WO2018092805A1 - Master batch composition and polypropylene resin composition containing same - Google Patents

Abstract

A master batch composition which is obtained by polymerizing propylene and ethylene with use of (A) a solid catalyst that contains, as essential components, magnesium, titanium, a halogen and an electron donor compound selected from among succinate compounds, (B) an organic aluminum compound and (C) a catalyst that contains an external electron donor compound, and which is configured such that: a propylene homopolymer is contained as a component (1) and a propylene-ethylene copolymer containing 55-80% by weight of a unit derived from ethylene is contained as a component (2); the weight ratio of the component (1) to the component (2) is 85-60:15-40; and the requirements (1)-(3) described below are satisfied. This composition has high elastic modulus, high impact strength at low temperatures and low linear expansion coefficient. Requirement (1): The xylene-insoluble fraction of this composition has an Mw/Mn of 6-20 as determined by GPC. Requirement (2): The xylene-soluble fraction of this composition has a limiting viscosity of 1-3 dl/g. Requirement (3): This composition has a melt flow rate of 1-50 g/10 minutes (at 230°C under a load of 21.18 N).

Description

Masterbatch composition and polypropylene resin composition containing the same

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

Polypropylene is widely used for automotive applications because it is inexpensive and has excellent physical properties. However, since polypropylene has an amorphous component, it is known that the coefficient of linear expansion is large. Therefore, there has been a problem in automobile parts such as a gap formed at the joint between the polypropylene resin and another material. Attempts have been made to add a large amount of an inorganic filler such as talc for the purpose of reducing the linear expansion coefficient, but this leads to an increase in weight, which is not preferable from the viewpoint of improving fuel consumption by reducing the weight of an 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) _A wide molecular weight distribution with an IV _s / IV _A ratio of 2 to 2.5, (A) a polydispersity index of 5 to 15 and a melt flow rate of 80 to 200 g / 10 min (according to ASTM-D1238, condition L) A polyolefin composition comprising 40-60% of a propylene polymer (component A) and (B) 40-60% of a partially xylene-insoluble olefin polymer rubber (component B) comprising at least 65% by weight of ethylene. Proposed. The composition is said to have a low coefficient of linear expansion.

Special Table 2002-528621

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

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

A composition having a high elastic modulus, a high impact strength at a low temperature, and a low linear expansion coefficient can be provided.

In the present invention, a composition containing components (1) and (2) as essential components and, if necessary, 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 “masterbatch composition” and at least one of an elastomer or a polypropylene-based resin different from the masterbatch composition and, if necessary, a filler is referred to as “polypropylene resin composition”. Hereinafter, the present invention will be described in detail. In the present invention, “X to Y” includes X and Y which are their end values. “X or Y” means either X or Y, or both.

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

(1) Component (1): Propylene Homopolymer As component (1) of the present invention, a propylene homopolymer (homopolypropylene) is used in order to satisfy the requirements of rigidity and heat resistance in the final product. The propylene homopolymer of the present invention is not more than 2.0% by weight, preferably not more than 1.0% by weight, to the extent that the gist of the invention is not impaired due to the presence of recycled monomers in the production process or the incorporation of transition products. A small amount of ethylene or one or more C4 to C10-α-olefin derived units may be included.

(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. A linear expansion coefficient increases that content of an ethylene origin unit is less than a lower limit. If the upper limit is exceeded, the linear expansion coefficient increases and the impact strength also decreases. Further, in the production, particularly when the content of the ethylene-derived unit is about 55% by weight, if the ratio of the component (2) is attempted to be 25 parts by weight or more, the polymer particles are easily bonded 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. When the amount of the component (2) exceeds this upper limit, the rigidity is remarkably reduced, and when it is less than the lower limit, the impact resistance is remarkably reduced. From this viewpoint, the ratio is preferably 75 to 60:25 to 40.

(4) Other components Further, the masterbatch composition includes an antioxidant, a chlorine absorbent, a heat stabilizer, a light stabilizer, an ultraviolet absorbent, an internal lubricant, an external lubricant, an antiblocking agent, an antistatic agent, and an antifogging agent. Olefin Polymers such as Agents, Crystal Nucleating Agents, Flame Retardants, Dispersants, Copper Damage Inhibitors, Neutralizers, Plasticizers, Anti-Bubbling Agents, Crosslinkers, Peroxides, Oils and Other Organic and Inorganic Pigments Conventional additives that are usually used may be added. The addition amount of each additive may be a known amount.

The master batch 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 inorganic fillers having crystal nucleating action such as talc, and organic crystal nucleating agents such as ertel phosphate, metal carboxylate, benzylidene sorbitol, and triaminobenzene derivatives. 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) Mw / Mn of XI
Mw / Mn measured by GPC of xylene insoluble matter (XI) of the composition is 6-20. Xylene insoluble matter 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 these components promote the orientation of polymer chains during molding. For this reason, a low linear expansion coefficient can be achieved. Furthermore, the high molecular weight component improves impact resistance, particularly impact resistance at low temperatures. From this viewpoint, Mw / Mn is preferably 7 to 20. Mw / Mn of XI is obtained by obtaining a component insoluble in xylene at 25 ° C. and measuring the component by GPC (gel permeation chromatography) method.

2) XSIV
The intrinsic viscosity (XSIV) of the xylene-soluble component (XS) of the composition is also an indicator of the molecular weight of the component having no crystallinity in the composition. XSIV is obtained by obtaining a component soluble in xylene at 25 ° C. and measuring the intrinsic viscosity of the component by a conventional method. In the present invention, XSIV is relatively low at 1 to 3 dl / g. The low XSIV is easy to stretch the component (2) in the injection-molded product, which is advantageous for achieving a low linear expansion coefficient. However, if it is too low, the impact resistance deteriorates. Therefore, it is considered that the low linear expansion coefficient and the high impact resistance can be achieved when XSIV is within this range. From this viewpoint, the intrinsic viscosity is preferably 1.5 to 2.5 dl / g.

3) Melt flow rate The melt flow rate (hereinafter also referred to as “MFR”) at 230 ° C. and a load of 21.18 N of the master batch composition is 1 to 50 g / 10 min. When the MFR is within this range, excellent moldability can be achieved. If the MFR exceeds the upper limit value, the MFR of the component (1) becomes very high (molecular weight is low), resulting in reduced impact resistance and difficulty in production. On the other hand, if the MFR value is less than the lower limit, the MFR of the polypropylene resin composition using the masterbatch composition is lowered, and molding such as injection molding becomes difficult. From this viewpoint, the melt flow rate is preferably 5 to 35 g / 10 min.

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

5) Linear Expansion Coefficient The master batch composition of the present invention preferably has a linear expansion coefficient in the MD direction of −30 to 80 ° C. of 60 to 80 × 10 ⁻⁶ / K, and 65 to 78 × 10 ^−6. / K is preferable. The linear expansion coefficient can be measured by performing thermal mechanical analysis (TMA) after annealing the molded product.

6) Impact strength The master batch composition of the present invention preferably has a Charpy impact strength at room temperature of 20 to 50 kJ / m ² and a Charpy impact strength at a low temperature (−30 ° C.) of 3 to 6 kJ / m ^2. It is preferable that

(6) Production method The masterbatch composition of the present invention contains the raw material monomer of component (1) and the raw material monomer of component (2), and (A) magnesium, titanium, halogen, and a succinate compound as an internal electron donor. And (B) an organoaluminum compound, and (C) a catalyst comprising a catalyst containing 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 a high molecular weight component and a 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 blend or pellet blend, or by increasing the number of steps in multi-stage polymerization, a polymer having a molecular weight distribution (measured value) similar to that of the present invention at first glance is obtained. It is also possible to obtain. However, the polymer obtained in this way and the polymer of the present invention differ in the degree of dispersion of the high molecular weight component and the low molecular weight component, and the present invention achieves a uniform degree of dispersion. The difference is remarkable in performances such as a low linear expansion coefficient and high impact resistance.

1) Solid catalyst (component A)
Component (A) can be prepared by a known method, for example, by bringing a magnesium compound, a titanium compound and an electron donor compound into contact with each other.

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 preferable. In the formula, R is a hydrocarbon group, X is a halogen, and 0 ≦ g ≦ 4. More specifically, titanium compounds include titanium halides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , and Ti (O _n —C ₄ H). _{9) Cl 3, Ti (OC} 2 H 5) Br 3, Ti (OisoC 4 H 9) trihalide, alkoxy titanium such as _{Br 3; Ti (OCH 3)} 2 Cl 2, Ti (OC 2 H 5) 2 Cl ₂ , dihalogenated alkoxytitanium such as Ti (O _n —C ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ 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 ) ₃ Br and other monohalogenated trialkoxytitanium; Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , tetraalkoxytitanium such as Ti (O _n —C ₄ H ₉ ) ₄ and the like. Among these, preferred are halogen-containing titanium compounds, particularly titanium tetrahalides, and more particularly preferred is titanium tetrachloride.

Magnesium compounds used for the preparation of component (A) include magnesium compounds having a magnesium-carbon bond or magnesium-hydrogen bond, such as dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, di- Examples include decylmagnesium, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butylethoxymagnesium, ethylbutylmagnesium, butylmagnesium hydride and the like. These magnesium compounds can also be used, for example, in the form of a complex compound with organic aluminum or the like, and may be liquid or solid. Further preferred magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, and the like. Alkoxymagnesium halides; allyloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium; phenoxy Allyloxy Magnesium like Magnesium, Dimethylphenoxy Magnesium ; Magnesium laurate, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

The electron donor compound used for the preparation of the component (A) is generally referred to as “internal electron donor”. In the present invention, it is preferable to use an internal electron donor that gives a broad molecular weight distribution. In general, it is known that the molecular weight distribution can be increased by performing polymerization in multiple stages, 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, the molecular weight distribution can be increased even when the molecular weight of XI is low. A composition polymerized using the catalyst is a composition having the same molecular weight distribution obtained by pelletizing or powder blending a polymer polymerized using another catalyst, and a composition having the same molecular weight distribution by multistage polymerization. Excellent fluidity and large swell compared to products. This is because the composition produced using the catalyst is united in a state where the high molecular weight component and the low molecular weight component are close to the molecular level, but the latter resin composition does not mix in the state close to the molecular level. This is thought to be due to the apparent molecular weight distribution. Hereinafter, preferred internal electron donors will be described.

In the present invention, a succinate compound is used as an internal electron donor. In the present invention, the succinate compound means a diester of succinic acid or a substituted succinic acid. Hereinafter, the succinate compound will be described in detail. The succinate compound preferably used in the present invention is represented by the following formula (I).

In which the radicals R ₁ and R ₂ are the same or different from one another and optionally contain heteroatoms, C ₁ -C ₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkyl An aryl group; the groups R ₃ to R ₆ are the same or different from each other and are hydrogen or, optionally, a heteroatom, a C ₁ to C ₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl, The groups R ₃ to R ₆ which are arylalkyl or alkylaryl groups and are bonded to the same carbon atom 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. Particularly preferred are compounds wherein R ₁ and R ₂ are selected from primary alkyls, especially branched primary alkyls. Examples of suitable R ₁ and R ₂ groups are C ₁ -C ₈ alkyl groups such as methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Ethyl, isobutyl, and neopentyl are particularly preferred.

One preferred group of compounds represented by formula (I) is a branched alkyl, cycloalkyl, aryl, arylalkyl, wherein R ₃ to R ₅ are hydrogen and R ₆ has 3 to 10 carbon atoms And an alkylaryl group. Preferred examples of such mono-substituted succinate compounds include diethyl-sec-butyl succinate, diethyl hexyl succinate, diethyl cyclopropyl succinate, diethyl norbornyl succinate, diethyl perihydrosuccinate, 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 isopenty Succinate, diethyl (1-trifluoromethylethyl) succinate, diethyl fluorenyl succinate, 1-ethoxycarbodiisobutylphenyl succinate, diisobutyl-sec-butyl succinate, diisobutyl hexyl succinate, diisobutylcyclopropyl succinate , Diisobutyl norbornyl succinate, diisobutyl perhydrosuccinate, diisobutyl trimethylsilyl succinate, diisobutyl methoxy succinate, diisobutyl-p-methoxyphenyl succinate, diisobutyl-p-chlorophenyl succinate, diisobutyl cyclohexyls Succinate, diisobutylbenzyl succinate, diisobutylcyclohexylmethyl succinate, diisobutyl-t-butylsuccine Diisobutyl isobutyl succinate, diisobutyl isopropyl succinate, diisobutyl neopentyl succinate, diisobutyl isopentyl succinate, diisobutyl (1-trifluoromethylethyl) succinate, diisobutyl fluorenyl succinate, dineopentyl-sec- Butyl succinate, dineopentyl texyl succinate, dineopentyl cyclopropyl succinate, dineopentyl norbornyl succinate, dineopentyl perhydrosuccinate, dineopentyltrimethylsilyl succinate Pentylmethoxy succinate, dineopentyl-p-methoxyphenyl succinate, dineopentyl-p-chlorophenyl succinate, dineopentylphenyl succinate, cine Opentyl cyclohexyl succinate, dineopentyl benzyl succinate, dineopentyl cyclohexyl methyl 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 scope of formula (I) are C ₁ -C ₂₀ linear, wherein at least two groups from R ₃ to R ₆ are different from hydrogen and optionally contain heteroatoms Or a branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl group. Particularly preferred are compounds in which two groups different from hydrogen are bonded to the same carbon atom. Specifically, R ₃ and R ₄ are different from hydrogen, and R ₅ and R ₆ are hydrogen atoms. Preferred 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 , 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- Sobutyl succinate, diethyl-2-phenyl-2-n-butyl succinate, diisobutyl-2,2-dimethyl succinate, diisobutyl-2-ethyl-2-methyl succinate, diisobutyl-2-benzyl- 2-isopropyl succinate, diisobutyl-2-cyclohexylmethyl-2-isobutyl succinate, diisobutyl-2-cyclopentyl-2-n-butyl succinate, diisobutyl-2,2-diisobutyl succinate, diisobutyl-2 -Cyclohexyl-2-ethyl succinate, diisobutyl-2-isopropyl-2-methyl succinate, diisobutyl-2-tetradecyl-2-ethyl succinate, diisobutyl-2-isobutyl-2-ethyl succinate, diisobutyl -2- (1-trifluoro Tilethyl) -2-methyl succinate, diisobutyl-2-isopentyl-2-isobutyl succinate, diisobutyl-2-phenyl-2-n-butyl succinate, dineopentyl-2,2-dimethyl succinate, dineopentyl -2-Ethyl-2-methyl succinate, dineopentyl-2-benzyl-2-isopropyl succinate, 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-methyl succinate, dineopentyl-2-tetradecyl-2-ethyl succinate , Dineopentyl-2-isobutyl-2-ethylsuccinate, dineopentyl-2- (1-trifluoromethylethyl) -2-methylsuccinate, dineopentyl-2-isopentyl-2-isobutylsuccinate, dineopentyl -2-Phenyl-2-n-butyl succinate.

Furthermore, compounds in which at least two groups different from hydrogen are bonded to different carbon atoms are particularly preferred. Specifically, it is a compound in which R ₃ and R ₅ are groups different from hydrogen. In this case, R ₄ and R ₆ may be a hydrogen atom or a group different from hydrogen, but it is preferable that either one is a hydrogen atom (trisubstituted succinate). Preferred 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-butylsuccinate, diethyl-2,3-diisobuty Succinate, diethyl-2,3-dineopentyl succinate, diethyl-2,3-diisopentyl 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-iso Ropil succinate, diisobutyl-2,3-diisopropyl-2-methyl succinate, diisobutyl-2,3-dicyclohexyl-2-methyl succinate, diisobutyl-2,3-dibenzyl succinate, diisobutyl-2 , 3-diisopropyl succinate, 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- 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-methyl succinate, dineopentyl-2- (3,3,3-trifluoropropyl) -3-methyl succinate, dineopentyl-2,3-bis (2-ethylbutyl) succinate, cine Pentyl-2,3-diethyl-2-isopropyl succinate, dineopentyl-2,3-diisopropyl-2-methyl succinate, dineopentyl-2,3-dicyclohexyl-2-methyl succinate, dineopentyl-2,3 Dibenzyl succinate, dineopentyl-2,3-diisopropyl succinate, dineopentyl-2,3-bis (cyclohexylmethyl) succinate, dineopentyl-2,3-di-t-butyl succinate, dineopentyl-2, 3-diisobutyl succinate, dineopentyl-2,3-dineopentyl succinate, dineopentyl-2,3-diisopentyl succinate, dineopentyl-2,3- (1-trifluoromethylethyl) succinate, dineopentyl -2,3-tetradeci Succinate, dineopentyl-2,3-fluorenyl succinate, dineopentyl-2-isopropyl-3-isobutyl succinate, dineopentyl-2-tert-butyl-3-isopropyl succinate, dineopentyl-2-isopropyl-3- They are cyclohexyl succinate, dineopentyl-2-isopentyl-3-cyclohexyl succinate, dineopentyl-2-tetradecyl-3-cyclohexyl methyl succinate, and dineopentyl-2-cyclohexyl-3-cyclopentyl succinate.

Of the compounds of formula (I), compounds in which some of the groups R ₃ to R ₆ are bonded together to form a ring can also be preferably used. As such compounds, compounds listed in JP-T-2002-542347, for example, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2,6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1- ( Ethoxyacetyl) -2,5-monodimethylcyclopentane, 1- (ethoxycarbonyl) -1- (ethoxyacetylmethyl) -2 monomethylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxy (cyclohexyl) acetyl) cyclohexane Can be mentioned. In addition, for example, cyclic succinate compounds such as diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate and diisobutyl cyclohexane-1,2-dicarboxylate as disclosed in WO2009 / 069483 are also suitable. Can be used. As another example of the cyclic succinate compound, a compound disclosed in International Publication No. 2009/057747 is also preferable.

Of the compounds of formula (I), when the groups R ₃ to R ₆ contain heteroatoms, the heteroatoms may be group 15 atoms including nitrogen and phosphorus atoms or group 16 atoms including oxygen and sulfur atoms preferable. Examples of the compound in which the groups R ₃ to R ₆ 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 R ₃ to R ₆ contain a Group 16 atom include compounds disclosed in JP-A No. 2004-131537.

In addition, an internal electron donor that gives a molecular weight distribution equivalent to that of the succinate compound may be used in combination. Examples of such internal electron donors include diphenyl dicarboxylic acid esters described in JP 2013-28704 A, cyclohexene dicarboxylic acid esters described in JP 2014-201602 A, and JP 2013-28705 A. And didiol dibenzoate described in Japanese Patent No. 4959920, and 1,2-phenylene dibenzoate described in WO 2010/078494.

2) Organoaluminum compound (component B)
The following are mentioned as an organoaluminum compound of a component (B).
Trialkylaluminum such as triethylaluminum, tributylaluminum;
Trialkenyl aluminum such as triisoprenyl aluminum:
Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
Partially halogenated alkylaluminums such as alkylaluminum dihalogenides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide and the like;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide.

3) Electron donor compound (component C)
The electron donor compound of component (C) is generally referred to as an “external electron donor”. Such an electron donor compound is preferably an organosilicon compound. The following is mentioned as a preferable organosilicon compound.
Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyl Dimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bism-tolyldimethoxysilane, bisp-tolyldimethoxysilane, bisp-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxy Silane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyl Riethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyl Triethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, texyltrimethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chloro Triethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxy Lan, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, Dimethyltetraethoxydisiloxane.

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 (perhydroisoquinoline 2- Yl) dimethoxysilane, bis (decahydroisoquinolin-2-yl) dimethoxysilane, tri (isopropenyloxy) phenylsilane, texyltrimethoxysilane, vinyltriethoxysilane, phenyltri Toxisilane, phenyltrimethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, i-butyli-propyldimethoxysilane, cyclopentyl t-butoxydimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, Cyclohexyl i-butyldimethoxysilane, cyclopentyl i-butyldimethoxysilane, cyclopentylisopropyldimethoxysilane, di-sec-butyldimethoxysilane, diethylaminotriethoxysilane, tetraethoxysilane, tetramethoxysilane, isobutyltriethoxysilane, phenylmethyldimethoxysilane, Phenyltriethoxylane, bis p-tolyldimeth Sisilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyldiethoxysilane, methyl (3,3,3-trifluoropropyl) dimethoxy Silane and ethyl silicate are preferred.

4) Polymerization Polymerization is performed by bringing the raw material monomer into contact with the catalyst prepared as described above. At this time, it is preferable to first perform prepolymerization using the catalyst. Preliminary polymerization is a step of forming a polymer chain as a foothold for subsequent polymerization of raw material monomers on a solid catalyst component. The prepolymerization can be performed by a known method. The prepolymerization is usually performed at 40 ° C or lower, preferably 30 ° C or lower, more preferably 20 ° C or lower.

Next, the prepolymerized catalyst is introduced into the polymerization reaction system to perform main polymerization of the raw material monomers. In the main polymerization, the raw material monomer of component (1) and the raw material monomer of component (2) are preferably polymerized using two or more reactors. The polymerization may be carried out in liquid phase, gas phase or liquid-gas phase. The polymerization temperature is preferably from room temperature to 150 ° C, more preferably from 40 ° C to 100 ° C. The polymerization pressure is preferably in the range of 3.3 to 6.0 MPa when carried out in the liquid phase, and in the range of 0.5 to 3.0 MPa when carried out in the gas phase. Conventional molecular weight regulators known in the art such as chain transfer agents (eg, hydrogen or ZnEt ₂ ) may be used.

Also, a polymerization vessel having a gradient of monomer concentration and polymerization conditions may be used. In such a polymerization vessel, for example, a monomer in which at least two polymerization regions are connected can be used, and the monomer can be polymerized by gas phase polymerization. Specifically, in the presence of a catalyst, a monomer is supplied and polymerized in a polymerization region including a riser, and a monomer is supplied and polymerized in a downcomer connected to the riser. The polymer product is recovered while circulating. This method comprises means for completely or partially preventing the gas mixture present in the riser from entering the downcomer. Also, a gas and / or liquid mixture having a different composition from the gas mixture present in the riser is introduced into the downcomer. As the above polymerization method, for example, the method described in JP-T-2002-520426 can be applied.

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

(1) Elastomer An elastomer is a polymer having elasticity and is added mainly 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 polymer of component (1) and component (2). For example, preferably the density of the elastomer is non but 0.850 ~ 0.890g / cm ³ limited, and 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 JP-A-2015-113363. The MFR of the elastomer is preferably 0.1 to 50 g / 10 min at 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 resins different from the masterbatch composition include propylene homopolymers, propylene random copolymers containing more than 0% by weight and less than 5% by weight of ethylene or one or more C4-C10-α-olefins, propylene Examples thereof include a polymerization mixture (also referred to as HECO) obtained by polymerizing ethylene and one or more C3-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 both 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 fillers and preparation of a masterbatch of filler and resin may be performed as necessary. Among the fillers, talc is preferable because it is easily mixed with a propylene (co) polymer and a copolymer of ethylene and α-olefin, and the rigidity of the molded product is easily improved. The amount of the filler is preferably more than 5% by weight and 40% by weight or less in the polypropylene resin composition, and more preferably 10 to 35% by weight.

(4) Other components The polypropylene resin composition of the present invention includes an antioxidant, a chlorine absorbent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an internal lubricant, an external lubricant, an antiblocking agent, an antistatic agent, Olefins such as antifogging agents, crystal nucleating agents, flame retardants, dispersants, copper damage prevention agents, neutralizing agents, plasticizers, antifoaming agents, crosslinking agents, peroxides, oil-extended and other organic and inorganic pigments You may add the usual additive normally used for a polymer. The addition amount of each additive may be a known amount.

(5) 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 preferred. 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 measuring a dry blend of the above components in an injection molding machine and kneading in a melt kneading part (cylinder). Thus, 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 is such that the propylene-ethylene copolymer component derived from the masterbatch composition and an elastomer (in some cases the masterbatch composition and Is considered to be a structure in which a copolymer of ethylene and α-olefin derived from different HECOs is dispersed, and the effect of the present invention is exhibited by forming the phase structure.

(6) Injection molding The masterbatch composition and the polypropylene resin composition of the present invention are suitable for injection molding. Since the polypropylene resin composition of the present invention has high rigidity, high impact resistance, and a low linear expansion coefficient, it is 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 / second.

1. Masterbatch composition [Example 1]
A masterbatch composition comprising 65.5% by weight of a polypropylene homopolymer as component (1) and 34.5% by weight of a propylene-ethylene copolymer having 65.7% by weight of ethylene-derived units as component (2) as follows: The thing was manufactured.

A solid catalyst component was prepared according to the preparation method described in Examples of JP2011-500907A. Specifically, it was prepared as follows.

In a 500 mL 4-neck round bottom flask purged with nitrogen, 250 mL of TiCl ₄ was introduced at 0 ° C. While stirring, 10.0 g of fine spherical MgCl ₂ .1.8C ₂ H ₅ OH (produced according to the method described in Example 2 of US Pat. No. 4,399,054, but operated at 3000 rpm instead of 10000 rpm) ) And 9.1 mmol of diethyl-2,3- (diisopropyl) succinate was added. The temperature was raised to 100 ° C. and held for 120 minutes. Next, stirring was stopped, the solid product was allowed to settle, and the supernatant liquid was siphoned off. The following procedure was then repeated twice: 250 mL of fresh TiCl ₄ was added and the mixture was allowed to react at 120 ° C. for 60 minutes and the supernatant was siphoned off. The solid was washed 6 times with anhydrous hexane (6 × 100 mL) at 60 ° C.

The solid catalyst, triethylaluminum (TEAL) and dicyclopentyldimethoxysilane (DCPMS) are mixed in an amount such that the weight ratio of TEAL to the solid catalyst is 18 and the weight ratio of TEAL / DCPMS is 10 at room temperature. Touched for a minute. The resulting catalyst system was prepolymerized by holding it in liquid propylene in suspension for 5 minutes at 20 ° C.

The obtained prepolymer is introduced into a first-stage liquid phase polymerization reactor to obtain a propylene homopolymer, and then the obtained polymer is introduced into a second-stage gas phase polymerization reactor. The polymer (propylene-ethylene copolymer) was polymerized. During the polymerization, temperature and pressure were adjusted, and hydrogen was used as a molecular weight modifier. The polymerization temperature and the ratio of the reactants are as follows: polymerization temperature and hydrogen concentration in the first reactor are 70 ° C. and 0.31 mol%, respectively, polymerization temperature, H2 / C2, C2 / C in the second reactor. (C2 + C3) were 80 ° C., 0.16 molar ratio, and 0.69 molar ratio, respectively. Moreover, the residence time distribution of the 1st stage and the 2nd stage was adjusted so that the quantity of a copolymer component might be 34.5 weight part in 100 weight part of polymers.

To 100 parts by weight of the obtained polypropylene polymer, 0.2 parts by weight of BASF B225 as an antioxidant, 0.05 parts by weight of calcium stearate manufactured by Tamnan Chemical Co., Ltd. as a neutralizer, After stirring and mixing with a Henschel mixer for 1 minute, the mixture was melt-kneaded at a cylinder temperature of 200 ° C. and extruded using a twin screw extruder (manufactured by Technobell, model number KZW15TW-30MG) with a screw diameter of 15 mm. The strand was cooled in water and then cut with a pelletizer to obtain a pellet. Next, the pellets were 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 / second. Various physical properties were evaluated using the test pieces. The evaluation method will be described later.

[Example 2]
The hydrogen concentration in the first reactor is 0.28 mol%, and H2 / C2 and C2 / (C2 + C3) in the second reactor are 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 distribution in the first and second stages was adjusted so that the amount of the component was 32.9 parts by weight in 100 parts by weight of the polymer. A masterbatch composition for this example was produced and evaluated in the same manner as in Example 1 using the polypropylene polymer.

[Example 3]
Pellets were prepared 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, and evaluated. The amount of talc (trade name HTP05L, manufactured by IMI Fabi) was 1 part by weight per 100 parts by weight of the polymer.

[Comparative Example 1]
A solid catalyst in which Ti and diisobutyl phthalate 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 above solid catalyst, triethylaluminum (TEAL) as the organoaluminum compound and dicyclopentyldimethoxysilane (DCPMS) as the external electron donor compound, the weight ratio of TEAL to the solid catalyst is 20, and the weight ratio of TEAL / DCPMS. Was contacted at 12 ° C. for 24 minutes. The resulting catalyst system was preliminarily polymerized by keeping it in suspension in liquid propylene at 20 ° C. for 5 minutes.

Using the resulting prepolymer, a propylene homopolymer was produced by multistage polymerization using two liquid phase polymerization reactors. The hydrogen concentration in the first polymerization reactor was 0.16 mol%, the hydrogen concentration in the second polymerization reactor was 1.70 mol%, the polymerization pressure was adjusted at a polymerization temperature of 70 ° C., and the respective ratios The residence time distribution was adjusted so as to be 50:50.

Subsequently, the obtained propylene homopolymer was introduced into a gas phase polymerization reactor, and a copolymer (propylene / ethylene copolymer) was polymerized in the same manner as in Example 1. During the polymerization, 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 in the first and second stages were adjusted so that the amount of the copolymer component was 30.0 parts by weight per 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 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, and evaluated. The amount of talc (trade name HTP05L, manufactured by IMI Fabi) was 1 part by weight per 100 parts by weight of the polymer.

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

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

[Comparative Example 5]
The hydrogen concentration in the first-stage reactor was 0.34 mol%, the hydrogen concentration in the second-stage reactor, and C2 / (C2 + C3) were 4.13 mol% and 0.19 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 polymer became 31.5 parts by weight in 100 parts by weight of the polymer. A comparative masterbatch composition was produced and evaluated in the same manner as in Example 1 using the polypropylene polymer thus obtained.

[Comparative Example 6]
Using the prepolymerization catalyst of Comparative Example 1, the hydrogen concentration in the first liquid phase polymerization reactor was 0.73 mol%, the hydrogen concentration in the second liquid phase polymerization reactor was 3.46 mol%, The H2 / C2 and C2 / (C2 + C3) of the phase polymerization reactor are 0.12 molar ratio and 0.68 molar ratio, respectively, and the amount of the copolymer component is 49.0 parts by weight in 100 parts by weight of the polymer. Thus, the polypropylene polymer was manufactured by adjusting the residence time distribution of the liquid phase reactor and the gas phase reactor. A comparative masterbatch composition was produced and evaluated in the same manner as in Example 1 using the polypropylene polymer thus obtained.

[Comparative Example 7]
The liquid phase reactor and the gas phase reactor are adjusted so that the hydrogen concentration in 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. A comparative masterbatch composition was produced and evaluated in the same manner as in Example 1 using the polypropylene polymer thus obtained.

The results are shown in Table 1.

2. Polypropylene resin composition [Example 4]
The residence time distribution of the first and second stages is adjusted so that the hydrogen concentration in the first stage reactor is 0.59 mol% and the amount of the copolymer component is 30.7 parts by weight per 100 parts by weight of the polymer. A polypropylene polymer was produced in the same manner as in Example 1 except that. Next, a master batch composition was produced in the same manner as in Example 1 using this polypropylene polymer. The master batch composition, talc (trade name HTP05L, manufactured by IMI Fabi) and elastomer (trade name Engage 8200, manufactured by Dow Chemical) were melt-kneaded in the same manner as in Example 1 to prepare pellets. Subsequently, the polypropylene resin composition was evaluated in the same manner as in Example 1.

[Example 5]
The hydrogen concentration in the first-stage reactor is 0.59 mol%, and H2 / C2 and C2 / (C2 + C3) in the second-stage reactor are 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 distribution in the first and second stages was adjusted so that the amount of the component was 29.5 parts by weight in 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.

[Example 6]
The hydrogen concentration in the first reactor is 0.59 mol%, and the H2 / C2 and C2 / (C2 + C3) in the second reactor are 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 distribution in the first and second stages was adjusted so that the amount of the component was 32.3 parts by weight in 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 master batch composition and the content of talc were changed as shown in Table 2.

[Example 7]
The residence time distributions in the first and second stages were adjusted so that the hydrogen concentration in the first stage reactor 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 and MFR of 1750 g / 10 minutes, and a propylene homopolymer having a xylene-soluble content of 2.3 wt% at 25 ° C. 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 that.

[Comparative Example 8]
Using the prepolymerization catalyst of Comparative Example 1, the hydrogen concentration in the first liquid phase polymerization reactor was 0.68 mol%, the hydrogen concentration in the second liquid phase polymerization reactor was 3.46 mol%, The H2 / C2 and C2 / (C2 + C3) in the phase polymerization reactor are 0.08 molar ratio and 0.68 molar ratio, respectively, and the amount of the copolymer component is 26.8 parts by weight per 100 parts by weight of the polymer. Thus, the polypropylene polymer was manufactured by adjusting the residence time distribution of the liquid phase reactor and the gas phase reactor. Next, a comparative polypropylene resin composition was produced and evaluated in the same manner as in Example 4 using this polypropylene polymer.

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

[Comparative Example 10]
The liquid phase reactor and the gas phase reaction are adjusted so that the hydrogen concentration in the first liquid phase polymerization reactor is 0.42 mol% and 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 polymer obtained by adjusting the residence time distribution of the vessel was used. Then, using this polypropylene polymer, a comparative polypropylene resin assembly composition was prepared in the same manner as in Example 4 except that the blending amount of the masterbatch composition and talc was changed to the same amount as in Example 6 shown in Table 2. Manufactured and evaluated.

The results are shown in Table 2.

3. Evaluation method [MFR]
According to JIS K 7210, the measurement was performed under the conditions of 230 ° C. and a load of 21.18 N.

[Ethylene concentration in copolymer and amount of copolymer in masterbatch composition]
A sample dissolved in a mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene was measured using a Bruker AVANCE III HD400 ( ¹³ C resonance frequency 100 MHz) at a measurement temperature of 120 ° C., a flip angle of 45 degrees, and a pulse interval of 7 A ¹³ C-NMR spectrum was obtained under the conditions of a second, a sample rotation number of 20 Hz, and an integration number of 5,000.

<Total ethylene content in masterbatch composition>
Using the spectrum obtained above, the total ethylene of the masterbatch composition was obtained 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 calculating in the same manner as the total ethylene amount, except that the integrated strength obtained by the following formula was used instead of the integrated strength of Tββ obtained above.
T′ββ = 0.98 × Sαγ × A / (1−0.98 × A)
Where A = Sαγ / (Sαγ + Sαδ)

<Amount of copolymer (component 2) in masterbatch composition>
The following formula was used.
Amount of component (2) (% by weight) = total ethylene amount / (ethylene concentration in copolymer / 100)

[Collecting xylene solubles]
Place 2.5 g of polymer in a flask containing 250 mL of o-xylene (solvent) and stir for 30 minutes at 135 ° C. while purging with nitrogen using a hot plate and a reflux device to completely dissolve the composition. Then, cooling was performed at 25 ° C. for 1 hour. The resulting solution was filtered using filter paper. 100 mL of the filtrate after filtration was collected, transferred to an aluminum cup or the like, evaporated and dried 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 xylene solubles as a sample, the intrinsic viscosity (IV) was measured in 135 ° C. tetrahydronaphthalene using an Ubbelohde viscometer (SS-780-H1, manufactured by Shibayama Scientific Instruments).

However, since the ethylene homopolymer of the component (2) of the masterbatch composition of Comparative Example 4 has almost no component soluble in xylene, the component (2) estimated from the ethylene content of the masterbatch composition The IV of component (2) was calculated from the ratio, the IV of the entire masterbatch composition, and the IV value of component (1), assuming the additivity of IV.

[Collecting xylene-insoluble matter]
As described above, when the xylene-soluble component is filtered, acetone is added to the residue (mixture of xylene-insoluble component and solvent) remaining on the filter paper and filtered, and then the unfiltered component is vacuumed at 80 ° C. In a drying oven, it was evaporated to dryness to obtain xylene-insoluble matter (XI).

[Mw and Mw / Mn of xylene insoluble matter]
Using the xylene-insoluble matter as a sample, the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured as follows.

PL GPC220 manufactured by Polymer Laboratories was used as the apparatus, 1,2,4-trichlorobenzene containing an antioxidant was used as the mobile phase, and UT-G (1), UT-807 (Showa Denko KK) was used as the column. 1) and UT-806M (2) connected in series were used, and a differential refractometer was used as a detector. Moreover, the same solvent as the mobile phase was used as a solvent for the sample solution of xylene-insoluble matter, and a measurement sample was prepared by dissolving at a sample concentration of 1 mg / mL for 2 hours while shaking at a temperature of 150 ° C. 500 μL of the sample solution thus obtained was injected into the column and measured at a flow rate of 1.0 mL / min, a temperature of 145 ° C., and a data acquisition interval of 1 second. For column calibration, a polystyrene standard sample (shodex STANDARD, manufactured by Showa Denko KK) having a molecular weight of 580 to 7.45 million was used and approximated by a cubic equation. The Mark-Houkins coefficients are K = 1.21 × 10 ⁻⁴ and α = 0.707 for the polystyrene standard sample, and K = 1.37 × 10 ⁻⁴ and α = 0. 75 was used.

[Bending elastic modulus]
A bending test was performed at room temperature (23 ° C.) according to JIS K6921-2. Measurements were made at a crosshead speed of 2 mm / min.

[Charpy impact strength]
A test piece (80 (length) × 10 (width) × 4 (thickness) mm ³ ) obtained by cutting the obtained polypropylene resin molded article (test piece for evaluating physical properties) was 23 ° C. in accordance with ISO 179-1. The Charpy impact strength at -30 ° C was measured.

[Linear expansion coefficient]
The center part (width 10 mm) of the obtained polypropylene resin molded article (physical property evaluation test piece, thickness 4 mm) was cut into a length of 10 mm along the flow direction (MD) of the resin, and placed in an 80 ° C. oven for 24 hours. Measurement was performed in accordance with JIS K7197 using the samples left as they were.
<Test equipment> Ulvac MTS9000 (manufactured by Vacuum Riko)
<Test conditions> Temperature increase rate: 5 ° C / min Load: 5.0 g weight Measurement temperature: -30 ° C to 80 ° C

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

Claims (8)

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