JP2001019825A - Propylene/ethylene block copolymer composition excellent in weather resistance and molding prepared by molding the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a block copolymer composition balanced between rigidity and impact resistance and being excellent in weather resistance by compounding a propylene/ethylene block copolymer with at least one compound selected from a weathering agent and a colorant. SOLUTION: This composition is prepared by compounding 100 pts.wt. (A) propylene/ ethylene block copolymer with 0.005-5 pts.wt. (B) weathering agent such as a hindered amide light stabilizer or a benzophenone ultraviolet absorber and a colorant and 0.001-1 pt.wt. dispersant such as a fatty acid metal salt. Component A has a melt flow rate of 0.01-1,000 g/10 min (as measured at 230 deg.C under a load of 2.16 kg) and a stereoregularity index fraction of at least 98.9% (a measured on a fraction insoluble in xylene at ordinary temperature by 13C-NMR spectroscopy). Further, it is one which has a content of a fraction soluble in xylene at ordinary temperature of 3-50 wt.%, in which the component having a T1 relaxation time as measured by pulsed NMR spectroscopy comprises a single relaxation component, and which satisfies the relationships [wherein y (millisecond) is the T1 relaxation time as measured by pulsed NMR spectroscopy and x (wt.%) is the ethylene content as determined by 13C-NMR spectroscopy].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene-ethylene block copolymer composition and a molded article obtained by molding the same. To a propylene-ethylene block copolymer composition and a molded article obtained by molding the same.

[0002]

2. Description of the Related Art Many attempts have been made to improve propylene-ethylene block copolymers with the aim of improving the balance between physical properties such as rigidity and impact resistance. There is an examination from.
That is, the influence on the strength physical properties that a solid structure composed of a propylene homopolymer portion forming the matrix of the copolymer and an ethylene-propylene copolymer portion forming the rubber-like elastic body is expressed, the respective component amounts, This is captured by the polymerization factors such as molecular weight and stereoregularity of each part, reflected in the polymer design, and fed back to the polymerization technology for producing the polymer.

As a result of these studies, it has become clear that the size of the molecular weight of the ethylene-propylene copolymer forming the rubber-like elastic body has a dominant effect on the balance of physical properties such as rigidity and impact resistance. Was. However, there is a long-awaited demand for an improved product that is further improved, especially in which impact resistance is improved. Further, the propylene-ethylene copolymer also needs to further improve the weather resistance.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a propylene-ethylene block copolymer composition having good balance of physical properties such as rigidity and impact resistance and excellent weatherability, and a molded article obtained by molding the same. It is intended to provide.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies and as a result, have found that a novel propylene resin satisfying specific conditions has been obtained.
The present invention has been accomplished by finding that a composition obtained by blending a weathering agent or a coloring agent with an ethylene block copolymer is suitable for this purpose. That is, the gist of the present invention is as follows. 1. (I) Propylene obtained by blending (ii) at least one compound selected from an antioxidant and an antirust agent with a propylene-ethylene block copolymer having the properties shown in (a) to (c) below. -An ethylene block copolymer composition. (A) Melt flow rate (MFR) (230 ° C, 2.
(16 kg load) is 0.01 to 1,000 g / 10 min, and (b) the stereoregularity index [mmmm] fraction measured by ¹³ C-NMR of the insoluble component at room temperature is 98.9% or more; (C) The component soluble in xylene at normal temperature is the following (c1) to
It satisfies the condition of (c3). (C1) 3 to 50% by weight, (c2) pulse N
(1) The T1 relaxation time component measured by MR is composed of a single relaxation component. (C3) T1 relaxation time y (millisecond) measured by pulse NMR, with the ethylene content measured by ¹³ C-NMR being x wt%. Satisfy the following relational expression. ^{y ≦ 0.0014x 3 -0.0897x 2 -1.0593x +} 231.6 ··· (1) 2. The total amount of component (ii) is 100
2. The propylene-ethylene block copolymer composition according to the above 1, wherein the amount is 0.005 to 2 parts by weight with respect to parts by weight. 3. The propylene-ethylene block copolymer composition according to the above 1 or 2, further comprising (iii) a heavy metal deactivator and / or (iv) a radical generator. 4. (I) Melt flow rate (MFR) of component (23)
The propylene-ethylene block copolymer composition according to any one of the above items 1 to 3, wherein the composition has a pressure of 0.3 to 300 g / 10 minutes at 0 ° C and a load of 2.16 kg). 5. (Ii) an ultraviolet absorber selected from (a) a hindered amine-based light stabilizer, (b) a benzotriazole-based, a benzophenone-based, an oxalic acid anilide-based, a formamidine-based, and a triazine ring-based, among the components (ii); The propylene-ethylene block copolymer composition according to any one of the above items 1 to 4, which is (c) a hydroxybenzoate-based light stabilizer or (d) a nickel-based quencher. 6. (Ii) a colorant among the components, (e) an inorganic pigment,
The propylene-ethylene block copolymer composition according to any one of the above 1 to 5, which is (f) an organic pigment, (g) an extender or (h) a dye. 7. A molded article obtained by molding the propylene-ethylene block copolymer composition according to any one of the above 1 to 6.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The propylene-ethylene block copolymer of component (i), which is a component of the present invention, is a composition comprising a propylene homopolymer as a main component, and an ethylene-propylene copolymer and an ethylene homopolymer, Typically, it can be produced by propylene-ethylene block copolymerization, but is not limited thereto, and may be a blend of the above polymers.

The most significant feature of the propylene-ethylene block copolymer (i) constituting the present invention is that the ethylene-propylene copolymer portion is occupied by a uniform rubber-like elastic material, and as a result, rigidity and other physical properties are reduced. The object is to form a block copolymer with improved impact resistance without loss. The propylene component (i) constituting the present invention
The ethylene block copolymer has a melt flow rate (M
FR) (230 ° C, 2.16 kg load) is 0.01 to
1,000 g / 10 min, preferably 0.3 to 30
0 g / 10 minutes. If it is less than 0.01 g / 10 minutes, molding is difficult, and if it is more than 1,000 g / 10 minutes, the physical strength is insufficient.

The propylene-ethylene block copolymer has a stereoregularity index [mmmm] fraction of 98.9% or more as measured by ¹³ C-NMR at room temperature. The details of the ¹³ C-NMR measurement method of the insoluble component at room temperature will be described later. The normal-temperature xylene-insoluble component is mainly a propylene homopolymer component, and the stereoregularity index [mmmm] fraction obtained by this measurement method is also referred to as an isotactic pentad fraction. It is the ratio of propylene monomer units that are present in five consecutive meso bonds in all propylene monomer units. Therefore, the higher the isotactic pentad fraction, the higher the proportion occupied by polypropylene having an isotactic structure. If the stereoregularity index [mmmm] fraction is less than 98.9%, rigidity, surface height, and heat resistance are inferior, which is not preferable.

In the propylene-ethylene block copolymer (i) constituting the present invention, the amount of the soluble component must be 3 to 50% by weight based on the xylene soluble component at normal temperature. The normal temperature xylene-soluble component is mainly an ethylene-propylene copolymer component. If the amount of the soluble component is less than 3% by weight, impact resistance is insufficient, and 50% by weight.
If it is larger, rigidity, surface height and heat resistance are inferior, which is not preferable.

Further, the propylene-ethylene block copolymer, which is the component (i) constituting the present invention, is obtained by first measuring T x of the xylene-soluble component at room temperature by pulse NMR.
One relaxation time component consists of a single relaxation component; and
T1 relaxation time y (millisecond) measured by pulse NMR, with the ethylene content measured by ¹³ C-NMR being x wt%
Satisfies the following relational expression. y ≦ 0.0014x ³ −0.0897x ² −1.0593x + 231.6 (1) The normal temperature xylene-soluble component is mainly an ethylene-propylene copolymer component and does not contain crystalline polyethylene. The method of measuring the T1 relaxation time measured by pulsed NMR will be described later, but the technical meaning is that the nuclear magnetic moment of the sample excited by irradiating an electromagnetic wave of a predetermined frequency with a pulse returns to the original state. The magnitude of the time indicates the level of molecular mobility of the sample. A small T1 corresponds to a low frequency range of molecular motion of the sample. The high impact resistance of a sample having a small T1 indicates that the time scale of the measurement of the impact test is close to the frequency range.

The fact that the T1 relaxation time component is a single component means that it has properties close to a uniform component. That is, the expression (1) means that the ethylene-propylene copolymer has a low frequency range of molecular motion with respect to the ethylene concentration, and is composed of a rubber-like elastic body close to a single component. The horizontal axis of the measurement result indicates the variable time τ (the irradiation time interval between the 180 ° pulse and the 90 ° pulse), and the vertical axis indicates the signal intensity M after the 90 ° pulse irradiation.
When plotting by taking ln {M (∞) -M (τ)} as (τ), T1 is given by a negative reciprocal value of the slope (downward to the right) of the straight line. Here, when T1 is small, the slope of the relaxation time is large, and the decay time is shorter. Further, when the line connecting the plotted points is composed of a plurality of straight lines having different slopes, the line is composed of a plurality of components. Therefore, it is necessary to constitute a single component to be a single component. .

[0012] The propylene-ethylene copolymer of the component (i) constituting the present invention is characterized in that the component soluble at room temperature xylene has a single T1 relaxation time component measured by pulsed NMR,
Poor impact strength. If the formula (I) is not satisfied, the impact strength decreases. The propylene-ethylene block copolymer shown above is a polymer in an unprecedented new territory, and its physical properties include rigidity and impact resistance, Rockwell hardness and impact resistance, heat deformation temperature and impact resistance. The balance of physical properties such as strength is balanced at a high level.

Next, a method for producing the propylene-ethylene block copolymer as the component (i) constituting the present invention will be described. The propylene component (i) constituting the present invention
If the ethylene block copolymer satisfies the above properties,
Although not limited to the production method, a polymer having a propylene homopolymer having high stereoregularity and excellent in copolymerizability with ethylene, particularly, having an MFR of 0.1.
In order to obtain a high molecular weight product of about 3 to 300 g / 10 minutes, it is preferable to use a Ziegler type catalyst rather than using a metallocene catalyst. Specifically, for example, (A) (a)
A solid catalyst component formed from a titanium compound, (b) a magnesium compound, (c) an electron donor, and optionally (d) a silicon compound, (B) an organoaluminum compound, and optionally (C) ) A catalyst comprising an electron-donating compound as the third component and a method of polymerizing using the catalyst. In particular, in the method for preparing a solid catalyst component used in the present invention, a magnesium compound and a titanium compound are brought into contact with each other at 120 to 150 ° C. in the presence of an electron-donating compound and, if necessary, a silicon compound, and then, It is preferred to wash at 150 ° C. with an inert solvent.

Hereinafter, each catalyst component, a preparation method, a polymerization method, and the like will be described. Each catalyst component (A) Solid catalyst component The solid catalyst component is formed from the following (a) a titanium compound, (b) a magnesium compound, (c) an electron donor, and if necessary, (d) a silicon compound. Things.

(A) Titanium Compound The titanium compound is not particularly limited, but a titanium compound represented by the general formula (I) TiX ¹ _p (OR ¹ ) _4-p (I) is preferably used. Can be. In the above general formula (I), X ¹ represents a halogen atom, among which a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. R ¹ is a hydrocarbon group, which may be a saturated group or an unsaturated group, a linear group, a branched group, or a cyclic group; , Oxygen, silicon, phosphorus and the like. Preferably, a hydrocarbon group having 1 to 10 carbon atoms, particularly an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and the like are preferable, and a linear or branched alkyl group is particularly preferable. When a plurality of OR ¹ are present, they may be the same or different. Specific examples of R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, Examples thereof include n-octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group, phenethyl group and the like. p shows the integer of 0-4.

Specific examples of the titanium compound represented by the above general formula (I) include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium,
Tetraalkoxy titanium such as tetraisobutoxytitanium, tetracyclohexyloxytitanium, tetraphenoxytitanium; titanium tetrahalide such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide; methoxytitanium trichloride, ethoxytitanium trichloride, propoxy Alkoxy titanium trihalides such as titanium trichloride, n-butoxy titanium trichloride, ethoxy titanium tribromide; dimethoxy titanium dichloride, diethoxy titanium dichloride, diisopropoxy titanium dichloride, di-n-propoxy titanium dichloride, diethoxy titanium dichloride Dihalogenated dialkoxytitanium such as bromide; trimethoxytitanium chloride, triethoxytitanium chloride, triisopropoxytitanium chloride, tri-n-propoxytitanium chloride De, etc. monohalogenated trialkoxy titanium such as tri -n- butoxy titanium chloride can be exemplified. Among these, a titanium compound having a high halogen content, particularly titanium tetrachloride, is preferred from the viewpoint of polymerization activity. These titanium compounds may be used alone or in combination of two or more.

(B) Magnesium compound The magnesium compound is not particularly limited, but is generally
Formula (II) MgR^TwoR^Three ... It is preferable to use a magnesium compound represented by the formula (II).
it can. In the above general formula (II), R^TwoAnd R^Three
Is a hydrocarbon group, OR^FourGroup (R ^FourIs a hydrocarbon group) or
Indicates a halogen atom. Where R^TwoAnd R^ThreeThe hydrocarbon
As the elementary group, an alkyl group having 1 to 12 carbon atoms, cyclo
When an alkyl group, an aryl group, an aralkyl group, etc.^FourBase
As R^FourIs an alkyl group having 1 to 12 carbon atoms,
Roalkyl, aryl, aralkyl, etc.
Examples of chlorine atoms include chlorine, bromine, iodine, and fluorine.
Can be Also, R^TwoAnd R^ThreeAre the same but different
May be.

Specific examples of the magnesium compound represented by the general formula (II) include dimethylmagnesium, diethylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium, diphenylmagnesium and dicyclohexylmagnesium. Alkylmagnesium, arylmagnesium; alkoxymagnesium such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dihexyloxymagnesium, dioctoxymagnesium, diphenoxymagnesium, dicyclohexyloxymagnesium, etc .; alloxymagnesium; ethylmagnesium Chloride, butylmagnesium chloride, hex Le chloride, isopropyl magnesium chloride, isobutyl magnesium chloride, t- butyl magnesium chloride, phenyl magnesium bromide, benzyl magnesium chloride,
Alkyl magnesium halides such as ethyl magnesium bromide, butyl magnesium bromide, phenyl magnesium chloride, and butyl magnesium iodide, aryl magnesium halides; butoxymagnesium chloride, cyclohexyloxymagnesium chloride, phenoxymagnesium chloride, ethoxymagnesium bromide, butoxymagnesium bromide, ethoxymagnesiumiodide Examples thereof include alkoxymagnesium halides such as dyed and allyloxymagnesium halides; and magnesium halides such as magnesium chloride, magnesium bromide and magnesium iodide.

Among these magnesium compounds, from the viewpoint of polymerization activity and stereoregularity, magnesium halide, alkoxymagnesium, alkylmagnesium,
Alkyl magnesium halides can be suitably used. The above magnesium compound can be prepared from metallic magnesium or a compound containing magnesium. One example is a method in which halogen and alcohol are brought into contact with metallic magnesium. Here, examples of the halogen include iodine, chlorine, fluorine, and bromine. Examples of the alcohol include methanol, ethanol, propanol, butanol, cyclohexanol, octanol and the like.

As another example, Mg (OR ⁵ ) ₂
In magnesium represented alkoxy compound (wherein, R ⁵
Represents a hydrocarbon group having 1 to 20 carbon atoms. ) May be contacted with a halide. Examples of the halide include silicon tetrachloride, silicon tetrabromide, tin tetrachloride, tin tetrabromide, and hydrogen chloride.
Among them, silicon tetrachloride is preferred from the viewpoint of polymerization activity and stereoregularity. As the above R ⁵ , methyl, ethyl, n-propyl, isopropyl, n-
Alkyl groups such as butyl group, isobutyl group, hexyl group, octyl group and cyclohexyl group; alkenyl groups such as propenyl group and butenyl group; aryl groups such as phenyl group, tolyl group and xylyl group; phenethyl group and 3-phenylpropyl group And the like. Further, the magnesium compound may be supported on a support such as silica, alumina, and polystyrene. The above magnesium compounds may be used alone or in combination of two or more. Further, it may contain halogen such as iodine or other elements such as silicon or aluminum, and may contain an electron donor such as alcohol, ether or ester.

(C) Electron Donor Examples of the electron donor include alcohols, phenols, ketones, aldehydes, esters of organic or inorganic acids, and ethers such as monoether, diether and polyether. Oxygen electron donors, ammonia,
Examples include nitrogen-containing electron donors such as amines, nitriles, and isocyanates. Among these, esters of polycarboxylic acids are preferred, and esters of aromatic polycarboxylic acids are more preferred. From the viewpoint of polymerization activity, monoesters and diesters of aromatic dicarboxylic acids are particularly preferred. Further, an aliphatic hydrocarbon in which the organic group in the ester portion is linear, branched or cyclic is preferred.

Specific examples include dialkyl esters of dicarboxylic acids. In that case, as the dicarboxylic acid, phthalic acid, naphthalene-1,2-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, 5,6,7,
8-tetrahydronaphthalene-1,2-dicarboxylic acid,
5,6,7,8-Tetrahydronaphthalene-2,3-dicarboxylic acid, indane-4,5-dicarboxylic acid, indane-5,6-dicarboxylic acid and the like can be mentioned. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1
-Methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-
Ethylbutyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl Pentyl, 3-methylpentyl, 2-ethylpentyl, 3-ethylpentyl and the like can be mentioned. Among these, phthalic acid diesters are preferred. Specific examples thereof include di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, and diethyl phthalate. Further, these compounds may be used alone,
Two or more kinds may be used in combination.

(D) Silicon compound In the preparation of the solid catalyst component, in addition to the above components (a), (b) and (c), if necessary, as a component (d),
Formula (III) Si (OR ⁶⁾ silicon compound represented by _{^{q X 2 4-q ··· (}} III) can be used. By using a silicon compound, the catalytic activity and stereoregularity can be improved, and the amount of fine powder in the produced polymer can be reduced.

In the above formula (III), X ² represents a halogen atom, of which a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred. R ⁶ is a hydrocarbon group, which may be a saturated group or an unsaturated group, a linear group, a branched group, or a cyclic group; , Oxygen, silicon, phosphorus and the like. Preferably a hydrocarbon group having 1 to 10 carbon atoms, particularly an alkyl group,
Alkenyl, cycloalkenyl, aryl and aralkyl are preferred. When a plurality of OR ⁶ are present, they may be the same or different. Specific examples of R ⁶ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl,
Examples include n-heptyl group, n-octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group, phenethyl group and the like. q shows the integer of 0-3.

Specific examples of the silicon compound represented by the above general formula (III) include silicon tetrachloride, methoxytrichlorosilane, dimethoxydichlorosilane, trimethoxychlorosilane, ethoxytrichlorosilane, diethoxydichlorosilane, triethoxychlorosilane, Examples thereof include propoxytrichlorosilane, dipropoxydichlorosilane, and tripropoxychlorosilane. Among these, silicon tetrachloride is particularly preferred. These silicon compounds may be used alone or in combination of two or more.

(B) Organoaluminum Compound The (B) organoaluminum compound used in the present invention is not particularly limited, but may be an alkyl group, a halogen atom,
Those having a hydrogen atom and an alkoxy group, aluminoxanes, and mixtures thereof can be preferably used.
Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, and trioctylaluminum; dialkyls such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, and dioctylaluminum monochloride Aluminum monochloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride; and chained aluminoxanes such as methylaluminoxane. Among these organoaluminum compounds, trialkylaluminum having a lower alkyl group having 1 to 5 carbon atoms,
Particularly, trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferred. These organoaluminum compounds may be used alone or in combination of two or more.

(C) Electron Donating Compound as Third Component In order to produce the polymer of component (i) of the present invention, (C) an electron donating compound as the third component is polymerized, if necessary. Sometimes added. As the electron-donating compound (C) as the third component, an organic silicon compound having a Si—O—C bond, a nitrogen-containing compound, a phosphorus-containing compound, and an oxygen-containing compound can be used. Among these, from the viewpoint of polymerization activity and stereoregularity, it is preferable to use an organic silicon compound having a Si-OC bond, ethers and esters, and particularly to use an organic silicon compound having a Si-OC bond. Is preferred.

Specific examples of the organosilicon compound having a Si—O—C bond include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, Triethylethoxysilane, ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-
t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-
Butylpropyldimethoxysilane, t-butylisopropyldimethoxysilane, t-butylbutyldimethoxysilane, t-butylisobutyldimethoxysilane, t-butyl (s-butyl) dimethoxysilane, t-butylamyldimethoxysilane, t-butylhexyldimethoxysilane , T-butylheptyldimethoxysilane, t-butyloctyldimethoxysilane, t-butylnonyldimethoxysilane, t-butyldecyldimethoxysilane, t-butyl
Butyl (3,3,3-trifluoromethylpropyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclopentyl-t
-Butyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3
-Dimethylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane,
Methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane,
s-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornanetrimethoxysilane, indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyl (t- Butoxy) dimethoxysilane, isopropyl (t-butoxy) dimethoxysilane, t-butyl (isobutoxy) dimethoxysilane, t
-Butyl (t-butoxy) dimethoxysilane, texyltrimethoxysilane, texylisopropoxydimethoxysilane, texyl (t-butoxy) dimethoxysilane, texylmethyldimethoxysilane, texylethyldimethoxysilane, texylisopropyldimethoxysilane, Texylcyclopentyldimethoxysilane, texylmyristyldimethoxysilane, texylcyclohexyldimethoxysilane and the like can be mentioned. The following general formula (IV)

[0029]

Embedded image

(Wherein, R ^{7 to} R ^{9 each} represent a hydrogen atom or a hydrocarbon group, which may be the same or different from each other, or may be bonded to an adjacent group to form a ring. ¹⁰ and R ¹¹ represent a hydrocarbon group, which may be the same or different, and may be bonded to an adjacent group to form a ring, and R ¹² and R ¹³ have 1 to 1 carbon atoms.
And represents 20 alkyl groups, which may be the same or different from each other. m is an integer of 2 or more, and n is an integer of 2 or more. ) Can be used.

In the above formula (IV), specifically, R ^{7 to} R ⁹ represent a hydrogen atom, a linear hydrocarbon group such as a methyl group, an ethyl group or an n-propyl group, an isopropyl group, Branched hydrocarbon groups such as isobutyl group, t-butyl group and texyl group, cyclobutyl group, cyclopentyl group,
Examples include a saturated cyclic hydrocarbon group such as a cyclohexyl group and an unsaturated cyclic hydrocarbon group such as a phenyl group and a pentamethylphenyl group. Among these, hydrogen and a straight-chain hydrocarbon group having 1 to 6 carbon atoms are preferable, and hydrogen, a methyl group and an ethyl group are particularly preferable.

In the above general formula (IV), R ¹⁰ and R ¹¹ are linear hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group,
Examples include branched hydrocarbon groups such as t-butyl group and texyl group, saturated cyclic hydrocarbon groups such as cyclobutyl group, cyclopentyl group and cyclohexyl group, and unsaturated cyclic hydrocarbon groups such as phenyl group and pentamethylphenyl group. it can.
These may be the same or different. Among these, a linear hydrocarbon group having 1 to 6 carbon atoms is preferable, and a methyl group and an ethyl group are particularly preferable.

In the above general formula (IV), R ¹²
And R ¹³ are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
sec-butyl group, t-butyl group, n-pentyl group, n
Straight-chain or branched alkyl groups such as -hexyl group and n-octyl group. These may be the same or different. Among these, a linear hydrocarbon group having 1 to 6 carbon atoms is preferable, and a methyl group is particularly preferable.

Preferred examples of the silicon compound represented by the general formula (IV) include neopentyl n
-Propyldimethoxysilane, neopentyl n-butyldimethoxysilane, neopentyl n-pentyldimethoxysilane, neopentyl n-hexyldimethoxysilane, neopentyl n-heptyldimethoxysilane, isobutyl n-propyldimethoxysilane, isobutyl n-
Butyldimethoxysilane, isobutyl n-pentyldimethoxysilane, isobutyl n-hexyldimethoxysilane, isobutyl n-heptyldimethoxysilane, 2-cyclohexylpropyl n-propyldimethoxysilane,
2-cyclohexylbutyl n-propyldimethoxysilane, 2-cyclohexylpentyl n-propyldimethoxysilane, 2-cyclohexylhexyl n-propyldimethoxysilane, 2-cyclohexylheptyl n-propyldimethoxysilane, 2-cyclopentylpropyln
-Propyldimethoxysilane, 2-cyclopentylbutyl n-propyldimethoxysilane, 2-cyclopentylpentyl n-propyldimethoxysilane, 2-cyclopentylhexyl n-propyldimethoxysilane, 2-cyclopentylheptyl n-propyldimethoxysilane,
Isopentyl n-propyldimethoxysilane, isopentyl n-butyldimethoxysilane, isopentyl n-pentyldimethoxysilane, isopentyl n-hexyldimethoxysilane, isopentyl n-heptyldimethoxysilane, isopentylisobutyldimethoxysilane, isopentylneopentyldimethoxysilane, diiso Pentyl dimethoxy silane, diisoheptyl dimethoxy silane, diisohexyl dimethoxy silane and the like can be mentioned.

Specific examples of particularly preferred compounds include neopentyl n-propyldimethoxysilane, neopentyl n-pentyldimethoxysilane, isopentylneopentyldimethoxysilane, diisopentyldimethoxysilane, diisoheptyldimethoxysilane, and diisohexyldimethoxysilane. Specific examples of more preferable compounds include neopentyl n-pentyldimethoxysilane and diisopentyldimethoxysilane. The silicon compound represented by the general formula (IV) can be synthesized by an arbitrary method. A typical synthetic route is as follows.

[0036]

Embedded image

In this synthetic route, the starting compound [1]
Is commercially available or can be obtained by known alkylation, halogenation and the like. An organosilicon compound represented by the general formula (IV) can be obtained by subjecting compound [1] to a known Grignard reaction. The above organosilicon compounds may be used alone or in combination of two or more.

Specific examples of the nitrogen-containing compound include 2,6
-Diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine, N-methyl2,2,6,6-
2,6-substituted piperidines such as tetramethylpiperidine; 2,5 such as 2,5-diisopropylazolidine and N-methyl 2,2,5,5-tetramethylazolidine
-Substituted azolidines; substituted methylenediamines such as N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetraethylmethylenediamine;
Substituted imidazolidines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine can be mentioned.

Specific examples of the phosphorus-containing compound include triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, and diethyl phenyl phosphite. Phosphites such as fight; Specific examples of the oxygen-containing compound include 2,6-substituted tetrahydrofurans such as 2,2,6,6-tetramethyltetrahydrofuran and 2,2,6,6-tetraethyltetrahydrofuran;
And dimethoxymethane derivatives such as -dimethoxy-2,3,4,5-tetrachlorocyclopentadiene, 9,9-dimethoxyfluorene and diphenyldimethoxymethane.

Preparation of Solid Catalyst Component The method for preparing the solid catalyst component (A) includes the above (a) titanium compound, (b) magnesium compound,
The (c) electron donor and, if necessary, the (d) silicon compound may be brought into contact by a usual method except for the contact temperature conditions, and the contact procedure is not particularly limited. For example, each component may be contacted in the presence of an inert solvent such as a hydrocarbon, or each component may be contacted after being diluted with an inert solvent such as a hydrocarbon. Examples of the inert solvent include aliphatic hydrocarbons such as octane, decane, and ethylcyclohexane, alicyclic hydrocarbons, and mixtures thereof.

The titanium compound is usually added in an amount of 0.1 to 1 mol of magnesium of the above magnesium compound.
5 to 100 moles, preferably 1 to 50 moles are used.
If the molar ratio is outside the above range, the catalytic activity may be insufficient. The above electron donor is used in an amount of usually 0.01 to 10 mol, preferably 0.05 to 1.0 mol, per 1 mol of magnesium of the above magnesium compound.
Use 0 moles. If the molar ratio deviates from the above range, catalytic activity and stereoregularity may be insufficient. Further, when a silicon compound is used, it is usually used in an amount of 0.001 mol per mol of magnesium of the above magnesium compound.
It is used in an amount of 1 to 100 mol, preferably 0.005 to 5.0 mol. If the molar ratio deviates from the above range, the effect of improving catalytic activity and stereoregularity may not be sufficiently exhibited, and the amount of fine powder in the produced polymer may increase.

The above components (a) to (d) are contacted at 120 to 150 ° C., preferably 125 to 150 ° C. after all the components have been added.
This is performed in a temperature range of 140 ° C. If the contact temperature is outside the above range, the effect of improving the catalytic activity and stereoregularity will not be sufficiently exhibited. The contact is usually performed for 1 minute to 24 hours, preferably for 10 minutes to 6 hours. The pressure at this time is
When using a solvent, depending on its type, contact temperature, etc.
The range varies, but is usually 0-50 kg / cm
² G, preferably in the range of 0 to 10 kg / cm ² G. In addition, during the contact operation, it is preferable to perform stirring in view of uniformity of contact and contact efficiency.

Further, it is preferable that the contact with the titanium compound is performed twice or more to sufficiently support the magnesium compound which functions as a catalyst carrier. When a solvent is used in the contacting operation, it is usually 5000 ml or less, preferably 10 to 10 mol per 1 mol of the titanium compound.
Use 1,000 ml of solvent. If this ratio deviates from the above range, contact uniformity and contact efficiency may deteriorate.

The solid catalyst component obtained by the above contact is
Wash with an inert solvent at a temperature of 00-150 ° C, preferably 120-140 ° C. When the washing temperature is outside the above range, the effect of improving the catalytic activity and stereoregularity is not sufficiently exhibited. Examples of the inert solvent include aliphatic hydrocarbons such as octane and decane; alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane;
Aromatic hydrocarbons such as xylene, tetrachloroethane,
Halogenated hydrocarbons such as chlorofluorocarbons or mixtures thereof can be mentioned. Of these, aliphatic hydrocarbons are preferably used.

The washing method is not particularly limited, but is preferably a method such as decantation or filtration. There are no particular restrictions on the amount of the inert solvent used, the washing time, and the number of washings.
00 to 100,000 ml, preferably 1,
The reaction is usually performed for 1 minute to 24 hours, preferably for 10 minutes to 6 hours, using 000 to 50,000 ml of a solvent. If the ratio deviates from the above range, the cleaning may be incomplete.

The range of the pressure at this time varies depending on the type of the solvent, the washing temperature and the like.
g / cm ² G, preferably in the range of 0 to 10 kg / cm ² G. During the washing operation, it is preferable to perform stirring from the viewpoint of uniformity of washing and washing efficiency. Furthermore,
Washing is preferably repeated 5 times or more to be effective. The obtained solid catalyst component can be stored in a dry state or in an inert solvent such as a hydrocarbon.

Polymerization Method The amount of the catalyst component used in the production of the component (i) of the present invention is not particularly limited, but the solid catalyst component of the component (A) is converted to titanium atoms in a reaction volume of 1%. The amount is usually in the range of 0.00005 to 1 mmol per liter, and the organoaluminum compound as the component (B) has an aluminum / titanium atomic ratio of usually 1 to 1,000.
An amount is used such that it is in the range of 0, preferably 10-500. If the atomic ratio is outside the above range, the catalytic activity may be insufficient. When an electron donating compound such as an organosilicon compound is used as the (C) third component, the molar ratio of (C) the electron donating compound / (B) the organoaluminum compound is usually 0.001 to 5.0, Preferably, an amount is used so as to be in the range of 0.01 to 2.0, more preferably 0.05 to 1.0. If the molar ratio is outside the above range, sufficient catalytic activity and stereoregularity may not be obtained. However, when pre-polymerization is performed, it can be further reduced.

In the block copolymerization of propylene and ethylene in the production of the component (i) of the present invention, first, propylene was preliminarily polymerized as required from the viewpoints of polymerization activity, stereoregularity and polymer powder form. Thereafter, main polymerization may be performed. In this case, propylene is usually added in the presence of a catalyst obtained by mixing (A) the solid catalyst component, (B) the organoaluminum compound and, if necessary, (C) the electron donating compound at a predetermined ratio. ~ 100
At normal pressure to 50 kg / cm ² at a temperature in the range of
Prepolymerization is performed at a pressure of about G, and then propylene and ethylene are fully polymerized in the presence of a catalyst and a prepolymerized product.

The olefin used in the prepolymerization includes:
Α-olefins represented by the following general formula (V) R ¹⁴ —CH ＝ CH ₂ (V) are preferred. In the above formula (V), R ¹⁴ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group may be a saturated group or an unsaturated group. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1
-Decene, 3-methyl-1-pentene, 4-methyl-1
-Pentene, vinylcyclohexene, butadiene, isoprene, piperylene and the like. These olefins may be used alone or in combination of two or more. Among them, ethylene and propylene are preferred.

The type of polymerization in this main polymerization is not particularly limited, and can be applied to any of solution polymerization, slurry polymerization, gas phase polymerization, bulk polymerization and the like. It is applicable to two-stage polymerization and multi-stage polymerization under different conditions. Regarding the method for producing the block copolymer of the component (i) of the present invention, in either the batch method or the continuous method, generally, a propylene homopolymer section is first formed, and then a copolymer section is formed.

For example, in the case of manufacturing by a continuous method, a raw material propylene gas and a hydrogen gas as a molecular weight modifier,
The catalyst is supplied, the polymerization amount is controlled by the polymerization time to produce a propylene homopolymer part, and then the propylene homopolymer is transferred to the subsequent polymerization tank, and the raw material propylene gas is further mixed with a copolymer monomer, hydrogen gas, and, if necessary, a catalyst. In addition, a copolymer can be produced to obtain a block copolymer.

Further, regarding the reaction conditions, the polymerization pressure is not particularly limited, and from the viewpoint of polymerization activity, it is generally atmospheric pressure to 80 kg / cm ² G, preferably ^{2 to} 50 kg / cm ^2.
2 G, the polymerization temperature is usually, 0 to 200 ° C., preferably,
It is appropriately selected within the range of 30 to 100 ° C. The polymerization time is usually about 5 minutes to 20 hours, preferably about 10 minutes to 10 hours.

The molecular weight can be adjusted by adding a chain transfer agent, preferably by adding hydrogen. Also,
An inert gas such as nitrogen may be present. Further, as for the catalyst component in the present invention, the components (A), (B) and (C) may be mixed at a predetermined ratio, brought into contact with each other, and then propylene may be immediately introduced to carry out polymerization. Then, after the contact, aging is performed for about 0.2 to 3 hours, and then polymerization may be performed by introducing propylene and ethylene. Further, this catalyst component can be supplied by suspending in an inert solvent or propylene.

In the present invention, the post-treatment after the polymerization can be carried out by a conventional method. That is, in the gas phase polymerization method, after polymerization, the polymer powder derived from the polymerization vessel,
In order to remove propylene, ethylene, and the like contained therein, the mixture may be passed through a nitrogen gas stream or the like, or may be pelletized by an extruder as desired, in which case the catalyst is completely deactivated. For this purpose, a small amount of water, alcohol, or the like can be added. In the bulk polymerization method, after the polymerization, the monomer can be completely separated from the polymer discharged from the polymerization vessel and then pelletized.

Next, the additive of the component (ii) to be added to the propylene-ethylene block copolymer of the component (i) and the additive of the component (iii) to be added as required will be described. (Ii) Ingredient (ii) of the components, for weathering agent, but are not limited to, (a) hindered amine light stabilizers, (b) benzotriazole, benzophenone, oxalic acid anilide based, form amidine UV absorber selected from the group consisting of a triazine ring system, (c) a hydroxybenzoate light stabilizer and (d) a nickel quencher.

As the hindered amine light stabilizer of the component (a), 4-hydroxy-2,2,6,6-tetramethylpiberidine, 1-allyl-4-hydroxy-2,
2,6,6-tetramethylpiveridine, 1-benzyl-
4-hydroxy-2,2,6,6-tetramethylpiberidine, 1- (4-t-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiberidine,
4-stearoyloxy-2,2,6,6-tetramethylpiberidine, 4-methacryloyloxy-1,2,2
2,6,6-pentamethylpiveridine, 1-benzyl-
2,2,6,6-tetramethyl-4-piberidyl malate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl -4-piberidyl) succinate, bis (2,
2,6,6-tetramethyl-4-piberidyl) adipate, bis (2,2,6,6-tetramethyl-4-piberidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Fumarate, bis (1,2,3,
6-tetramethyl-2,6-diethyl-4-piberidyl) sebacate, bis (1-allyl-2,2,6,6-
Tetramethinol-4-piperidyl) phthalate, bis (1,2,2,6,6-pentamethyl-4-piberidyl) sebacate, 1,1 ′-(1,2-ethanediyl)
Bis (3,3,5,5-tetramethylpiperazinone),
2-methyl-2- (2,2,6,6-tetramethyl-4
-Piperidyl) imino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, 2-methyl-2- (1,2,2,6,6-pentamethyl-4-piperidyl) imino -N- (1,2,2,6,6-pentamethyl-4-piperidyl) propionamide, 1-propargyl-4-β-cyanoethyloxy-2,2,6,6
-Tetramethylpiperidine, 1-acetyl-2,2,
6,6-tetramethyl-4-piperidyl-acetate,
Trimellitic acid-tris (2,2,6,6-tetramethyl-4-piperidyl) ester, 1-acryloyl-4
-Benzyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl-4
-Piperidyl) dibutylmalonate, bis (1,2,2
2,6,6-pentamethyl-4-piperidyl) dibenzylmalonate, bis (1,2,3,6-tetramethyl-
2,6-diethyl-4-piperidyl) dibenzyl-malonate, bis (1,2,2,6,6-pentamethyl-4)
-Piberidyl) -2- (3,5-di-t-butyl-4-
(Hydroxybenzyl) -2-n-butylmalonate, bis (2,2,6,6-tetramethyl-4-piperidyl)
-1,5-dioxaspiro [5.5] undecane-3,
3-dicarboxylate, bis (1,2,2,6,6-
Pentamethyl-4-piperidyl) -1,5-dioxaspiro [5.5] undecane-3,3-dicarboxylate, bis (1-acetyl 2,2,6,6-tetramethyl-4-piperidyl) -1, 5-dioxaspiro [5.
5] undecane-3,3-dicarboxylate, 1,3
-Bis [2,2 '-[bis (2,2,6,6-tetramethyl-4-piperidyl) -1,3-dioxacyclohexane-5,5-dicarboxylate]], bis (2
2,6,6-tetramethyl-4-piperidyl) -2-
[1-methylethyl] -1,3-dioxacyclohexane-5,5-dicarboxylate]], 1,2-bis [2,2 ′-[bis (2,2,6,6-tetramethyl-
4-piperidyl) -2-methyl-1,3-dioxacyclohexane-5,5-dicarboxylate]], bis (2,2,6,6-tetramethyl-4-piperidyl)-
2- [2- (3,5-di-tert-butyl-4-hydroxyphenyl)] ethyl-2-methyl-1,3-dioxacyclohexane-5,5-dicarboxylate, bis (2,6 6-tetramethyl-4-piperidyl) -1,
5-dioxaspiro [5.11] heptadecane-3,3
-Dicarboxylate, hexane-1 ', 6'-bis-
4-carbamoyloxy-1-n-butyl-2,2,
6,6-tetramethylpiperidine), toluene-2 ',
4'-bis (4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine), dimethyl-bis (2,2,6,6-tetramethylpiperidine-
4-oxy) -silane, phenyl-tris (2,2,
6,6-tetramethylpiperidine-4-oxy) -silane, tris (1-propyl-2,2,6,6-tetramethyl-4-piperidyl) -phosphite, tris (1-
Propyl-2,2,6,6-tetramethyl-4-piperidyl) -phosphate, phenyl- [bis (1,2,2
2,6,6-pentamethyl-4-piperidyl)]-phosphonate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1, 2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-
Tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarbonamide, tetrakis (1,2,2,2)
6,6-pentamethyl-4-piberidyl) 1,2,3
4-butanetetracarbonamide, 2-dibutylamino-4,6-bis (9-aza-3-ethyl-8,8,1
0,10-tetramethyl-1,5-dioxaspiro [5.5] -3-undecylmethoxy) -s-triazine, 2-dibutylamino-4,6-bis (9-aza-3)
-Ethyl-8,8,9,10,10-pentamethyl-
1,5-dioxaspiro [5.5] -3-undecylmethoxy) -s-triazine, tetrakis (9-aza-3)
-Ethyl-8,8,10,10-tetramethyl-1,5
-Dioxaspiro [5.5] -3-undecylmethyl)
-1,2,3,4-butanetetracarboxylate, tetrakis (9-aza-3-ethyl-8,8,9,10,
10-pentamethyl-1,5-dioxaspiro [5.
5] -3-undecylmethyl) -1,2,3,4-butanetetracarboxylate, tridecyl tris (2
2,6,6-tetramethyl-4-piperidyl) 1,2,2
3,4-butanetetracarboxylate, tridecyl
Tris (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, di (tridecinol) bis (2,2,6,6-tetramethyl-4 -Piberidyl) 1,2,3,4-butanetetracarboxylate, di (tridecyl) bis (1,
2,2,6,6-pentamethyl-4-piperidyl) 1,
2,3,4-butanetetracarboxylate, 2,2
4,4-Tetramethyl-7-oxa-3,20-diazaspiro [5,1,11,2] heneicosan-21
On, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarberoxy) ethyl]-
2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-bentamethyl-4-piperidyl) Oxycarbonyl) butylcarberoxydiethyl] -2,4,8,10-tetraoxaspiro [5.
5] undecane, poly (2,2,6,6-tetramethyl-4-piperidyl acrylate), poly (1,2,2,
6,6-pentamethyl-4-piperidyl acrylate), poly (2,2,6,6-tetramethyl-4-piperidyl methacrylate), poly (1,2,2,6,6-
Pentamethyl-4-piperidyl methacrylate), poly [[bis (2,2,6,6-tetramethyl-4-piperidyl) itaconate] [vinyl butyl ether]], poly [[bis (1,2,2,6,6 -Bentamethyl-4-
Piperidyl) itaconate] [vinyl butyl ether]], poly [[bis (2,2,6,6-tetramethyl-4-piperidyl) itaconate] [vinyl octyl ether]], poly [[bis (1,2,2, 6,6-pentamethyl-4-piperidyl) itaconate] [vinyl octyl ether]], dimethyl succinate-2- (4
-Hydroxy-2,2,6,6-tetramethylpiperidyl) ethanol condensate, poly [hexamethylene [(2,
2,6,6-tetramethyl-4-piperidyl) imino]], poly [ethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6 -Tetramethylene-4-piperidyl) imino]], poly [[1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-
4-piperidyl) imino] hexamethylene [(2,2
6,6-tetramethyl-4-piperidyl) imino]],
Poly [[6- (diethylimino) -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piberidyl) imino] hexamethylene [(2,2 , 6,6-tetramethyl-4-piberidyl)
Imino]], poly [[6-[(2-ethylhexyl) imino] -1,3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6-
[(1,1,3,3-tetramethylbutyl) imino]-
1,3,5-triazine-2,4-diyl] [(2
2,6,6-tetramethyl-4-piperidyl) imino]
Hexamethylene [(2,2,6,6-tetramethyl-4
-Piperidyl) imino]], poly [[6- (cyclohexylimino) -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6-
Morpholino-1,3,5-triazine-2,4-diinol] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl- 4-piperidyl) imino]], poly [[6-
(Butoxyimino) -1,3,5-triazine-2,4
-Diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6
-Tetramethyl-4-piperidyl) imino]], poly [[6-[(1,1,3,3-tetramethylbutyl) oxy] -1,3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piberidyl) imino]], poly [oxy [6
-[(1-piperidyl) -1,3,5-triazine-
2,4-diyloxy-1,2-ethanediyl]
[(2,2,6,6-tetramethyl-3-oxo-1,
4-piperidyl) -1,2-ethanediyl]] [(3,
3,5,5-tetramethyl-2-oxo-1,4-piberidyl) -1,2-ethanediyl]], poly [oxy [6-[(1,1,3,3-tetramethylbutyl) imino]] -1,3,5-Triazine-2,4-diyloxy-1,2-ethanediyl] [(2,2,6,6-tetramethyl-3-oxo-1,4-piperidyl) -1,2-
Ethanediyl] [(3,3,5,5-tetramethyl-2
-Oxo-1,4-piperidyl) -1,2-ethanediyl]], poly [[6-[(ethylacetyl) imino]-
1,3,5-triazine-2,4-diyl] [(2
2,6,6-tetramethyl-4-piperidyl) imino]
Hexamethylene [(2,2,6,6-tetramethyl-4
-Piberidyl) imino]], poly [[6-[(2,2,
6,6-tetramethyl-4-piberidyl) butylimino] -1,3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], 1,6,11-tris [{4,6-bis (N-butyl-N- (2,2 ,
6,6-tetramethyl-4-piperidyl) amino)-
1,3,5-triazin-2-yl {amino] undecane, 1,6,11-tris [{4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl- 4-piperidyl) amino) -1,3,5-triazin-2-yl {amino] undecane, 1,6,11-tris [{4,6-bis (N-octyl-N- (2,2,6) ,
6-tetramethyl-4-piperidyl) amino) -1,
3,5-triazin-2-yl) amino] undecane,
1,6,11-tris [@ 4,6-bis (N-octyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazine-2 -Yl @ amino] undecane, polymethyl-propyl-3-
Oxy [1 (2,2,6,6-tetramethyl) piperidyl] siloxane, 1,1 ′, 1 ″-[1,3,5-triazine-2,4,6-triyl-tris [(cyclohexylimino) -2,1-ethanediyl]]-tris [3,3,5,5-tetramethylpiperazin-2-one], 1,1,1-tris [polyoxypropylene-
｛4,6-bis (N-butyl-N- (2,2,6,6-
Tetramethyl-4-piperidyl) amino) -1,3,5
-Triazin-2-yl {aminoethermethyl] propane, 1,1,1-tris [polyoxyethylene-
｛4,6-bis (N-butyl-N- (2,2,6,6-
Tetramethyl-4-piperidyl) amino) -1,3,5
-Triazin-2-yl {aminoethermethyl] propane, 1,1,1-tris [polyoxyethylene-
｛4,6-bis (N-butyl-N- (1,2,2,6,
6-pentamethyl-4-piperidyl) amino) -1,
3,5-triazin-2-yl {aminoethermethyl] propane, 1,1,1-tris [polyoxypropylene- {4,6-bis (N-butyl-N- (2,2,
6,6-tetramethyl-4-piperidyl) amino)-
1,3,5-triazin-2-yl {aminoethermethyl] propane, 1,1,1-tris [polyoxypropylene- {4,6-bis (N-butyl-N- (1,2,2
2,6,6-pentamethyl-4-piberidyl) amino)
-1,3,5-triazin-2-yl {aminoethermethyl] propane, 1,5,8,12-tetrakis [4,6-bis (N- (2,2,6,6-tetramethyl-4 -Piperidyl) -butylamino) -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [4,6-bis (N -(1,2,2,6,6-pentamethyl-4-piperidyl) -butylamino) -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane and the like. be able to.

As the benzotriazole-based ultraviolet absorber among the components (b), 2- (2′-hydroxy-5′-)
Methylphenyl) benzotriazole, 2- [2'-hydroxy-3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 2- (2'-hydroxy-3', 5'-di- t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'- Jee
t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octyl) Phenyl) benzotriazole, 2,2′-methylene-bis [4- (1,1,3,
3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl-3- [3-
Condensation product of t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol, 2- (2-hydroxyphenyl) benzotriazole copolymer, 2-
(2′-hydroxy-4′-octyloxyphenyl)
-2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4,
5,6-tetrahydrophthalimidylmethyl) phenol, 2,2′-methylenebis (4-t-butyl-6)
-2H-benzotriazolylphenol), 2,2'-
Methylene bis (4-t-octyl-6-2H-benzotriazolylphenol) and the like can be mentioned.

Of the component (b), benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
-Hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-
Dihydroxy-4,4'-dimethoxybenzophenone,
Examples thereof include 2,2 ′, 4,4′-tetrahydroxybenzophenone and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.

The oxalic acid anilide ultraviolet absorbers of the component (b) include N, N'-diethyl oxalic acid-bis-anilide and 2-ethoxy-2 '.
-Ethyl oxalic acid-bis-anilide, 2-
Ethoxy-5-tert-butyl-2'-ethyloxalic acid-bis-anilide and 2-ethoxy-5-t
-Butyl-2'-ethyl-4'-t-butyloxalic acid-bis-anilide. As the formamidine-based ultraviolet absorber of the component (b), N- (4-ethoxycarbonylphenyl) -N ′
-Methyl-N'-phenylformamidine, N- (4
-Ethoxycarbonylphenyl) -N'-ethyl-N '
-Phenylformamidine, N- (4-ethoxycarbonylphenyl) -N'-ethoxyl-N'-phenylformamidine and N- (4-ethoxycarbonylphenyl) -N ', N'-diphenylformamidine Can be.

As the triazine ring ultraviolet absorber of the component (b), 2- [4,6-di (2,4-xylyl) -1,2
3,5-Triazin-2-yl] -5-octyloxyphenol, 2- (4,6-diphenyl-1,3,5-
Triazin-2-yl) -5-[(hexyl) oxy]
-Phenol and the like. As the hydroxybenzoate-based light stabilizer of the component (c), 2,4-
Di-tert-butylphenyl-3 ', 5'-di-tert-butyl-4'-hydroxybenzoate, 2,6-di-tert-butylphenyl-3', 5'-di-tert-butyl-4 ' -Hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate and n-
Octadecyl-3,5-di-t-butyl-4-hydroxybenzoate and the like can be mentioned.

As the nickel-based quencher of the component (d),
Nickel-bis [2,2′-thio-bis (4-t-octylphenolate)], nickel-bis [Ot-butyl- (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate ], Ecker-bis [O-ethyl-
(3,5-di-t-butyl-4-hydroxybenzyl)
Phosphonate], 2,2′-thio-bis (4-t-octylphenolate) -butylamino-nickel (II),
2,2′-thio-bis (4-t-octylphenolate) -cyclohexylamino-nickel (II), 2,
2'-thio-bis (4-t-octylphenolate)-
Diethanolamino-nickel (II), 2,2'-thio-bis (4-t-octylphenolate) -phenyl-
Diethanolamino-nickel (II), 2,2′-thio-bis (4-t-octylphenolate) -i-octylamino-nickel (II), 2,2′-thio-bis (4
-T-octylphenolate) -octylamino-nickel (II), 2,2'-thio-bis (4-t-octylphenolate) -cyclohexyl-diethanolamino-nickel (II), nickel dibutyldithiocarbamate and the like. Can be mentioned. The above (a),
By using the light stabilizer of the component (c) and the ultraviolet absorber of the component (b) in combination, the weather resistance is further improved.

Among the components (ii), colorants include, for example, inorganic pigments such as titanium oxide, zinc oxide, red iron oxide, fired titanium oxide pigments, ultramarine blue, cobalt aluminate, carbon black, azo pigments, quinacridone pigments, and the like. Organic pigments such as anthraquinone, perylene, isoindolinone, phthalocyanine, quinophthalone, sulene, and diketopyrrolopyrrole; extender pigments such as barium sulfate and calcium carbonate; basic dyes; acid dyes; And the like.

The amount of the component (ii) is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, per 100 parts by weight of the propylene-ethylene block copolymer of the component (i). Parts by weight, particularly preferably 0.02
１1 part by weight. If the amount is too small, the effect of improving the stability of weather resistance may not be sufficient.If the amount is too large, the effect of improving the weather resistance may not be commensurate with the amount, and the tensile strength or the like may decrease. There are cases.

( Iii) Component In the composition of the present invention, the dispersibility of the component (ii) can be improved by using a dispersant in combination, if necessary. As dispersants, fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid, linoleic acid, oleic acid, linolenic acid, hydroxystearic acid, calcium stearate, magnesium stearate, lithium stearate, stearin Fatty acid metal salts such as zinc acid, aluminum stearate, calcium linoleate, magnesium hydroxystearate, etc., fatty acid esters such as ethyl stearate, ethyl laurate, butyl oleate, dioctyl adipate, monoglyceride stearate, stearamide, olein Acid amide, erucamide, N,
Fatty acid amides such as N'-ethylenebisstearic amide and lauric amide, and anionic, cationic and nonionic surfactants and the like can be used.

The above-mentioned component (iii) may be used alone or in combination of two or more kinds. The compounding amount thereof is based on 100 parts by weight of the propylene-ethylene block copolymer of the component (i). And preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight. If the amount is too small, the effect of improving the dispersibility may not be obtained, and if the amount is too large, the effect of improving the dispersibility may not be commensurate with the amount, and the tensile strength may be reduced.

The molded article according to the second invention of the present application can be obtained by molding using the above propylene-ethylene block copolymer composition. Examples of the molded article of the present invention include automotive interior materials, housing materials for call products, films, sheets, and the like. As the molding method, injection molding, compression molding, injection compression molding,
Examples thereof include a gas assist injection molding method, an extrusion molding method, and a blow molding method.

The molded article of the present invention may be added to the propylene-ethylene block copolymer composition, if desired, by adding additives for surface functions such as an antistatic agent and an antifogging agent, an antiblocking agent, an antioxidant, Contains known additives such as rust inhibitors, lubricants, nucleating agents, metal deactivators, radical generators, drip-free agents, flame retardants, flame retardant aids, antibacterial agents, and inorganic or organic fillers. May be manufactured after preparing the resin composition.

[0068]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the test method used in the said text and an Example is as follows. (1) Measurement of melt flow rate (MFR) 230 ° C., 2.16 k in accordance with JIS K 7210
Measure with g load. (2) Measurement of the Amount of Xylene-Soluble Components at Room Temperature The xylene-soluble and insoluble components at room temperature (25 ° C.) were obtained as follows. 5 ± 0.05 g of sample is precisely weighed and put into a 1,000 ml eggplant-shaped flask, and further BHT (antioxidant)
After adding 1 ± 0.05 g, 700 ± 10 ml of the rotor and para-xylene are charged. Next, a condenser is attached to the eggplant-shaped flask, and the flask is heated in an oil bath at 140 ± 5 ° C. for 120 ± 30 minutes while the rotor is operated to dissolve the sample in para-xylene. Next, after pouring the contents of the flask into a 1,000 ml beaker, the solution in the beaker is allowed to cool to room temperature (25 ° C.) (8 hours or more) while stirring with a stirrer. Filter out. The filtrate was further filtered through filter paper, and the filtrate was poured into 2,000 ± 100 ml of methanol contained in a 3,000 ml beaker, and the solution was stirred with a stirrer at room temperature (25 ° C.). And leave for 2 hours or more. Next, the precipitate is collected by filtration with a wire mesh, air-dried for 5 hours or more, and dried in a vacuum dryer at 100 ± 5 ° C for 240 to 270 minutes to recover a xylene-soluble component at 25 ° C. On the other hand, the precipitate collected by wire mesh in the above was dissolved again in para-xylene according to the method described above, and then quickly and hot transferred to 2,000 ± 100 ml of methanol contained in a 3,000 ml beaker, After stirring with a stirrer for 2 hours or more, it is left overnight at room temperature (25 ° C.). Next, the precipitate is collected by filtration with a wire mesh, air-dried for 5 hours or more, and dried in a vacuum dryer at 100 ± 5 ° C. for 240 to 270 minutes to recover xylene insoluble components at 25 ° C. 25 ° C
The content (w) of the soluble component with respect to xylene is represented by w (% by weight) = 100 × C / A, where Ag is the weight of the sample and Cg is the weight of the soluble component collected above. The content of the component is represented by (100-w)% by weight.

(3) ¹³ C-NM of xylene soluble components at normal temperature
Measurement of ethylene content by R All measurements of ¹³ C-NMR are performed by the following method. That is, 220 mg of a sample was collected in an NMR sample tube, and 3 ml of a 1,2,4-trichlorobenzene / deuterated benzene mixed solvent (volume ratio: 90/10) was added thereto. After dissolution, ¹³ C-NMR measurement is performed under the following measurement conditions. Apparatus: JNM-EX400 manufactured by JEOL Ltd. Pulse width: 9 μs (45 °) Pulse repetition time: 4 seconds Spectrum width: 20,000 Hz Measurement temperature: 130 ° C. Number of times of integration: 1,000 times

The ethylene unit content of the soluble component and the ethylene unit content of the insoluble component with respect to xylene at 25 ° C. are values determined by the following methods. That is, the sample
¹³ C-NMR was measured, and 35 to
First, based on the seven peak intensities in the 21 ppm [tetramethylsilane (TMS) chemical shift standard] region, the triad chain fraction (mol%) of ethylene (E) and propylene (P) is calculated by the following equation. f _EPE = [K (Tδδ) / T] × 100 f _PPE = [K (Tβδ) / T] × 100 f _EEE = [K (Sγδ) / 4T + K (Sδδ) / 2T]
× 100 f _PPP = [K (Tββ) / T] × 100 f _PEE = [K (Sβδ) / T] × 100 f _PEP = [K (Sββ) / T] × 100 where T = K (Tδδ) + K (Tβδ) + K (Sγ
δ) / 4 + K (Sδδ) / 2 + K (Tββ) + K (Sβ
δ) + K (Sββ) Here, for example, f _EPE indicates the EPEtrid chain fraction (mol%), and K (Tδδ) indicates the integrated intensity of the peak attributed to the Tδδ carbon.

Next, the ethylene unit content (% by weight) was increased.
It is calculated by the following equation using the above triad chain fraction. Ethylene unit content (% by weight) = 28 / 3f_EEE+2
(F_PEE+ F_EPE) + F _PPE+ F_PEP｝ × 100 / [2
8 ｛3f_EEE+2 (f_PEE+ F_EPE) + F_PPE+
f_PEP｝ +42 ｛3f_PPP+2 (f_PPE+ F_PEP) + F
_EPE+_PEE｝)

(4) ¹³ C-NM of xylene insoluble component at normal temperature
Measurement of Stereoregularity Index by R The stereoregularity index is a value obtained by the following method. That is, ¹³ C of insoluble component in xylene at 25 ° C.
-In the NMR spectrum, the signal of methyl carbon varies from a low magnetic field to a high magnetic field under the influence of stereoregularity,
m + rrrm, rmrm, rrrr, mrrr, mrr
It is split into 9 peaks of m and observed. Among these nine lines, mmmm, mmrr, mmrr,
Focusing on the six peaks of mmrm + rrrmr, rrrr, and mrrm, the stereoregularity index of the insoluble component is calculated by the following equation.

Stereoregularity index (%) = L _mmmm × 100 /
(L _mmmm + L _mmmr + L _mmrr + L _{mmrm + rrmr} + L _rrrr + L
_mrrm ) where L _mmmm , L _mmmr , L _mmrr , L _{mmrm + rrmr} , L
_rrrr and L _mrrm are respectively mmmm, mmmr, mmrr, mmrm + rr in the ¹³ C-NMR spectrum.
The height of the mr, rrrr, and mrrm peaks from the baseline. However, the peak of mmmm is composed of a plurality of discrete points having different chemical shifts and peak heights, and the peak of mmmr is on the tailing of the main peak of mmmm. Is corrected according to a conventional method.

(5) Pulse NM of xylene soluble component at normal temperature
Measurement of T1 Relaxation Time Measured by R T1 is the time constant of the recovery of the magnetization in the longitudinal direction, and the most common measurement method is the inversion recovery method (180 ° -τ-90 ° pulse method). First, magnetization is given in the −z ′ direction by a pulse of θ = 180 ° at t = 0, and then the thermal equilibrium value M ₀
Starts to recover. When a 90 ° pulse is given after the elapse of τ time, the magnetization rotates in the y′-axis direction, and an FID signal proportional to the magnitude of the magnetization is observed. If τ is continuously changed, a recovery curve of the signal strength M (τ) can be obtained. Based on Bloch's equation, with the initial condition of M (0) = − M ₀ , the recovery of the magnetization in the longitudinal direction is expressed as M = M ₀ {1-2exp (−τ / T1)}. Further, practically, ln ｛M (∞) -M
(Τ)｝ = ln ｛2M (∞)｝ − τ / T1, and ln
T1 can be determined by the slope of the straight line obtained from the plot of {M (∞) -M (τ)} to τ.

When performing a series of measurements including repeated experiments of integration, it is necessary to wait until the magnetization returns to the thermal equilibrium state, and a wait time of at least 5T1 (9 times at 5T1).
M (∞) is τ> 5.
An M (τ) value for τ that satisfies T1 was adopted. The measurement was performed under the following conditions using a pulse NMR apparatus CXP-90 manufactured by Bruker. Measurement nucleus: Hydrogen nucleus Measurement frequency: 90 MHZ Measurement temperature: 30 ° C. Measurement method: Inversion recovery method (180 ° -τ-90 ° pulse method) 180 °: 180 ° pulse 90 °: 90 ° pulse τ: Variable time, 90 ° Pulse width: 2.3 to 2.4 μsec

(6) Measurement of Impact Resistance According to JIS K 7110, an injection-molded product at 23 ° C.
The notched Izod impact strength at −30 ° C. is measured. (7) Measurement of flexural modulus The flexural modulus is measured according to JIS K7203. (8) Measurement of surface hardness Rockwell hardness (R) according to JIS K 7202
Scale). (9) Measurement of Heat Deformation Temperature A load distortion temperature (high load) is measured according to JIS K 7207. (10) Evaluation of weather resistance A 1.0 mm-thick tensile test piece press-molded at a molding temperature of 200 ° C. was subjected to black panel temperature 83 ° C., 12 minutes / 60.
It was left in a xenon weathering tester (manufactured by Suga Test Instruments Co., Ltd.) under conditions of minute rainfall. Thereafter, the test piece was taken out at an appropriate time and subjected to a tensile test according to a conventional method, thereby obtaining a relational expression between the time left during the weathering test and the elongation at break of the test piece. The elongation at break L of the test piece at the time of leaving for 0 hours in the weathering tester was measured, and the elongation at break was L /
The standing time in the resistance tester, which was 2, was determined and used as an index of weather resistance.

[Preparation of Polymerization Catalyst] (1) Preparation of Catalyst A (Preparation of Solid Catalyst Component)
60 g were charged. Further dehydrated octane is 600
Milliliter was added. Heat to 40 ° C and add silicon tetrachloride 2
4 ml was added and stirred for 20 minutes, and 16 ml of dibutyl phthalate was added. The temperature of the solution was raised to 80 ° C., and titanium tetrachloride was added to the solution using a dropping funnel.
70 ml was dropped. The contact was performed at an internal temperature of 125 ° C. for 2 hours. Thereafter, the stirring was stopped to allow the solid to settle, and the supernatant was extracted. 100 ml of dehydrated octane was added, the temperature was raised to 125 ° C. with stirring, and the temperature was maintained for 1 minute. Then, the stirring was stopped to precipitate the solid, and the supernatant was taken out. This washing operation was repeated seven times. Further, 1220 ml of titanium tetrachloride was added, and the internal temperature was adjusted to 125.
° C and contacted for 2 hours. Thereafter, washing with 125 ° C. dehydrated octane was repeated six times to obtain a solid catalyst component. (Preliminary polymerization) 48 g of the solid catalyst component was charged into a 1-liter three-necked flask equipped with a stirrer and purged with nitrogen. Further, 400 ml of dehydrated n-heptane was added. The mixture was heated to 40 ° C., and 2.0 ml of triethylaluminum and 6.3 ml of dicyclopentyldimethoxysilane were added. Propylene gas was allowed to flow at normal pressure and reacted for 2 hours. Thereafter, the solid component was sufficiently washed with dehydrated n-heptane to obtain Catalyst A.

(2) Preparation of Catalyst B (Preparation of Solid Catalyst Component) 160 g of diethoxymagnesium was charged into a three-necked flask equipped with a stirrer having an internal volume of 5 liter and purged with nitrogen. Further, 600 ml of dehydrated n-heptane was added. The mixture was heated to 40 ° C., 24 ml of silicon tetrachloride was added, the mixture was stirred for 20 minutes, and 25 ml of dibutyl phthalate was added. 80 solution
C., and 770 ml of titanium tetrachloride was added dropwise using a dropping funnel. The contact was performed at an internal temperature of 110 ° C. for 2 hours. Thereafter, washing was performed seven times using dehydrated n-heptane at 90 ° C. Add 12 parts of titanium tetrachloride
20 ml was added, the internal temperature was set to 110 ° C., and contact was made for 2 hours. Thereafter, washing was performed six times using dehydrated n-heptane at 60 ° C. to obtain a solid catalyst component. (Preliminary polymerization) 48 g of the solid catalyst component was charged into a 1-liter three-necked flask equipped with a stirrer and purged with nitrogen. Further, 400 ml of dehydrated heptane was added. Heat to 40 ° C and triethylaluminum 2.0
Milliliter and 6.3 ml of dicyclopentyldimethoxysilane were added. Propylene gas was allowed to flow at normal pressure and reacted for 2 hours. Thereafter, the solid component was sufficiently washed with dehydrated n-heptane to obtain a catalyst B.

(3) Preparation of Catalyst C (Preparation of Solid Catalyst Component) 160 g of diethoxymagnesium was charged into a 5-liter three-necked flask equipped with a stirrer and purged with nitrogen. Further, 600 ml of dehydrated n-heptane was added. The mixture was heated to 40 ° C., 24 ml of silicon tetrachloride was added, the mixture was stirred for 20 minutes, and 23 ml of diethyl phthalate was added. 80 solution
C., and 770 ml of titanium tetrachloride was added dropwise using a dropping funnel. The contact was performed at an internal temperature of 110 ° C. for 2 hours. Thereafter, washing was performed seven times using dehydrated n-heptane at 90 ° C. Add 12 parts of titanium tetrachloride
20 ml was added, the internal temperature was set to 110 ° C., and contact was made for 2 hours. Thereafter, washing was performed six times using dehydrated n-heptane at 90 ° C. to obtain a solid catalyst component. (Preliminary polymerization) 48 g of the solid catalyst component was charged into a 1-liter three-necked flask equipped with a stirrer and purged with nitrogen. Further, 400 ml of dehydrated heptane was added. Hold at 10 ° C. and triethylaluminum 2.7
Milliliter and 2 ml of cyclohexylmethyldimethoxylane were added. Propylene gas was allowed to flow at normal pressure and reacted for 2 hours. Thereafter, the solid component was sufficiently washed with dehydrated n-heptane to obtain a catalyst C.

[Production Example 1] A stainless steel autoclave with a stirrer having an internal volume of 5 liters, which was thoroughly dried with nitrogen gas and then replaced with propylene gas, was maintained at 70 ° C.
The pressure was increased to 0.5 kg / cm ² G with propylene gas. In this state, 5.5 kg / cm ² G of hydrogen gas was charged, and the pressure was gradually increased to 28 kg / cm ² G with propylene gas. Next, 20 ml of n-heptane, 4 mmol of triethylaluminum, 1 mmol of dicyclopentyldimethoxysilane, and 0.02 mmol of catalyst A were respectively collected into a 60 ml catalyst charging tube purged with nitrogen gas, and then charged into an autoclave. Propylene was polymerized for a minute to prepare a homopolymer. Thereafter, the autoclave was depressurized to an external pressure, sampled for measurement of intrinsic viscosity [η] in a nitrogen atmosphere, and once degassed under vacuum. Then, ethylene gas / propylene gas was mixed in a ratio of 1:
10 kg / cm ² G at a molar ratio of ²
At 10 ° C. and 10 kg / cm ² G, propylene ethylene copolymerization was carried out for 40 minutes. Thereafter, the pressure was released to the atmospheric pressure, and the temperature was lowered to room temperature. Then, the autoclave was opened, and the produced polymer powder was recovered. [Production Example 2] The same operation as in Production Example 1 was carried out except that the molar ratio of ethylene / propylene was 1: 1. [Production Example 3] The same operation as in Production Example 1 was carried out except that the polymerization time of the homopolymerization part was changed to 30 minutes.

[Production Example 4] 0.5 g of hydrogen gas was added to the copolymerized part.
The same operation as in Production Example 1 was carried out except that kg / cm ² G was applied. [Production Example 5] The same operation as in Production Example 1 was carried out except that the polymerization time in the copolymerized part was changed to 20 minutes. [Production Example 6] The same procedure as in Production Example 1 was carried out except that the polymerization time in the copolymerized part was changed to 90 minutes. [Production Example 7] The same operation as in Production Example 1 was carried out except that Catalyst B in Production Example 1 was used instead of Catalyst A. [Production Example 8] The same operation as in Production Example 1 was carried out except that Catalyst B was used instead of Catalyst A in Production Example 1, and the molar ratio of ethylene / propylene gas was 1: 1.

[Production Example 9] The same procedure as in Production Example 1 was carried out except that the catalyst B was used in place of the catalyst A in Production Example 1, and the polymerization time in the homopolymerized part was changed to 30 minutes. [Production Example 10] The same operation as in Production Example 1 was carried out except that the catalyst B was used in place of the catalyst A in Production Example 1, and the polymerization time of the copolymerized part was changed to 20 minutes. [Production Example 11] The same operation as in Production Example 1 was carried out except that the catalyst C was used in place of the catalyst A in Production Example 1, and that cyclohexylmethyldimethoxysilane was used instead of dicyclopentyldimethoxysilane. [Production Example 12] Using Catalyst C in place of Catalyst A in Production Example 1, using cyclohexylmethyldimethoxysilane in place of dicyclopentyldimethoxysilane, and injecting 0.5 kg / cm ² G of hydrogen gas into the copolymerized part. The same operation as in Production Example 1 was performed, except that the molar ratio of ethylene gas / propylene gas was 1: 4.

[Production Example 13] Catalyst C was used in place of Catalyst A in Production Example 1, and cyclohexylmethyldimethoxysilane was used in place of dicyclopentyldimethoxysilane.
The same operation as in Production Example 1 was carried out except that the molar ratio of ethylene gas / propylene gas was 1: 5. [Production Example 14] Using catalyst C in place of catalyst A in Production Example 1, using cyclohexylmethyldimethoxysilane instead of dicyclopentyldimethoxysilane, and injecting 0.1 kg / cm ² G of hydrogen gas into the copolymerized part. The same operation as in Production Example 1 was performed, except that the molar ratio of ethylene gas / propylene gas was 1: 4. [Production Example 15] Except that Catalyst C was used in place of Catalyst A in Production Example 1, cyclohexylmethyldimethoxysilane was used instead of dicyclopentyldimethoxysilane, and the molar ratio of ethylene gas / propylene gas was 1: 4. Was carried out in the same manner as in Production Example 1.

Examples 1 to 19 and Comparative Examples 1 to 9 The additives shown in Table 1 were added to 100 parts by weight of the block polypropylene powders obtained in the above Production Examples 1 to 15 in the proportions shown in Table 1. Further, 0.1 parts by weight of calcium stearate (manufactured by NOF Corporation) and 0.05 parts by weight of DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.)
As antioxidants, 0.075 parts by weight of P-EPQ (manufactured by Clariant) and 0.15 parts by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals) were added, mixed well, and then 20 mm uniaxial kneading. The mixture was melt-kneaded and granulated by an extruder to prepare pellets. For a part of the pellet, predetermined resin properties (structural properties) were measured, and the remaining pellets were injection-molded to produce various test pieces, and mechanical properties were measured and weather resistance was evaluated in the manner described above. . Table 1 shows the results.

[0085]

[Table 1]

[0086]

[Table 2]

[0087]

[Table 3]

[0088]

[Table 4]

[0089]

[Table 5]

[0090]

[Table 6]

The additives used in the examples and comparative examples are as follows. A1: Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate [Sanol LS-770, manufactured by Sankyo Co., Ltd., hindered amine light stabilizer] A2: Dimethyl succinate-2- (4-hydroxy-
2,2,6,6-tetramethylpiperidyl) ethanol condensate [Tinuvin 622LD, Ciba Specialty
A hindered amine light stabilizer manufactured by Chemicals Co., Ltd.] A3: 2- (2′-hydroxy-3 ′, 5′-di-t-)
Butylphenyl) -5-chlorobenzotriazole [Tinuvin 327, Ciba Specialty Chemicals Co., Ltd., benzotriazole ultraviolet absorber] A4: 2,4-di-t-butylphenyl-3 ′, 5′-
Di-t-butyl-4'-hydroxybenzoate [Tinuvin 120, manufactured by Ciba Specialty Chemicals,
Hydroxybenzoate light stabilizer] A5: 2,2'-thio-bis (4-t-octylphenolate) -i-octylamino-nickel (II) [Seesorb 612NH, manufactured by Cipro Kasei, nickel-based quencher]

B1: Carbon black (HCF # 230)
B2: Titanium oxide (Taipec RF-690, manufactured by Ishihara Sangyo Co., Ltd.) B3: Copper phthalocyanine (Heliogen Blue K690)
BAS: Azo-based pigment (CROMOPHTAL RED B)
G, Ciba Specialty Chemicals) C1: Calcium stearate (calcium stearate G, manufactured by NOF Corporation, dispersant)

In Table 1, when Examples 1 to 15, 17 showing almost the same Izod impact strength (−30 ° C.) and Comparative Examples 1, 5 are compared, the propylene-ethylene block copolymer composition of the present invention is It can be seen that the flexural modulus, Rockwell hardness, and heat deformation temperature are high and excellent. Similarly, the same can be said for the comparison between Example 18 and Comparative Examples 4, 8, and 9, and between Example 16 and Comparative Example 3. In addition, it is clear from the comparison between Examples 1 to 19 and Comparative Example 9 that the use of a weathering agent or a coloring agent also improved the weather resistance.

[0094]

The propylene-ethylene block copolymer composition of the present invention has a flexural modulus and Izod impact strength (-30 ° C, 23 ° C), Rockwell hardness and Izod impact strength (-30 ° C, 23 ° C). , Heat deformation temperature (high load)
And the Izod impact strength (−30 ° C., 23 ° C.). It is also clear that the weather resistance has been improved by using a weathering agent or a coloring agent.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA75 AA88 AH11 AH12 BB01 BB03 BB05 BB06 4J002 BP021 EJ016 EN076 ER006 EU076 EU176 EU186 EU206 EV236 EZ006 FD056 FD086 FD090 GN00 GQ00 4J026 HA04 HA27 HA32 HA34 HA27 HA34 HB35 HB39 HB42 HB43 HB48 HB49 HE01

Claims (7)

[Claims] (1) A propylene-ethylene block copolymer having the following properties (a) to (c):
(Ii) A propylene-ethylene block copolymer composition containing at least one compound selected from a weathering agent and a coloring agent. (A) Melt flow rate (MFR) (230 ° C, 2.
(16 kg load) is 0.01 to 1,000 g / 10 min, and (b) the stereoregularity index [mmmm] fraction measured by ¹³ C-NMR of the insoluble component at room temperature is 98.9% or more; (C) The component soluble in xylene at normal temperature is the following (c1) to
It satisfies the condition of (c3). (C1) 3 to 50% by weight, (c2) pulse N
(1) The T1 relaxation time component measured by MR is composed of a single relaxation component. (C3) T1 relaxation time y (millisecond) measured by pulse NMR, with the ethylene content measured by ¹³ C-NMR being x wt%. Satisfy the following relational expression. ^{y ≦ 0.0014x 3 -0.0897x 2 -1.0593x +} 231.6 ··· (1) 2. The compounding amount of the component (ii) is (i)
The propylene-ethylene block copolymer composition according to claim 1, wherein the amount is 0.005 to 5 parts by weight based on 100 parts by weight of the component. 3. The propylene-ethylene block copolymer composition according to claim 1, further comprising (iii) a dispersant. 4. The melt flow rate (MF) of the component (i)
R) (230 ° C, 2.16 kg load) 0.3-300
The propylene-ethylene block copolymer composition according to any one of claims 1 to 3, which is g / 10 minutes. 5. The weathering agent of component (ii) is selected from (a) hindered amine light stabilizers, (b) benzotriazoles, benzophenones, oxalic acid anilides, formamidines and triazine ring systems. The propylene-ethylene block copolymer composition according to any one of claims 1 to 4, which is an ultraviolet absorber, (c) a hydroxybenzoate-based light stabilizer, or (d) a nickel-based quencher. 6. The method according to claim 1, wherein the colorant in the component (ii) is (e) an inorganic pigment, (f) an organic pigment, (g) an extender pigment, or (h) a dye. Propylene-
An ethylene block copolymer composition. 7. A molded article obtained by molding the propylene-ethylene block copolymer composition according to claim 1.