JP5613032B2 - Polypropylene resin composition - Google Patents

Description

  The present invention relates to a polypropylene resin composition. More specifically, the present invention relates to a resin composition capable of producing a molded article having excellent mechanical properties, a flow mark or the like being inconspicuous, having a good appearance, excellent low gloss, and good scratch resistance.

  Automobile interior parts made of resin molded products are usually scratch-resistant and low gloss (for the purpose of giving the molded product a high-class feel and suppressing the transfer to window glass in consideration of safety) In order to conceal the appearance defects such as the flow mark, it is often used after a post-process such as painting or skin bonding. Therefore, the excellent economic efficiency of the resin molded product is not fully enjoyed.

  Patent Document 1 describes a polypropylene resin composition as a material having good scratch resistance, low gloss, and good flow mark appearance. However, the reduction in gloss was still insufficient. Further, since a high molecular weight ethylene / α-olefin / diene copolymer was used, the dispersibility was poor, and the surface of the molded product was liable to be generated. In addition, when ethylene / α-olefin / diene copolymer is used, there is a problem that raw material costs increase.

Patent Document 2 describes a propylene resin composition having good moldability and molding appearance (flow mark appearance, texture appearance). However, sufficient mechanical properties cannot be obtained with this propylene resin composition.
Patent Document 3 describes a propylene resin composition that has good moldability, and in particular, a molded product molded by injection molding is excellent in terms of flow mark, low gloss, and weld appearance. However, the scratch resistance was not sufficient.

JP 2009-079117 A JP 2009-155627 A JP 2000-143904 A

  The present invention provides a polypropylene-based resin composition that is excellent in mechanical properties, has a low flow mark and the like, has low gloss and scratch resistance, and can produce a molded product applicable to automobile interior parts. Objective.

According to the present invention, the following polypropylene resin compositions and the like are provided.
1. The following (A) component 100 weight part, (B) component 7-14 weight part, (C) component 7-20 weight part, (D) component 24-36 weight part, (E) component 0.1-3.5 A polypropylene resin composition containing parts by weight and 0.2 to 3.0 parts by weight of component (F).
(A) Propylene / ethylene block copolymer A satisfying the following (a1) to (d1), or a mixture of the copolymer A and polypropylene:
(A1) The room temperature decane soluble part is 16 wt% or more and 25 wt% or less (b1) The ethylene content of the room temperature decane soluble part is 45 mol% or more and 65 mol% or less (c1) The intrinsic viscosity of the room temperature decane soluble part [η ] Is 2.4 dl / g or more and 4.0 dl / g or less (d1) Melt flow rate (MFR: 230 ° C., under 2.16 kg load) is 10 g / 10 min or more and 53 g / 10 min or less (B) The following (a2) Propylene / ethylene block copolymer B satisfying (d2):
(A2) Room temperature decane soluble part: 36 wt% or more and 55 wt% or less (b2) Ethylene content of room temperature decane soluble part is 25 mol% or more and 35 mol% or less (c2) Intrinsic viscosity of room temperature decane soluble part [η ] Is 7.0 dl / g or more and 10.0 dl / g or less (d2) MFR (230 ° C., under 2.16 kg load) is 0.08 g / 10 min or more and 2.0 g / 10 min or less (C) MFR (230 ° C. Inorganic filler (E) acid having an average particle diameter of 1 μm or more and 14 μm or less, and an ethylene / α-olefin copolymer (D) having a load of 2.16 kg and a weight of 0.8 g / 10 min to 20 g / 10 min 1. Modified polypropylene (F) lubricant 2. The polypropylene resin composition according to 1, wherein the room temperature decane soluble part (a2) of the component (B) is 40 wt% or more and 55 wt% or less.
3. The room temperature decane soluble part of the component (A) is from 16% by weight to 20% by weight, the room temperature decane soluble part of the component (B) is from 40% by weight to 47% by weight, 3. The polypropylene resin composition according to 1 or 2, wherein the amount of the component is 7 to 15 parts by weight.
4). The polypropylene resin composition according to any one of 1 to 3, wherein the inorganic filler (D) is talc.
5. The polypropylene resin composition according to any one of 1 to 4, wherein the lubricant (F) is a fatty acid amide.
6). The polypropylene resin composition according to any one of 1 to 5, wherein MFR (230 ° C., under a load of 2.16 kg) is 10 g / 10 min or more and 45 g / 10 min or less.
7). A molded product formed by molding the polypropylene resin composition according to any one of 1 to 6 above.
8). The molded article according to claim 7, which is used for an instrument panel of an automobile.

  A molded article made of the polypropylene resin composition of the present invention is less noticeable in flow marks and the like, and is excellent in low gloss and scratch resistance. Therefore, it is possible to omit subsequent processes such as painting and skin lamination.

The polypropylene resin composition of the present invention is characterized by containing the following components (A) to (F).
(A) Propylene / ethylene block copolymer A or a mixture of copolymer A and polypropylene: 100 parts by weight (B) Propylene / ethylene block copolymer B: 7 to 14 parts by weight (C) MFR (230 ° C., 2.16 kg of ethylene / α-olefin copolymer having a load of 0.8 g / 10 min to 20 g / 10 min: 7 to 20 parts by weight (D) Inorganic filling having an average particle size of 1 μm to 14 μm Material: 24-36 parts by weight (E) Acid-modified polypropylene: 0.1-3.5 parts by weight (F) Lubricant: 0.2-3.0 parts by weight A predetermined amount of the above components (A) to (F) is contained. By doing so, it is possible to obtain a molded product in which a flow mark or the like is not conspicuous and is excellent in low glossiness and scratch resistance. In particular, by mixing the component (A) having a high proportion of the ethylene part (the amount of ethylene in the room temperature decane-soluble part) and the component (B) having a low proportion of the ethylene part, the polypropylene parts of the components (A) and (B) The interfacial strength of the rubber part is improved, and the impact resistance and tensile elongation are improved. Also, the flow mark is less noticeable.
Hereinafter, each component will be described.

(A) Component (A)
Component (A) is a propylene / ethylene block copolymer A or a mixture of copolymer A and polypropylene. The component (A) satisfies the following (a1) to (d1).
(A1) The room temperature decane soluble part is 16 wt% or more and 25 wt% or less (b1) The ethylene content of the room temperature decane soluble part is 45 mol% or more and 65 mol% or less (c1) The intrinsic viscosity of the room temperature decane soluble part [η ] Is 2.4 dl / g or more and 4.0 dl / g or less (d1) MFR (230 ° C., under 2.16 kg load) is 10 g / 10 min or more and 53 g / 10 min or less

With respect to the above (a1), the room temperature decane soluble part of the propylene / ethylene block copolymer A used in the present invention is 16% by weight or more and 25% by weight or less, preferably 16% by weight or more and 20% by weight or less. .
When the room temperature decane-soluble part is less than 16% by weight, the impact resistance of the obtained molded product becomes insufficient. On the other hand, if it exceeds 25% by weight, the flexural modulus decreases.

  Regarding (b1) above, the ethylene content in the room temperature decane soluble part of the propylene / ethylene block copolymer A is 45 mol% or more and 65 mol% or less, and preferably 47 mol% or more and 60 mol% or less. If the ethylene content in the room temperature decane soluble part is less than 45 mol%, the target low glossiness cannot be obtained. On the other hand, if it exceeds 65 mol%, the target low gloss can be obtained, but sufficient impact properties and tensile elongation cannot be obtained.

Regarding the above (c1), the intrinsic viscosity [η] of the room temperature decane soluble part of the propylene / ethylene block copolymer A is 2.4 dl / g or more and 4.0 dl / g or less, preferably 2.7 dl / g. This is 3.7 dl / g or less.
When [η] is less than 2.4 dl / g, there is no effect of lowering the gloss of the molded product, and sufficient low gloss cannot be imparted. On the other hand, if it exceeds 4.0 dl / g, the resin fluidity is lowered and it becomes difficult to mix with other resins at the time of kneading, so that the appearance of the molded product is deteriorated and the appearance is deteriorated, and the mechanical properties can be lowered. There is sex.

  With respect to the above (d1), the MFR of the propylene / ethylene block copolymer A is 10 g / 10 min or more and 53 g / 10 min or less, preferably 30 g / 10 min or more and 45 g / 10 min or less. When the melt flow rate is less than 10 g / 10 minutes, the fluidity is lowered and the moldability is deteriorated. On the other hand, if it exceeds 53 g / 10 minutes, impact resistance and tensile elongation will decrease.

As the component (A), a mixture obtained by adding homopolypropylene to the above-described propylene / ethylene block copolymer A may be used. The mixture also satisfies the above requirements (a1) to (d1). The reason for selecting this requirement is the same as the reason for selecting (a1) to (d1) for the propylene / ethylene block copolymer. By adding homopolypropylene, the rigidity of the molded product can be adjusted. The addition amount of homopolypropylene can be appropriately determined according to the purpose, but is usually added so as to be 15 to 35% by weight with respect to the total of copolymer A and homopolypropylene.
The MFR of homopolypropylene can be appropriately selected according to the purpose, but is usually 10 to 53 g / 10 minutes.

(B) Propylene / ethylene block copolymer B
The propylene / ethylene block copolymer B satisfies the following (a2) to (d2).
(A2) Room temperature decane soluble part: 36 wt% or more and 55 wt% or less (b2) Ethylene content of room temperature decane soluble part is 25 mol% or more and 35 mol% or less (c2) Intrinsic viscosity of room temperature decane soluble part [η ] Is 7.0 (dl / g) or more and 10.0 (dl / g) or less (d2) MFR (230 ° C., under 2.16 kg load) is 0.08 g / 10 min or more and 2.0 g / 10 min or less

  With regard to the above (a2), the normal temperature decane soluble part of the propylene / ethylene block copolymer B is 36 wt% or more and 55 wt% or less, preferably 40 wt% or more and 55 wt% or less, particularly preferably 40 wt%. % By weight or more and 47% by weight or less. When the decane-soluble part is less than 36% by weight, the impact resistance is lowered, the starting point of the flow mark is shortened, and the appearance of the molded product is deteriorated. On the other hand, if it exceeds 55% by weight, the resin fluidity is lowered and the moldability is deteriorated.

  With regard to (b2), the ethylene content in the room temperature decane soluble part of the propylene / ethylene block copolymer B is 25 mol% or more and 35 mol% or less, preferably 25 mol% or more and 30 mol% or less. When the ethylene content in the room temperature decane soluble part is less than 25 mol% and exceeds 35 mol%, sufficient impact resistance cannot be obtained.

  With respect to the above (c2), the intrinsic viscosity [η] of the decane soluble part of the propylene / ethylene block copolymer B is 7.0 dl / g or more and 10.0 dl / g or less, preferably 8.0 dl / g or more. It is 9.5 dl / g or less. When [η] is less than 7.0 dl / g, the flow mark starting point is shortened and the appearance of the molded product is deteriorated. In addition, impact resistance and tensile elongation decrease. On the other hand, if it exceeds 10.0 dl / g, the resin fluidity will be lowered and it will be difficult to mix with other resins during kneading, and the molded product will be crumpled and the appearance will deteriorate.

  Regarding the above (d2), the MFR of the propylene / ethylene block copolymer B is 0.08 g / 10 min or more and 2.0 g / 10 min or less, preferably 0.1 g / 10 min or more and 0.7 g / 10 min. It is as follows. When MFR is less than 0.08 g / 10 minutes, the resin fluidity during molding is lowered. On the other hand, when it exceeds 2.0 g / 10 minutes, the impact resistance of the molded product is lowered.

  The compounding amount of the propylene / ethylene block copolymer B is 7 to 14 parts by weight, preferably 8 to 12 parts by weight, based on 100 parts by weight of the component (A) described above. When the blending amount of the copolymer B is less than 7 parts by weight, the start point of the flow mark is shortened and the appearance of the molded product is deteriorated. In addition, impact resistance and tensile elongation decrease. On the other hand, when it exceeds 14 parts by weight, the resin fluidity is lowered and the moldability is deteriorated.

  The propylene / ethylene block copolymers A and B used in the present invention are, for example, an olefin polymerization catalyst containing the following solid titanium catalyst component (I) and organometallic compound catalyst component (II). It can be produced by polymerization and further copolymerization of propylene and ethylene. Hereinafter, the catalyst component and the polymerization method will be described.

[Solid titanium catalyst component (I)]
The solid titanium catalyst component (I) is characterized by containing titanium, magnesium, halogen, and, if necessary, an electron donor. As this solid titanium catalyst component (I), a known solid titanium catalyst component can be used without limitation. The example of the manufacturing method of solid titanium catalyst component (I) is shown below.

In the preparation of the solid titanium catalyst component (I) of the present invention, there are many examples in which a magnesium compound and a titanium compound are used.
Specific examples of magnesium compounds include magnesium halides such as magnesium chloride and magnesium bromide; alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride and phenoxymagnesium chloride; ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, 2 -Alkoxymagnesium such as ethylhexoxymagnesium; aryloxymagnesium such as phenoxymagnesium; and known magnesium compounds such as magnesium carboxylates such as magnesium stearate.

  These magnesium compounds may be used alone or in combination of two or more. These magnesium compounds may be complex compounds with other metals, double compounds, or mixtures with other metal compounds.

  Among these, a magnesium compound containing a halogen is preferable, and a magnesium halide, particularly magnesium chloride is preferably used. In addition, alkoxymagnesium such as ethoxymagnesium is also preferably used. The magnesium compound may be derived from another substance, for example, obtained by contacting an organic magnesium compound such as a Grignard reagent with a halogenated titanium, a halogenated silicon, a halogenated alcohol or the like. Good.

As a titanium compound, the tetravalent titanium compound shown by a following formula can be mentioned, for example.
Ti (OR) _g X _4-g
(In the formula, R is a hydrocarbon group, X is a halogen atom, and g is 0 ≦ g ≦ 4.)

More specifically, titanium tetrahalides such as TiCl ₄ and TiBr ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Trihalogenated alkoxytitanium such as Ti (OC ₂ H ₅ ) Br ₃ and Ti (O-isoC ₄ H ₉ ) Br ₃ ; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl _{2 and the} like Dihalogenated alkoxytitanium; monohalogenated alkoxytitanium such as Ti (OCH ₃ ) ₃ Cl, Ti (On-C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ And tetraalkoxytitanium such as Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₄ H ₉ ) ₄ , and Ti (O-2-ethylhexyl) ₄ .

  Among these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more.

  As said magnesium compound and titanium compound, the compound described in detail in Unexamined-Japanese-Patent No. 57-63310, Unexamined-Japanese-Patent No. 5-170843 etc. can be mentioned, for example.

  Preferable specific examples of the preparation of the solid titanium catalyst component (I) used in the present invention include the following methods (P-1) to (P-4).

(P-1) An inert hydrocarbon solvent comprising a solid adduct comprising an electron donor component (a) such as a magnesium compound and alcohol, an electron donor component (b) described later, and a titanium compound in a liquid state A method of contacting in suspension in the presence of coexistence.
(P-2) A method in which a solid adduct composed of a magnesium compound and an electron donor component (a), an electron donor component (b), and a titanium compound in a liquid state are contacted in a plurality of times.
(P-3) A solid adduct comprising a magnesium compound and an electron donor component (a), an electron donor component (b), and a liquid titanium compound are suspended in the presence of an inert hydrocarbon solvent. The method of making it contact in a state and making it contact in multiple times.
(P-4) A method in which a magnesium compound in a liquid state comprising a magnesium compound and an electron donor component (a), a titanium compound in a liquid state, and an electron donor component (b) are brought into contact.

The preferred reaction temperature is in the range of −30 ° C. to 150 ° C., more preferably −25 ° C. to 130 ° C., still more preferably −25 to 120 ° C.
In addition, the production of the above solid titanium catalyst component can be carried out in the presence of a known medium, if necessary. Examples of the medium include aromatic hydrocarbons such as toluene having a slight polarity, and known aliphatic hydrocarbons and alicyclic hydrocarbon compounds such as heptane, octane, decane, and cyclohexane. Group hydrocarbons are preferred examples.

  As the electron donor component (a) used for forming the solid adduct or the magnesium compound in a liquid state, a known compound that can solubilize the magnesium compound in a temperature range of about room temperature to about 300 ° C. is preferable. For example, alcohol, aldehyde, amine, carboxylic acid and a mixture thereof are preferable. Examples of these compounds include compounds described in detail in JP-A-57-63310 and JP-A-5-170843.

  More specifically, the alcohol having the ability to solubilize the magnesium compound includes methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, and n-octanol. Aliphatic alcohols such as 2-ethylhexanol, decanol and dodecanol; alicyclic alcohols such as cyclohexanol and methylcyclohexanol; aromatic alcohols such as benzyl alcohol and methylbenzyl alcohol; and alkoxy groups such as n-butyl cellosolve. Examples thereof include aliphatic alcohols.

  Examples of the carboxylic acid include organic carboxylic acids having 7 or more carbon atoms such as caprylic acid and 2-ethylhexanoic acid. Examples of the aldehyde include aldehydes having 7 or more carbon atoms such as capric aldehyde and 2-ethylhexyl aldehyde.

  Examples of the amine include amines having 6 or more carbon atoms such as heptylamine, octylamine, nonylamine, laurylamine, 2-ethylhexylamine.

  As said electron donor component (a), said alcohol is preferable, and especially ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, decanol, etc. are preferable.

  The composition ratio of magnesium and the electron donor component (a) in the obtained solid adduct or liquid magnesium compound varies depending on the type of compound used, and thus cannot be defined unconditionally. On the other hand, the electron donor component (a) is preferably in a range of 2 mol or more, more preferably 2.3 mol or more, still more preferably 2.7 mol or more and 5 mol or less.

  Particularly preferable examples of the electron donor used as necessary for the solid titanium catalyst component (I) used in the present invention include an aromatic carboxylic acid ester and / or two or more ethers via a plurality of carbon atoms. A compound having a bond (hereinafter also referred to as “electron donor component (b)”) may be contained.

  Examples of the electron donor component (b) include known aromatic carboxylic acid esters and polyether compounds that have been preferably used in conventional olefin polymerization catalysts, such as JP-A Nos. 5-170843 and 2001-354714. Etc. can be used without limitation.

  Specific examples of the aromatic carboxylic acid ester include aromatic polycarboxylic acid esters such as phthalic acid esters, in addition to aromatic carboxylic acid monoesters such as benzoic acid esters and toluic acid esters. Among these, aromatic polycarboxylic acid esters are preferable, and phthalic acid esters are more preferable. As the phthalic acid esters, phthalic acid alkyl esters such as ethyl phthalate, n-butyl phthalate, isobutyl phthalate, hexyl phthalate, and heptyl phthalate are preferable, and diisobutyl phthalate is particularly preferable.

  Moreover, as a polyether compound, the compound represented by the following formula | equation (1) is mentioned more specifically.

In the above formula (1), m is an integer of 1 ≦ m ≦ 10, more preferably an integer of 3 ≦ m ≦ 10, and R ^{11 to} R ³⁶ are each independently a hydrogen atom, carbon, hydrogen, oxygen , Fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron, and silicon, and a substituent having at least one element selected from silicon.

When m is 2 or more, a plurality of R ¹¹ and R ¹² may be the same or different. Arbitrary R ^{11 to} R ³⁶ , preferably R ¹¹ and R ¹² may jointly form a ring other than a benzene ring.

  Specific examples of some of such compounds include 2-isopropyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane and the like. Substituted dialkoxypropanes; 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2 -Methyl-2-cyclohexyl-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl ) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-di Sobutyl-1,3-dibutoxypropane, 2,2-di-s-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 2-substituted dialkoxypropanes such as 3-dimethoxypropane and 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane; 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1 , 4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4 -Diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, Dialkoxyalkanes such as 1,4-diisoamyl-1,5-dimethoxypentane; 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane And trialkoxyalkanes such as 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane, and the like.

  Of these, 1,3-diethers are preferable, and in particular, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl. -1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, and 2,2-bis (cyclohexylmethyl) 1,3-dimethoxypropane are preferred.

  These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the solid titanium catalyst component (I) used in the present invention, the halogen / titanium (atomic ratio) (that is, the number of moles of halogen atom / number of moles of titanium atom) is 2 to 100, preferably 4 to 90. It is desirable that the electron donor component (a) and the electron donor component (b) have an electron donor component (a) / titanium atom (molar ratio) of 0 to 100, preferably 0 to 10. The electron donor component (b) / titanium atom (molar ratio) is 0-100, preferably 0-10.

  Magnesium / titanium (atomic ratio) (that is, the number of moles of magnesium atoms / the number of moles of titanium atoms) is 2 to 100, preferably 4 to 50.

  Except for using the electron donor component (b) as a more detailed preparation condition of the solid titanium catalyst component (I), for example, EP585869A1 (European Patent Application Publication No. 0585869) and JP-A-5-170843. The conditions described in the gazette and the like can be preferably used.

  Next, the organometallic compound catalyst component (II) containing a metal element selected from Group 1, Group 2, and Group 13 of the periodic table will be described.

[Organometallic Compound Catalyst Component (II)]
As the organometallic compound catalyst component (II), a compound containing a Group 13 metal, for example, an organoaluminum compound, a complex alkylated product of a Group 1 metal and aluminum, an organometallic compound of a Group 2 metal, or the like is used. it can. Among these, an organoaluminum compound is preferable.

  Specific examples of the organometallic compound catalyst component (II) include organometallic compound catalyst components described in known documents such as EP585869A1.

Unless the object of the present invention is impaired, a known electron donor component (c) may be used in combination with the electron donor component (a) or the electron donor component (b).
Such an electron donor component (c) is preferably an organosilicon compound. As this organosilicon compound, for example, a compound represented by the following formula can be exemplified.
R _n Si (OR ′) _4-n
(In the formula, R and R ′ are hydrocarbon groups, and n is an integer of 0 <n <4.)

  Specific examples of the organosilicon compound represented by the above formula include diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, and cyclohexylmethyldimethoxy. Silane, cyclohexylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyltri Ethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, dicyclopenta Chill methyl methoxy silane, dicyclopentyl ethyl silane, cyclopentyl dimethylethoxysilane or the like is used.

  Of these, vinyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, and dicyclopentyldimethoxysilane are preferably used.

Moreover, the silane compound represented by the following formula described in the pamphlet of International Publication No. 2004/016662 is also a preferable example of the organosilicon compound.
Si (OR ^a ) ₃ (NR ^b R ^c )

In the formula, R ^a is a hydrocarbon group having 1 to 6 carbon atoms, and examples of ^Ra include an unsaturated or saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, particularly preferably 2 carbon atoms. ˜6 hydrocarbon groups. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n- A hexyl group, a cyclohexyl group, etc. are mentioned, Among these, an ethyl group is particularly preferable.

R ^b is a hydrocarbon group having 1 to 12 carbon atoms or hydrogen, and examples of R ^b include an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or hydrogen. Specific examples include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, an n-pentyl group, an iso-pentyl group, and a cyclopentyl group. , N-hexyl group, cyclohexyl group, octyl group and the like, among which ethyl group is particularly preferable.

R ^c is a hydrocarbon group having 1 to 12 carbon atoms, and examples of R ^c include an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or hydrogen. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n- A hexyl group, a cyclohexyl group, an octyl group, etc. are mentioned, Among these, an ethyl group is particularly preferable.

  Specific examples of the compound represented by the above formula include dimethylaminotriethoxysilane, diethylaminotriethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, diethylaminotri-n-propoxysilane, di-n-propylaminotriethoxysilane, Examples include methyl n-propylaminotriethoxysilane, t-butylaminotriethoxysilane, ethyl n-propylaminotriethoxysilane, ethyl iso-propylaminotriethoxysilane, and methylethylaminotriethoxysilane.

Other examples of the organosilicon compound include compounds represented by the following formula.
RNSi (OR ^a ) ₃

In the formula, RN represents a cyclic amino group. Examples of the cyclic amino group include a perhydroquinolino group, a perhydroisoquinolino group, a 1,2,3,4-tetrahydroquinolino group, and 1,2,3. , 4-tetrahydroisoquinolino group, octamethyleneimino group and the like.
Specific examples of the compound represented by the above formula include (perhydroquinolino) triethoxysilane, (perhydroisoquinolino) triethoxysilane, (1,2,3,4-tetrahydroquinolino) triethoxysilane, (1,2,3,4-tetrahydroisoquinolino) triethoxysilane, octamethyleneiminotriethoxysilane and the like.

  These organosilicon compounds can be used in combination of two or more.

  The propylene / ethylene block copolymer is obtained by polymerizing propylene in the presence of the above-described olefin polymerization catalyst, and then in the presence of a prepolymerization catalyst obtained by copolymerizing propylene and ethylene or by prepolymerization. It can be produced by a method such as polymerizing propylene and then copolymerizing propylene and ethylene.

The prepolymerization is performed by prepolymerizing the olefin in an amount of usually 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g per 1 g of the olefin polymerization catalyst.
In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used.
The concentration of the solid titanium catalyst component (I) in the prepolymerization is usually about 0.001 to 200 mmol, preferably about 0.01 to 50 mmol, and particularly preferably about 0.1 to 50 mmol in terms of titanium atom per liter of the liquid medium. A range of 1 to 20 mmol is desirable.

  The amount of the organometallic compound catalyst component (II) in the prepolymerization should be such that an amount of 0.1 to 1000 g, preferably 0.3 to 500 g of polymer is usually produced per 1 g of the solid titanium catalyst component (I). The amount is usually about 0.1 to 300 mol, preferably about 0.5 to 100 mol, particularly preferably 1 to 50 mol, per mol of titanium atom in the solid titanium catalyst component (I). Is desirable.

  In the prepolymerization, the electron donor component or the like can be used as necessary. In this case, these components are usually from 0.1 to 50 per mole of titanium atom in the solid titanium catalyst component (I). It is used in an amount of mol, preferably 0.5 to 30 mol, more preferably 1 to 10 mol.

The prepolymerization can be performed under mild conditions by adding an olefin and the above catalyst components to an inert hydrocarbon medium.
In this case, specific examples of the inert hydrocarbon medium used include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, methylcyclopentane, cyclohexane, cyclohexane And alicyclic hydrocarbons such as heptane, methylcycloheptane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; or a mixture thereof. .
Of these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Thus, when using an inert hydrocarbon medium, it is preferable to perform prepolymerization by a batch type.

  On the other hand, prepolymerization can be carried out using olefin itself as a solvent, or it can be prepolymerized in a substantially solvent-free state. In this case, it is preferable to perform preliminary polymerization continuously.

The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described later, but is preferably propylene.
The temperature during the prepolymerization is usually -20 to + 100 ° C, preferably -20 to + 80 ° C, more preferably 0 to + 40 ° C.

Next, the main polymerization carried out after passing through the preliminary polymerization or without going through the preliminary polymerization will be described.
The main polymerization is divided into a process for producing a propylene polymer component and a process for producing a propylene-ethylene copolymer rubber component.
The prepolymerization and the main polymerization can be performed by any of a liquid phase polymerization method such as a bulk polymerization method, a solution polymerization and a suspension polymerization, or a gas phase polymerization method. A preferred process for producing the propylene polymer component is liquid phase polymerization such as bulk polymerization or suspension polymerization or gas phase polymerization. Further, a preferable process for producing the propylene-ethylene copolymer rubber component is a liquid phase polymerization or gas phase polymerization method such as bulk polymerization or suspension polymerization, and a more preferable method is a gas phase polymerization method.

  When the main polymerization takes the form of slurry polymerization, the reaction solvent may be an inert hydrocarbon used during the above-described prepolymerization, or an olefin that is liquid at the reaction temperature and pressure.

  In the main polymerization, the solid titanium catalyst component (I) is usually about 0.0001 to 0.5 mmol, preferably about 0.005 to 0.1 mmol in terms of titanium atom per liter of polymerization volume. Used in quantity. The organometallic compound catalyst component (II) is used in an amount of usually about 1 to 2000 mol, preferably about 5 to 500 mol, per 1 mol of titanium atom in the prepolymerized catalyst component in the polymerization system. It is done. If the electron donor component is used, it is 0.001 to 50 mol, preferably 0.01 to 30 mol, particularly preferably 0.001 mol, per 1 mol of the organometallic compound catalyst component (II). Used in an amount of 05 to 20 mol.

If the main polymerization is carried out in the presence of hydrogen, the molecular weight of the resulting polymer can be adjusted (lowered), and a polymer having a high melt flow rate can be obtained. The amount of hydrogen necessary to adjust the molecular weight varies depending on the type of production process used, the polymerization temperature, and the pressure, and may be adjusted as appropriate.
In the step of producing the propylene polymer component, the MFR can be adjusted by adjusting the polymerization temperature and the amount of hydrogen. Moreover, also in the process of producing a propylene-ethylene copolymer rubber component, the intrinsic viscosity can be adjusted by adjusting the polymerization temperature, pressure, and amount of hydrogen.

In the main polymerization, the polymerization temperature of the olefin is usually about 0 to 200 ° C, preferably about 30 to 100 ° C, more preferably 50 to 90 ° C. The pressure (gauge pressure) is usually set to normal pressure to 100 kgf / cm ² (9.8 MPa), preferably about ^{2 to} 50 kgf / cm ² (0.20 to 4.9 MPa).
In the method for producing a propylene / ethylene block copolymer, the polymerization can be carried out by any of batch, semi-continuous and continuous methods. Furthermore, the reactor can be tubular or tank type. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions. In this case, a tubular shape and a tank shape can be combined.

Further, the ethylene / (ethylene + propylene) gas ratio is controlled in order to obtain a propylene / ethylene copolymer.
The ethylene / (ethylene + propylene) gas ratio is controlled to be 5 to 80 mol%, preferably 10 to 70 mol%, more preferably 15 to 60 mol%.

The method for producing the propylene / ethylene block copolymer used in the present invention will be described in more detail.
According to the knowledge of the present inventors, the portion (Dinsol) insoluble in room temperature n-decane constituting the propylene / ethylene block copolymer is mainly composed of a propylene polymer component.
On the other hand, the portion soluble in room temperature n-decane (Dsol) is mainly composed of a propylene-ethylene copolymer rubber component.

Therefore, by continuously carrying out the following two polymerization steps (polymerization step 1 and polymerization step 2), it is possible to obtain a propylene / ethylene block copolymer satisfying the above-mentioned requirements (hereinafter, this method is referred to as “method”). This is called “straight weight method”).
[Polymerization step 1]
A step of producing a propylene polymer component by polymerizing propylene in the presence of a solid titanium catalyst component (a propylene polymer production step).
[Polymerization step 2]
A step of producing a propylene-ethylene copolymer rubber component by copolymerizing propylene and ethylene in the presence of a solid titanium catalyst component (copolymer rubber production step).

  The propylene / ethylene block copolymer used in the present invention is preferably produced by the production method described above, and it is more preferred that the polymerization step 1 is performed in the preceding stage and the polymerization step 2 is performed in the subsequent stage. Each polymerization step (polymerization step 1, polymerization step 2) can also be performed using two or more polymerization vessels. What is necessary is just to adjust the polymerization time (residence time) of the process 1 and the process 2 for content of the decane soluble part in a block copolymer.

(C) Ethylene / α-olefin copolymer The ethylene / α-olefin copolymer used in the present invention has an MFR (230 ° C., under a load of 2.16 kg) of 0.8 g / 10 min to 20 g / 10 min. It is preferably 2 g / 10 min or more and 13 g / 10 min or less. When the MFR is less than 0.8 g / 10 minutes, the resin fluidity is lowered and the dispersion is poor during kneading, which leads to the deterioration of physical properties such as impact resistance and the appearance of the molded product surface. On the other hand, if it exceeds 20 g / 10 minutes, sufficient impact resistance cannot be obtained, and the gloss of the surface of the molded product is increased.

Examples of the ethylene / α-olefin copolymer include a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms. As the α-olefin, propylene, 1-butene, 1-hexene, 1-octene and the like are preferable. The α-olefin may be used alone or in combination of two or more.
The amount of α-olefin in the ethylene / α-olefin copolymer is preferably 15% by weight to 65% by weight.
As the ethylene / α-olefin copolymer, an ethylene-octene copolymer and an ethylene-butene copolymer are preferable.

  The compounding amount of the ethylene / α-olefin copolymer is 7 to 20 parts by weight, preferably 7 to 15 parts by weight based on 100 parts by weight of the component (A) described above. When the blending amount is less than 7 parts by weight, sufficient impact resistance cannot be obtained. On the other hand, if it exceeds 20 parts by weight, sufficient rigidity (flexural modulus) cannot be obtained, and glossiness increases. Further, the scratch resistance performance is also reduced.

(D) Inorganic filler having an average particle diameter of 1 μm or more and 14 μm or less The inorganic filler used in the present invention is not particularly limited, and a known inorganic filler can be used. Examples include talc, mica, calcium carbonate, barium sulfate, glass fiber, gypsum, magnesium carbonate, magnesium oxide, titanium oxide and the like. Of these, talc is particularly preferable.
The average particle size of the inorganic filler is 1 μm or more and 14 μm or less, preferably 3 μm or more and 7 μm or less. If the average particle size is smaller than 1 μm, the inorganic filler aggregates to cause dispersion failure, so that mechanical properties such as impact resistance and tensile elongation decrease. On the other hand, when the thickness is larger than 14 μm, mechanical properties such as impact resistance and tensile elongation are lowered.
The average particle diameter is a value measured by a laser diffraction method.

  The compounding quantity of an inorganic filler is 24-36 weight part with respect to 100 weight part of component (A) mentioned above, Preferably it is 27-33 weight part. When the amount is less than 24 parts by weight, the rigidity is lowered. On the other hand, if it exceeds 36 parts by weight, impact resistance and tensile elongation will decrease.

(E) Acid-modified polypropylene In the polypropylene resin composition of the present invention, the acid-modified polypropylene is 0.1 to 3.5 parts by weight, preferably 0.1 to 2 parts per 100 parts by weight of the component (A). .5 parts by weight is blended. When the addition amount of the acid-modified polypropylene is less than 0.1 parts by weight, the effect of improving scratch resistance is not exhibited. On the other hand, if it exceeds 3.5 parts by weight, the impact resistance may be lowered.

The acid-modified polypropylene is obtained by acid-modifying polypropylene. Examples of methods for modifying polypropylene include graft modification and copolymerization.
Examples of the unsaturated carboxylic acid used for modification include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, angelic acid, and phthalic acid. It is done. The derivatives include acid anhydrides, esters, amides, imides, metal salts, and the like, such as maleic anhydride, itaconic anhydride, citraconic anhydride, nadic anhydride, phthalic anhydride, methyl acrylate, Examples thereof include methyl acid, ethyl acrylate, butyl acrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, maleimide, N-butylmaleimide, sodium acrylate, sodium methacrylate and the like. Among these, unsaturated dicarboxylic acids and derivatives thereof are preferable, and maleic anhydride or phthalic anhydride is particularly preferable.

In the case of acid modification in the melt-kneading process, polypropylene and unsaturated carboxylic acid or its derivative are kneaded in an extruder using an organic peroxide, and the unsaturated carboxylic acid or its derivative is graft copolymerized and modified. Turn into.
Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, dicumyl peroxide, t-butyl hydroperoxide, α, α′-bis (t-butylperoxydiisopropyl). ) Benzene, bis (t-butyldioxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylper) Oxy) hexyne-3, di-t-butyl peroxide, cumene hydroperoxide and the like.

In the present invention, an acid-modified polypropylene modified with an unsaturated dicarboxylic acid or a derivative thereof is preferable as the acid-modified polypropylene, and maleic anhydride-modified polypropylene is particularly preferable.
The acid content in the acid-modified polypropylene is preferably 0.5% by weight to 7.0% by weight, and more preferably 0.8% by weight to 5.0% by weight.
The acid content can be measured from the absorption characteristic of the acid used for modification by measuring the IR vector of acid-modified polypropylene. In the case of maleic anhydride, there is absorption in the vicinity of 1780 cm ⁻¹ , and in the case of methacrylic acid ester, there is absorption in the vicinity of 1730 cm ⁻¹ , which can be determined from the peak area.
The intrinsic viscosity (135 ° C., in tetralin) of the acid-modified polypropylene can be about 0.1 to 3 dl / g.

  Examples of acid-modified polypropylene include commercial products such as Admer made by Mitsui Chemicals, Yumex made by Sanyo Kasei Co., Ltd., MZ series made by DuPont, Exxoror made by Exxon, and Polybond series made by Toyo Kasei Co., Ltd. (Both maleic anhydride-modified polypropylene) can be used.

(F) Lubricant Examples of the lubricant include fatty acid amides. Examples of the fatty acid include saturated and unsaturated fatty acids having about 15 to 30 carbon atoms.
Specific examples of fatty acid amides include oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, palmitic acid amide, myristylic acid amide, lauric acid amide, caprylic acid amide, caproic acid amide, n-oleyl palmi And toamide, n-oleyl erucamide, and their dimers. Of these, dimers of oleic acid amide, stearic acid amide, erucic acid amide and erucic acid amide are preferable.
These can be used alone or in combination.

  The compounding quantity of a lubricant is 0.2-3.0 weight part with respect to 100 weight part of component (A) mentioned above, Preferably, it is 0.2-1.5 weight part. When the addition amount of the lubricant is less than 0.2 parts by weight, a sufficient effect of improving scratch resistance is not recognized. On the other hand, if it exceeds 3.0 parts by weight, the surface modifier may bleed from the composition and adhere to the mold during molding, which may lead to mold contamination.

  In the polypropylene resin composition of the present invention, if necessary, heat stabilizer, antistatic agent, weathering stabilizer, light stabilizer, antioxidant, fatty acid metal salt, dispersant, colorant, lubricant, pigment, etc. Other additives can be blended within a range that does not impair the object of the present invention.

  In the polypropylene resin composition of the present invention, the MFR (230 ° C., under a load of 2.16 kg) of the entire composition is preferably 10 g / 10 min or more and 45 g / 10 min or less, particularly 10 g / 10 min or more and 30 g. / 10 minutes or less is preferable.

  The polypropylene composition of the present invention can be produced by mixing the above-described components (A) to (F) and other additives as required by a known method. For example, each component may be mixed with various mixers, tumblers, or the like, and the mixture may be melt-kneaded with an extruder or the like. Furthermore, in order to improve the operability of molding, the composition of the present invention may be processed into pellets and the like.

  The composition of the present invention can be processed into various molded products by known processing methods such as injection molding and extrusion molding. The molded product of the present invention is less noticeable for flow marks and the like, and has excellent low gloss and scratch resistance. Therefore, it can be used as a product without providing a post-process such as painting or skin lamination. Therefore, it is particularly suitable as an automobile interior material (instrument panel, pillar, door trim, etc.).

Hereinafter, the present invention will be described more specifically with reference to examples.
In addition, the measurement of the characteristic of each component and the polypropylene resin composition of this invention, and the evaluation method of the polypropylene resin composition and molded article of this invention are shown below.

(1) Room temperature decane soluble part The amount of the decane soluble component of the propylene / ethylene block copolymer at room temperature (25 ° C) was determined as follows. First, 5 g of a sample was precisely weighed, placed in a 1,000 ml eggplant-shaped flask, 1 g of BHT (dibutylhydroxytoluene, phenolic antioxidant) was added, and then a rotor and 700 ml of n-decane were added. .
Next, a condenser was attached to the eggplant-shaped flask, and the flask was heated in an oil bath at 135 ° C. for 120 minutes while operating the rotor, so that the sample was dissolved in n-decane.
Next, after pouring the contents of the flask into a 1,000 ml beaker, the solution in the beaker was allowed to cool to room temperature (25 ° C.) while stirring with a stirrer (8 hours or longer), and then a precipitate was formed. Was filtered with a wire mesh. The filtrate was further filtered with a filter paper, and then poured into 2,000 ml of methanol contained in a 3,000 ml beaker. This solution was stirred at room temperature (25 ° C.) with a stirrer for 2 hours. I left it above.
Next, the obtained precipitate was filtered with a wire mesh, air-dried for 5 hours or more, and then dried in a vacuum dryer at 100 ° C. for 240 to 270 minutes, and the n-decane soluble part at 25 ° C. was recovered.
The content (x) of the n-decane soluble part at 25 ° C. is x (mass%) = 100 × C / A, where Ag is the sample weight and Cg is the weight of the recovered n-decane soluble part. expressed.

(2) Ethylene content in room temperature decane soluble part Measured by Fourier transform infrared spectroscopy (FT-IR).

(3) Intrinsic viscosity [η]
Measured with decalin at 135 ° C.

(4) Measurement of melt flow rate:
In accordance with ASTM D1238, the test load was 2.16 kg and the test temperature was 230 ° C.

(5) Average particle diameter of the inorganic filler It measured by the laser diffraction method.

(6) Acid-modified group content 2 g of acid-modified polypropylene was sampled and completely dissolved by heating in 500 ml of boiling p-xylene. After cooling, it was put into 1200 ml of acetone, and the precipitate was filtered and dried to obtain a purified polymer. A film having a thickness of 20 μm was produced by hot pressing. The infrared absorption spectrum of this produced film was measured and determined from the peak area at 1780 cm ⁻¹ . ¹

(7) Izod impact strength (J / m)
According to ASTM D256, measurement was performed under the conditions of notching, hammer capacity of 40 kg · cm, and measurement temperature of 23 ° C.

(8) Tensile elongation rate Measured according to ASTM D638. The test conditions were a test speed of 10 mm / min, a gap between chucks of 115 mm, and a measurement temperature of 23 ° C.

(9) Measurement of flexural modulus Based on ASTM D790, measurement was performed under the conditions of a span interval of 100 mm, a bending speed of 2 mm / min, and a measurement temperature of 23 ° C.

(10) Flow mark measurement method Molding temperature of 210 ° C, mold temperature of 40 ° C, injection speed of 25 mm / s, holding pressure of 30 MPa, holding pressure of 10 sec. The distance at which the flow mark can be visually observed was measured.

(11) Mirror surface gloss Molded at a molding temperature of 210 ° C. and a mold temperature of 40 ° C. The length of the molded product is 130 mm, the width is 120 mm, and the thickness is 3 mm. The surface of the molded product is irradiated with a light source by a gloss meter (NDH-300 manufactured by Nippon Denshoku Industries Co., Ltd.). The specular gloss was measured at an angle of 60 °.

(12) Scratch resistance Ford 5-Finger Test using a molded product with a molding temperature of 210 ° C., a mold temperature of 40 ° C., a length of 130 mm, a width of 120 mm, and a thickness of 2 mm, and the surface of the square plate is subjected to grain C graining. Thus, the maximum load (N) at which no whitening was visually observed was evaluated.

[Propylene / ethylene block copolymers A and B]
Propylene / ethylene block copolymers (A-1) to (A-11), (B-1) and (B-2) shown in Table 1 were produced. (A-1) to (A-6) correspond to the propylene / ethylene block copolymer A, and (A-7) to (A-11) are comparative copolymers. (B-1) corresponds to propylene / ethylene block copolymer B, and (B-2) is a comparative copolymer thereof.

Production Example A-1
(1) Preparation of solid titanium catalyst component 952 g of anhydrous magnesium chloride, 4420 ml of decane and 3906 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to obtain a homogeneous solution. To this solution was added 213 g of phthalic anhydride, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.
After cooling the homogeneous solution thus obtained to 23 ° C., 750 ml of this homogeneous solution was dropped into 2000 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 52.2 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours. Held on. Next, the solid part was collected by hot filtration, and the solid part was resuspended in 2750 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours.
After the heating, the solid part was again collected by hot filtration, and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.
The solid titanium catalyst component prepared as described above was stored as a hexane slurry. A part of the catalyst was dried to examine the catalyst composition. The solid titanium catalyst component contained 2% by weight of titanium, 57% by weight of chlorine, 21% by weight of magnesium and 20% by weight of DIBP.

(2) Preparation of prepolymerization catalyst 87.5 g of solid titanium catalyst component, 99.8 mL of triethylaluminum, 28.4 ml of diethylaminotriethoxysilane, and 12.5 L of heptane were inserted into an autoclave with a stirrer having an internal volume of 20 L, and an internal temperature of 15 875 g of propylene was inserted while maintaining the temperature at ˜20 ° C., and reacted while stirring for 100 minutes. After completion of the polymerization, the solid component was allowed to settle, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 0.7 g / L.

(3) Main polymerization In a jacketed circulation tubular polymerizer with an internal capacity of 58 L, propylene is 40 kg / hour, hydrogen is 170 NL / hour, the catalyst slurry produced in (2) is 0.34 g / hour as a solid catalyst component, triethylaluminum 2.3 ml / hour and diethylaminotriethoxysilane 0.93 ml / hour were continuously fed, and polymerization was carried out in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.5 MPa / G.
The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. To the polymerization vessel, propylene was supplied at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 5.8 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.3 MPa / G.
The obtained slurry was transferred to a transfer tube having an internal volume of 2.4 L, and the slurry was gasified and subjected to gas-solid separation to obtain a polypropylene homopolymer powder. Homopolymer powder was fed to carry out ethylene / propylene copolymerization. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization vessel is ethylene / (ethylene + propylene) = 0.39 (molar ratio) and hydrogen / ethylene = 0.071 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.1 MPa / G.
The resulting propylene / ethylene block copolymer was vacuum dried at 80 ° C.

Production Example A-2
In the main polymerization, propylene, ethylene, hydrogen so that the gas composition in the gas phase polymerization vessel is ethylene / (ethylene + propylene) = 0.31 (molar ratio) and hydrogen / ethylene = 0.052 (molar ratio). Was carried out in the same manner as in Production Example A-1, except that was continuously fed.

Production Example A-3
In the main polymerization, propylene, ethylene, hydrogen so that the gas composition in the gas phase polymerizer is ethylene / (ethylene + propylene) = 0.32 (molar ratio) and hydrogen / ethylene = 0.094 (molar ratio). Was carried out in the same manner as in Production Example A-1, except that was continuously fed.

Production Example A-4
In the main polymerization, propylene, ethylene, hydrogen so that the gas composition in the gas phase polymerizer is ethylene / (ethylene + propylene) = 0.47 (molar ratio) and hydrogen / ethylene = 0.086 (molar ratio). Was carried out in the same manner as in Production Example A-1, except that was continuously fed.

Production Example A-5
The production of the solid catalyst and the production of the prepolymerized catalyst were the same as in Production Example A-1 (1) (2).
For the main polymerization, a jacketed circulation type tubular polymerizer having an internal volume of 58 L was charged with 40 kg / hour of propylene, 97 NL / hour of hydrogen, 0.34 g / hour of the catalyst slurry produced in (2) as a solid catalyst component, and triethylaluminum 2 .2 ml / hour, diethylaminotriethoxysilane 0.88 ml / hour was continuously fed, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.4 MPa / G.
The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. To the polymerization reactor, propylene was supplied at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 2.8 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.1 MPa / G.
The obtained slurry was transferred to a transfer tube having an internal volume of 2.4 L, and the slurry was gasified and subjected to gas-solid separation to obtain a polypropylene homopolymer powder. Homopolymer powder was fed to carry out ethylene / propylene copolymerization. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization vessel is ethylene / (ethylene + propylene) = 0.33 (molar ratio) and hydrogen / ethylene = 0.122 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.1 MPa / G.
The resulting propylene / ethylene block copolymer was vacuum dried at 80 ° C.

Production Example A-6
In the main polymerization, propylene, ethylene, hydrogen so that the gas composition in the gas phase polymerizer is ethylene / (ethylene + propylene) = 0.36 (molar ratio) and hydrogen / ethylene = 0.086 (molar ratio). Was carried out in the same manner as in Production Example A-1, except that was continuously fed.

Production Example A-7
In the main polymerization, propylene, ethylene, hydrogen so that the gas composition in the gas phase polymerizer is ethylene / (ethylene + propylene) = 0.10 (molar ratio) and hydrogen / ethylene = 0.160 (molar ratio). Was carried out in the same manner as in Production Example A-1, except that was continuously fed.

Production Example A-8
In the main polymerization, propylene, ethylene, hydrogen so that the gas composition in the gas phase polymerizer is ethylene / (ethylene + propylene) = 0.35 (molar ratio) and hydrogen / ethylene = 0.134 (molar ratio). Was carried out in the same manner as in Production Example A-1, except that was continuously fed.

Production Example A-9
The production of the solid catalyst and the production of the prepolymerized catalyst were the same as in Production Example A-1 (1) (2).
For the main polymerization, propylene is 40 kg / hour, hydrogen is 186 NL / hour, and the catalyst slurry produced in (2) is 0.33 g / hour, triethylaluminum 2 .2 ml / hour, diethylaminotriethoxysilane 0.88 ml / hour was continuously fed, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 69 ° C., and the pressure was 3.4 MPa / G.
The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. To the polymerization reactor, propylene was supplied at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 6.0 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.2 MPa / G.
The obtained slurry was transferred to a transfer tube having an internal volume of 2.4 L, and the slurry was gasified and subjected to gas-solid separation to obtain a polypropylene homopolymer powder. Homopolymer powder was fed to carry out ethylene / propylene copolymerization. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization reactor is ethylene / (ethylene + propylene) = 0.33 (molar ratio) and hydrogen / ethylene = 0.094 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.1 MPa / G.
The resulting propylene / ethylene block copolymer was vacuum dried at 80 ° C.

Production Example A-10
In the main polymerization, propylene, ethylene, hydrogen so that the gas composition in the gas phase polymerizer is ethylene / (ethylene + propylene) = 0.54 (molar ratio) and hydrogen / ethylene = 0.086 (molar ratio). Was carried out in the same manner as in Production Example A-1, except that was continuously fed.

Production Example A-11
In the main polymerization, propylene, ethylene, hydrogen so that the gas composition in the gas phase polymerizer is ethylene / (ethylene + propylene) = 0.33 (molar ratio) and hydrogen / ethylene = 0.079 (molar ratio). Was carried out in the same manner as in Production Example A-1, except that was continuously fed.

Production Example B-1
(1) Preparation of solid titanium catalyst component 952 g of anhydrous magnesium chloride, 4420 ml of decane and 3906 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to obtain a homogeneous solution. To this solution, 213 g of phthalic anhydride was added, and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.
After cooling the homogeneous solution thus obtained to 23 ° C., 750 ml of this homogeneous solution was dropped into 2000 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 52.2 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours. Held on. Next, the solid part was collected by hot filtration, and the solid part was resuspended in 2750 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours.
After the heating, the solid part was again collected by hot filtration, and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.
The solid titanium catalyst component prepared as described above was stored as a hexane slurry. A part of the catalyst was dried to examine the catalyst composition. The solid titanium catalyst component contained 2% by weight of titanium, 57% by weight of chlorine, 21% by weight of magnesium and 20% by weight of DIBP.

(2) Production of pre-polymerization catalyst First, 2 L of heptane was charged into a reaction tank equipped with a stirrer with an internal volume of 14 L, and 53.4 mL of triethylaluminum, 18.3 mL of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 60 g of the solid titanium catalyst component prepared in (1) was charged, and heptane was added so that the amount of heptane was 6.5 L. After maintaining the internal temperature at 10 ° C. or lower and stirring for 10 minutes, 560 g of propylene was charged over about 50 minutes, and then reacted with stirring for 60 minutes. After completion of the polymerization, the solid component was allowed to settle, and the supernatant was removed and washed with heptane twice. The obtained prepolymerized catalyst was transferred to a reaction tank equipped with an internal volume 200 L stirrer, and then adjusted with heptane so that the solid catalyst component concentration was 0.8 g / L. This prepolymerized catalyst contained 10 g of polypropylene per 1 g of the solid catalyst component.

(3) Main polymerization 70 L of propylene, 6.0 mL of triethylaluminum, and 2.2 mL of dicyclopentyldimethoxysilane were charged into a vessel polymerization vessel with a stirrer having an internal volume of 100 L. The temperature was 60 ° C., and hydrogen was supplied so that the hydrogen concentration in the gas phase was 16.4 mol%. 0.8 g of the catalyst slurry produced in the above (2) was charged as a solid catalyst component, and polymerization was started. Polymerization was performed for 1 hour while supplying a polymerization temperature of 60 ° C., a pressure of 3.2 MPa / G, and hydrogen so that the hydrogen concentration in the gas phase was 16.4 mol%.
The obtained slurry was gasified and subjected to gas-solid separation to obtain a polypropylene homopolymer powder, and then the entire amount of the polypropylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L to carry out ethylene / propylene copolymerization. . Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor would be ethylene / (ethylene + propylene) = 0.17 molar ratio and hydrogen / ethylene = 0.002 molar ratio. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.75 MPa / G for 4.0 hours, and 27 kg of a propylene / ethylene block polymer was obtained.
The resulting propylene / ethylene block copolymer was vacuum dried at 80 ° C.

Production Example B-2
The production of the solid catalyst and the production of the prepolymerized catalyst were the same as in Production Example B-1 (1) (2).
For the main polymerization, 70 L of propylene, 6.0 mL of triethylaluminum, and 2.2 mL of dicyclopentyldimethoxysilane were charged into a vessel polymerization apparatus with a stirrer having an internal volume of 100 L. The temperature was 60 ° C., and hydrogen was supplied so that the hydrogen concentration in the gas phase was 16.4 mol%. 0.8 g of the catalyst slurry produced in the above (2) was charged as a solid catalyst component, and polymerization was started. Polymerization was performed for 1 hour while supplying a polymerization temperature of 60 ° C., a pressure of 3.2 MPa / G, and hydrogen so that the hydrogen concentration in the gas phase was 16.4 mol%.
The obtained slurry was gasified and subjected to gas-solid separation to obtain a polypropylene homopolymer powder, and then the entire amount of the polypropylene homopolymer powder was transferred to a gas phase polymerization vessel having an internal volume of 480 L to carry out ethylene / propylene copolymerization. . Propylene, ethylene, and hydrogen were supplied so that the gas composition in the gas phase polymerization reactor would be ethylene / (ethylene + propylene) = 0.18 molar ratio and hydrogen / ethylene = 0.007 molar ratio. Polymerization was carried out for 1.1 hours at a polymerization temperature of 70 ° C. and a pressure of 0.75 MPa / G, and 27 kg of a propylene / ethylene block polymer was obtained.
The resulting propylene / ethylene block copolymer was vacuum dried at 80 ° C.

Examples 1-13, Comparative Examples 1-15
As shown in Tables 2 to 5, each component was blended and dry blended with a tumbler. The obtained mixture was kneaded with a twin-screw extruder (trade name: TEX, manufactured by Nippon Steel) to produce polypropylene resin composition pellets. The kneading conditions were a kneading temperature of 180 ° C., a screw rotation speed of 600 rpm, and a discharge rate of 50 kg / h.
The obtained pellets were molded into the evaluation item samples described above by injection molding and evaluated. The results are shown in Tables 2-5.

About the component (A) and (B) in a table | surface, the copolymer manufactured by the manufacture example mentioned above was used (refer Table 1). The following commercially available products were used for components (C) to (F) and others.
J-3000GV: Homopolypropylene (manufactured by Prime Polymer Co., Ltd., product name: J-3000GV) MFR = 30 g / 10 min, room temperature decane soluble part: 0% by weight
Component (C): ethylene-α / olefin copolymer (C-1) ethylene-octene random copolymer (product name: EG8200, manufactured by Dow Elastomer Co., Ltd.)
MFR = 9 g / 10 min, α-olefin (octene) content: 37.4% by weight
(C-2) Ethylene-butene random copolymer (Mitsui Chemicals product name: A4050S)
MFR = 8 g / 10 min, α-olefin (butene) content: 29.1% by weight

Ingredient (D): Inorganic filler Talc 1 (Product name: JM209 average particle diameter (laser diffraction): 5 μm, manufactured by Asada Flour Milling Co., Ltd.)
Talc 2 (Nippon Talc product name: UG agent average particle size (laser diffraction): 15 μm)

Component (E): acid-modified polypropylene (E-1) maleic anhydride-modified polypropylene (product name: Admer QX-100, manufactured by Mitsui Chemicals)
[Η] = 0.43 dl / g (measured at 135 ° C. with tetralin), maleic acid-modified group content = 3.0% by weight
(E-2) Maleic anhydride-modified polypropylene (product name: Umex 1010 manufactured by Sanyo Chemical Industries)
[Η] = 0.28 dl / g (measured at 135 ° C. with tetralin), maleic acid-modified group content = 4.5% by weight

Ingredient (F): Lubricant Erucamide (Product name: Neutron S)

Other additives Irganox 1010 (BASF Corp.) 0.1 parts by weight as an antioxidant, Irgafos 168 (BASF Corp.) 0.1 parts by weight, LA-52 (manufactured by ADEKA Corp.) 0.2 Part by weight, 0.1 part by weight of calcium stearate (Nippon Oil & Fats Co., Ltd.) as a lubricant, and 3 parts by weight of MB PPCM 802Y-307 (manufactured by Tokyo Ink Co., Ltd.) as a black pigment were blended.

  A molded product formed by molding the resin composition of the present invention can be used for automobile interior materials (instrument panels, pillars, door trims, etc.), home appliance parts, and the like. This molded product has a low glossiness and scratch resistance, such that the flow mark or the like is not noticeable. Therefore, it can be used as a product without providing a post-process such as painting or skin lamination.

Claims (7)

The following (A) component 100 weight part, (B) component 7-14 weight part, (C) component 7-20 weight part, (D) component 24-36 weight part, (E) component 0.1-3.5 A polypropylene resin composition containing parts by weight and 0.2 to 3.0 parts by weight of component (F).
(A) Propylene / ethylene block copolymer A satisfying the following (a1) to (d1), or a mixture of the copolymer A and homopolypropylene :
(A1) The room temperature decane soluble part is 16 wt% or more and 25 wt% or less (b1) The ethylene content of the room temperature decane soluble part is 45 mol% or more and 65 mol% or less (c1) The intrinsic viscosity of the room temperature decane soluble part [η ] Is 2.4 dl / g or more and 4.0 dl / g or less (d1) Melt flow rate (MFR: 230 ° C., under 2.16 kg load) is 10 g / 10 min or more and 53 g / 10 min or less
The melt flow rate (MFR: 230 ° C., under a load of 2.16 kg) of the homopolypropylene is 10 g / 10 min or more and 53 g / 10 min or less,
The addition amount of homopolypropylene in the mixture of copolymer A and homopolypropylene is 15 to 35% by weight based on the total of copolymer A and homopolypropylene,
The mixture of the copolymer A and homopolypropylene satisfies the above (a1) to (d1).
(B) Propylene / ethylene block copolymer B satisfying the following (a2) to (d2):
(A2) Room temperature decane soluble part: 36 wt% or more and 55 wt% or less (b2) Ethylene content of room temperature decane soluble part is 25 mol% or more and 35 mol% or less (c2) Intrinsic viscosity of room temperature decane soluble part [η ] Is 7.0 dl / g or more and 10.0 dl / g or less (d2) MFR (230 ° C., under 2.16 kg load) is 0.08 g / 10 min or more and 2.0 g / 10 min or less (C) MFR (230 ° C. Inorganic filler (E) acid having an average particle diameter of 1 μm or more and 14 μm or less, and an ethylene / α-olefin copolymer (D) having a load of 2.16 kg and a weight of 0.8 g / 10 min to 20 g / 10 min Modified polypropylene (F) fatty acid amide   The polypropylene resin composition according to claim 1, wherein the room temperature decane-soluble part (a2) of the component (B) is 40 wt% or more and 55 wt% or less.   The room temperature decane soluble part of the component (A) is from 16% by weight to 20% by weight, the room temperature decane soluble part of the component (B) is from 40% by weight to 47% by weight, The polypropylene resin composition according to claim 1 or 2, wherein the amount of the component is 7 to 15 parts by weight.   The polypropylene resin composition according to any one of claims 1 to 3, wherein the inorganic filler (D) is talc. MFR (230 degreeC, 2.16kg load) is 10 g / 10min or more and 45 g / 10min or less, The polypropylene resin composition in any one of Claims 1-4 . A molded product formed by molding the polypropylene resin composition according to any one of claims 1 to 5 . The molded article according to claim 6 , which is used for an instrument panel of an automobile.