were prepared and evaluated by melt-kneading in the same manner as in Example 1 except that talc was further added to the polypropylene polymer obtained in Comparative Example 1. The blending amount of talc (trade name: HTP05L, manufactured by IMI Fabi) was 1 part by weight with respect to 100 parts by weight of the polymer.

[Comparative Example 3]
The hydrogen concentration of the first-stage reactor was 0.44 mol%, the hydrogen concentration of the second-stage reactor, C2 / (C2 + C3) was 2.04 mol% and 0.37 mol ratio, respectively, and the copolymer component was set. A polypropylene polymer was produced in the same manner as in Example 1 except that the residence time distributions of the first and second stages were adjusted so that the amount of the polymer was 35.6 parts by weight based on 100 parts by weight of the polymer. Using the polypropylene polymer thus obtained, a comparative masterbatch composition was produced and evaluated in the same manner as in Example 1.

[Comparative Example 4]
Using the same prepolymerization catalyst as in Example 1, a propylene homopolymer was produced in the first-stage reactor at a polymerization temperature and hydrogen concentration of 70 ° C. and 0.29 mol%, respectively, and unreacted monomers were purged. Later, ethylene was introduced into the second-stage polymerization reactor to produce an ethylene homopolymer. The polymerization temperature and H2 / C2 of the second-stage reactor were set to 80 ° C. and 0.16 molar ratio, respectively, and the pressure was adjusted so that the amount of ethylene homopolymer was 29.8 parts by weight out of 100 parts by weight of the polymer. The residence time distributions of the first and second stages were adjusted so as to obtain a polypropylene polymer. A masterbatch composition for comparison was produced and evaluated in the same manner as in Example 1 except that the polymer was used.

[Comparative Example 5]
The hydrogen concentration of the first stage reactor was 0.34 mol%, the hydrogen concentration of the second stage reactor, C2 / (C2 + C3) was 4.13 mol% and 0.19 mol ratio, respectively, and the copolymer component was set. A polypropylene polymer was produced in the same manner as in Example 1 except that the residence time distributions of the first and second stages were adjusted so that the amount of the polymer was 31.5 parts by weight based on 100 parts by weight of the polymer. Using the polypropylene polymer thus obtained, a comparative masterbatch composition was produced and evaluated in the same manner as in Example 1.

[Comparative Example 6]
Using the prepolymerization catalyst of Comparative Example 1, the hydrogen concentration of the first liquid phase polymerization reactor was 0.73 mol%, and the hydrogen concentration of the second liquid phase polymerization reactor was 3.46 mol%. H2 / C2 and C2 / (C2 + C3) of the phase polymerization reactor are set to 0.12 mol ratio and 0.68 mol ratio, respectively, and the amount of the copolymer component is 49.0 parts by weight out of 100 parts by weight of the polymer. As described above, the residence time distributions of the liquid phase reactor and the gas phase reactor were adjusted to produce a polypropylene polymer. Using the polypropylene polymer thus obtained, a comparative masterbatch composition was produced and evaluated in the same manner as in Example 1.

[Comparative Example 7]
The hydrogen concentration of the first-stage liquid-phase polymerization reactor is 1.86 mol%, and the amount of the copolymer component is 37.0 parts by weight in 100 parts by weight of the polymer. A polypropylene polymer was produced in the same manner as in Comparative Example 6 except that the residence time distribution was adjusted. Using the polypropylene polymer thus obtained, a comparative masterbatch composition was produced and evaluated in the same manner as in Example 1.
The above results are shown in Table 1.

2. 2. Polypropylene resin composition [Example 4]
The hydrogen concentration of the first stage reactor was set to 0.59 mol%, and the residence time distributions of the first and second stages were adjusted so that the amount of the copolymer component was 30.7 parts by weight out of 100 parts by weight of the polymer. A polypropylene polymer was produced in the same manner as in Example 1 except for the above. Next, a masterbatch composition was produced using this polypropylene polymer in the same manner as in Example 1. The masterbatch composition, talc (trade name: HTP05L, manufactured by IMI Fabi) and an elastomer (trade name: Engage8200, manufactured by Dow Chemical) were melt-kneaded in the same manner as in Example 1 to prepare pellets. Next, the polypropylene resin composition was evaluated in the same manner as in Example 1.

[Example 5]
The hydrogen concentration of the first-stage reactor was 0.59 mol%, and the H2 / C2 and C2 / (C2 + C3) of the second-stage reactor were 0.14 mol ratio and 0.56 mol ratio, respectively. A polypropylene polymer was produced in the same manner as in Example 1 except that the residence time distributions of the first and second stages were adjusted so that the amount of the components was 29.5 parts by weight based on 100 parts by weight of the polymer. Next, a polypropylene resin composition was produced using this polypropylene polymer in the same manner as in Example 4, and evaluated.

[Example 6]
The hydrogen concentration of the first-stage reactor was 0.59 mol%, and the H2 / C2 and C2 / (C2 + C3) of the second-stage reactor were 0.12 mol% and 0.59 mol ratio, respectively. A polypropylene polymer was produced in the same manner as in Example 1 except that the residence time distributions of the first and second stages were adjusted so that the amount of the components was 32.3 parts by weight based on 100 parts by weight of the polymer. Next, using this polypropylene polymer, a polypropylene resin composition was produced and evaluated in the same manner as in Example 4 except that the contents of the masterbatch composition and talc were changed as shown in Table 2.

[Example 7]
The residence time distributions of the first and second stages were adjusted so that the hydrogen concentration of the reactor in the first stage was 0.39 mol% and the amount of the copolymer component was 37.5 parts by weight in 100 parts by weight of the polymer. Except for the above, a polypropylene polymer was produced in the same manner as in Example 4. Next, using this polypropylene polymer, a masterbatch composition, talc, MFR of 1750 g / 10 minutes, and a propylene homopolymer having a xylene-soluble content at 25 ° C. of 2.3% by weight were blended in the amounts shown in Table 2. A polypropylene resin composition was produced and evaluated in the same manner as in Example 4 except for the above.

[Comparative Example 8]
Using the prepolymerization catalyst of Comparative Example 1, the hydrogen concentration of the first liquid phase polymerization reactor was 0.68 mol%, and the hydrogen concentration of the second liquid phase polymerization reactor was 3.46 mol%. H2 / C2 and C2 / (C2 + C3) of the phase polymerization reactor are set to 0.08 molar ratio and 0.68 molar ratio, respectively, and the amount of the copolymer component is 26.8 parts by weight out of 100 parts by weight of the polymer. As described above, the residence time distributions of the liquid phase reactor and the gas phase reactor were adjusted to produce a polypropylene polymer. Next, using this polypropylene polymer, a polypropylene resin composition for comparison was produced and evaluated in the same manner as in Example 4.

[Comparative Example 9]
Using the prepolymerization catalyst of Comparative Example 1, the hydrogen concentration of the first-stage polymerization reactor was 1.44 mol%, and the hydrogen concentration of the second-stage polymerization reactor, C2 / (C2 + C3), was 1.75 mol, respectively. %, 0.22 molar ratio, and the residence time distribution of the liquid phase reactor and the gas phase reactor was adjusted so that the amount of the copolymer component was 26.4 parts by weight out of 100 parts by weight of the polymer. Manufactured coalescing. Next, using this polypropylene polymer, a polypropylene resin composition for comparison was produced and evaluated in the same manner as in Example 4.

[Comparative Example 10]
The hydrogen concentration of the first liquid phase polymerization reactor is 0.42 mol%, and the vapor phase reaction with the liquid phase reactor is such that the amount of the copolymer component is 28.0 parts by weight in 100 parts by weight of the polymer. A polypropylene polymer was produced in the same manner as in Comparative Example 8 except that the obtained polymer having an adjusted residence time distribution of the vessel was used. Next, using this polypropylene polymer, a polypropylene resin assembly composition for comparison was prepared in the same manner as in Example 4 except that the blending amounts of the masterbatch composition and talc were changed to the same amounts as in Example 6 shown in Table 2. Manufactured and evaluated.
The above results are shown in Table 2.

3. 3. Evaluation method [MFR]
The measurement was performed under the conditions of 230 ° C. and a load of 21.18 N according to JIS K 7210.
[Ethylene concentration in copolymer and amount of copolymer in masterbatch composition]
For a sample dissolved in a mixed solvent of 1,2,4-trichlorobenzene / benzene dehydride, Bruker's AVANCE III HD400 ( ¹³ C resonance frequency 100 MHz) was used, the measurement temperature was 120 ° C, the flip angle was 45 degrees, and the pulse interval was 7. A ¹³ C-NMR spectrum was obtained under the conditions of seconds, sample rotation speed of 20 Hz, and integration number of 5000 times.
<Total ethylene content in masterbatch composition>
Using the spectrum obtained above, total ethylene in the masterbatch composition by the method described in the literature of Kakugo, Y.Naito, K.Mizunuma and T.Miyatake, Macromolecules, 15, 1150-1152 (1982). The amount (% by weight) was determined.
<Ethylene concentration in copolymer (component (2))>
The ethylene concentration in the copolymer was determined by the same method as the total amount of ethylene except that the integrated intensity obtained by the following formula was used instead of the integrated intensity of Tββ obtained above.
T'ββ = 0.98 × Sαγ × A / (1-0.98 × A)
Here, A = Sαγ / (Sαγ + Sαδ)
<Amount of copolymer (component 2) in masterbatch composition>
It was calculated by the following formula.
Amount of component (2) (% by weight) = total ethylene amount / (ethylene concentration in copolymer / 100)

[Collection of xylene-soluble components]
2.5 g of polymer was placed in a flask containing 250 mL of o-xylene (solvent) and stirred for 30 minutes at 135 ° C. using a hot plate and a reflux device while purging nitrogen to completely dissolve the composition. After that, the mixture was cooled at 25 ° C. for 1 hour. The resulting solution was filtered using filter paper. 100 mL of the filtered filtrate was collected, transferred to an aluminum cup or the like, evaporated to dryness at 140 ° C. while purging with nitrogen, and allowed to stand at room temperature for 30 minutes to obtain a xylene-soluble component (XS).

[XSIV]
Using the above xylene-soluble component as a sample, the ultimate viscosity (IV) was measured in tetrahydronaphthalene at 135 ° C. using an Ubbelohde viscometer (SS-780-H1, manufactured by Shibayama Kagaku Kikai Seisakusho).
However, since the ethylene homopolymer of the component (2) of the masterbatch composition of Comparative Example 4 contains almost no component soluble in xylene, the component (2) estimated from the ethylene content of the masterbatch composition The IV of the component (2) was calculated from the ratio, the IV of the entire masterbatch composition, and the IV value of the component (1), assuming the additivity of IV.

[Collection of xylene insoluble matter]
When the xylene-soluble component was filtered as described above, acetone was added to the residue (mixture of xylene-insoluble component and solvent) remaining on the filter paper and filtered, and then the unfiltered component was vacuumed at 80 ° C. It was evaporated to dryness in a drying oven to obtain xylene insoluble matter (XI).
[Mw and Mw / Mn of xylene insoluble matter]
Using the above xylene insoluble component as a sample, the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were measured as follows.
PL GPC220 manufactured by Polymer Laboratories is used as an apparatus, 1,2,4-trichlorobenzene containing an antioxidant is used as a mobile phase, and UT-G (1) and UT-807 (1) manufactured by Showa Denko KK as columns. One) and UT-806M (two) were connected in series, and a differential refractometer was used as a detector. The same solvent as the mobile phase was used as the solvent for the xylene-insoluble sample solution, and the sample was dissolved at a sample concentration of 1 mg / mL for 2 hours while shaking at a temperature of 150 ° C. to prepare a measurement sample. 500 μL of the sample solution thus obtained was injected into the column, and measurements were taken at a flow rate of 1.0 mL / min, a temperature of 145 ° C., and a data acquisition interval of 1 second. A polystyrene standard sample having a molecular weight of 580 to 7.45 million (shodex STANDARD, manufactured by Showa Denko KK) was used for column calibration, and the column was calibrated by a cubic approximation. The coefficients of Mark-Hokins are K = 1.21 × 10 ^-4 , α = 0.707 for polystyrene standard samples, and K = 1.37 × 10 ^-4 , α = 0. For polypropylene-based polymers. 75 was used.

[Flexural modulus]
A bending test was performed at room temperature (23 ° C.) according to JIS K6921-2. The measurement was performed at a crosshead speed of 2 mm / min.

[Charpy impact strength]
A test piece (80 (length) x 10 (width) x 4 (thickness) mm ³ ) obtained by cutting the obtained polypropylene resin molded body (test piece for evaluation of physical properties) was subjected to ISO179-1 and 23 ° C. The Charpy impact strength at −30 ° C. was measured.

[Coefficient of linear expansion]
The central portion (width 10 mm) of the obtained polypropylene resin molded product (test piece for evaluation of physical properties, thickness 4 mm) was cut out to a length of 10 mm along the resin flow direction (MD), and placed in an oven at 80 ° C. for 24 hours. The left-standing sample was used for measurement in accordance with JIS K7197.
<Test equipment> ULVAC MTS9000 (manufactured by Vacuum Riko)
<Test conditions> Temperature rise rate: 5 ° C / min
Load: 5.0 g weight
Measurement temperature: -30 ° C to 80 ° C

It is clear that the masterbatch composition of the present invention has a low coefficient of linear expansion, high rigidity, and high impact resistance. Furthermore, it is clear that the polypropylene resin composition produced by using the masterbatch composition also has a low coefficient of linear expansion, high rigidity, and high impact resistance.

Claims (7)

(A) A solid catalyst containing an electron donor compound selected from magnesium, titanium, halogen, and succinate compounds as an essential component;
A masterbatch composition obtained by polymerizing propylene and ethylene using a catalyst containing (B) an organoaluminum compound and (C) an external electron donor compound.
The component (1) contains a propylene homopolymer, and the component (2) contains a propylene-ethylene copolymer containing 55 to 80% by weight of ethylene-derived units.
The weight ratio of the components (1): (2) is 75 to 60:25 to 40 .
The following requirements:
1) Mw / Mn of the xylene-insoluble component of the composition measured by GPC is 6 to 20. 2) The ultimate viscosity of the xylene-soluble component of the composition is 1 to 3 dl / g. 3) The composition. A masterbatch composition that satisfies a melt flow rate (230 ° C., load 21.18 N) of 1 to 50 g / 10 min. The masterbatch composition according to claim 1, wherein the ethylene-derived unit of the propylene-ethylene copolymer in the component (2) is 60 to 75% by weight. The masterbatch composition according to claim 1 or 2 , wherein the melt flow rate is 10 to 35 g / 10 minutes. The masterbatch composition according to any one of claims 1 to 3 , which contains 0.01 to 5 parts by weight of a crystal nucleating agent with respect to 100 parts by weight of the composition. The masterbatch composition according to any one of claims 1 to 4 is mixed with at least one of an elastomer different from the component (2) of the masterbatch composition or a polypropylene resin different from the masterbatch composition. A polypropylene resin composition. A polypropylene resin composition containing a filler of more than 5% by weight and 40% by weight or less in the composition according to claim 5 . An injection-molded product obtained by injection-molding the polypropylene resin composition according to claim 5 or 6 .