JP2001011261A - Crystalline polypropylene resin composition and molded article prepared by molding same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crystalline polypropylene resin composition excellent in stiffness, resistances to heat and scratch, and antistatic properties and/or antifogging properties by compounding an antistatic agent and/or an antifogging agent into a crystalline polypropylene of which the soluble content at a specified temperature by temperature-rise fractionation and the intrinsic viscosity in tetralin at a specified temperature satisfy specific relations. SOLUTION: A resin composition for molding is prepared by compounding 0.05-2 pts.wt. antistaic agent and/or 0.1-5 pts.wt. antifogging agent into 100 pts.wt. crystalline polypropylene of which the 0 deg.C soluble content α (wt.%) by temperature-rise fractionation and the intrinsic viscosity [η](dl/g) at 135 deg.C in tetralin satisfy the relation represented by the formula: α<=1.11×[η]0.42+1.40. Preferably, the crystalline PP has an elution-curve peak temperature Tp( deg.C) by temperature-rise fractionation and an intrinsic viscosity [η](dl/g) at 135 deg.C in tetralin satisfying the relation represented by the formula: Tp>1.21×[η]+116.5, and the intrinsic viscosity is preferably 0.5-4.0 dl/g. The composition can give thin-walled lightweight molded articles and is effective in resource conservation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline polypropylene composition and a molded product obtained by molding the same, and more particularly, to an excellent rigidity, heat resistance and scratch resistance, and an antistatic property and / or The present invention relates to a crystalline polypropylene composition having excellent antifogging properties and a molded article obtained by molding the same.

[0002]

2. Description of the Related Art Polypropylene resin has excellent heat resistance, chemical resistance, and electrical properties, and also has good rigidity, tensile strength, optical characteristics, and workability. Injection molding, film molding, sheet molding, and blow molding. It is used for molding. Further, it has a light specific gravity and is widely used in the fields of containers, packaging materials and the like. However, depending on the application, these properties are not sufficiently satisfied and the use is restricted.

[0003] Among the above-mentioned properties, polypropylene is inferior to polystyrene and ABS resin in rigidity, heat resistance and scratch resistance. Therefore,
Polypropylene cannot be used as a material for manufacturing molded articles requiring rigidity, heat resistance and scratch resistance, and is equivalent to the polystyrene and ABS resin as a material for molded articles requiring rigidity and heat resistance. In order to satisfy the quality of the molded product, the molded product must be thick. This hinders the thinning of the molded article and increases the cost of the molded article, and the use of polypropylene or the polypropylene composition cannot be expanded. If polypropylene has excellent rigidity, heat resistance, scratch resistance, etc., such polypropylene can be used as an alternative to polystyrene and ABS resin, and its use can be expanded. Since it can be finished into a molded product, resource saving and cost reduction can be expected. In some applications, polypropylene resins are required to have antistatic properties and antifogging properties, and particularly in the fields of films, sheets, containers and the like, excellent antistatic properties and antifogging properties are required.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made from the above viewpoint, and has a novel crystallinity excellent in rigidity, heat resistance and scratch resistance, and excellent in antistatic and / or antifogging properties. An object of the present invention is to provide a polypropylene resin composition and a molded article obtained by molding the same.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the amount of soluble matter at 0 ° C. measured by the temperature rising fractionation method and the intrinsic viscosity [η] (η) measured at 135 ° C. in a tetralin solvent. (Deciliters / g) and a novel crystalline polypropylene satisfying a specific relationship with an antistatic agent and / or an anti-fogging agent. It is.

That is, the gist of the present invention is as follows. 1. (I) Soluble amount α at 0 ° C. by weight fractionation method (% by weight)
The intrinsic viscosity [η] (deciliter / g) measured at 135 ° C. in a tetralin solvent is represented by the following formula (1) α ≦ 1.11 × [η] ^−0.42 + 1.40 (1) A crystalline polypropylene resin composition comprising (ii) an antistatic agent and / or (iii) an antifogging agent mixed with a crystalline polypropylene to be filled. 2. 2. The crystalline polypropylene resin composition according to the above item 1, wherein the amount of the component (ii) is 0.05 to 2 parts by weight per 100 parts by weight of the component (i). 3. The crystalline polypropylene resin composition according to 1 or 2, wherein the amount of the component (iii) is 0.1 to 5 parts by weight based on 100 parts by weight of the component (i). 4. In the component (i), the elution curve peak temperature T _P (° C.) and intrinsic viscosity was measured at 135 ° C. in tetralin solvent using a Atsushi Nobori separation method [eta] (dl / g) is the following formula (2) T _P> 1.21 × [η] +116.5 (1) above which is crystalline polypropylene satisfying the following relationship:
The crystalline polypropylene resin composition according to any one of the above. 5. (I) In component, 135 degreeC in a tetralin solvent.
The crystalline polypropylene having an intrinsic viscosity [η] measured in the range of 0.5 to 4.0 deciliter / g.
The crystalline polypropylene resin composition according to any one of the above.
6. A molded article obtained by molding the crystalline polypropylene resin composition according to any one of the above 1 to 5.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The crystalline polypropylene of the component (i), which is a component of the present invention, has a soluble content α (% by weight) of 0 ° C. by a temperature rising fractionation method and an intrinsic viscosity [η] (decile / g) must satisfy the relationship of the following equation (1). α ≦ 1.11 × [η] ^{−0.42 +} 1.40 (1) Preferably, the relationship of the following expression (3) is satisfied. further,
Preferably, the relationship of the following equation (4) is satisfied. α ≦ 1.11 × [η] ^{−0.42 +} 1.00 (3) α ≦ 1.11 × [η] ^−0.42 + 0.50 (4) When the relationship of Expression (1) is not satisfied In addition, the rigidity when the resin composition is molded decreases.

Further, it is preferable that the crystalline polypropylene has an elution curve peak temperature T _P (° C.) and [η] obtained by a temperature rising fractionation method satisfying the following equation (2). T _P > 1.21 × [η] +116.5 (2) More preferably, the relationship of the following expression (5) is satisfied. T _P > 1.21 × [η] +117.0 (5) If the relationship of the above formula (2) is not satisfied, the rigidity when the resin composition is molded may decrease.

[0009] The soluble component α (% by weight) at 0 ° C. and the peak temperature _TP (° C.) of the elution curve of the crystalline polypropylene obtained by the temperature raising fractionation method were determined according to the following methods. . Sample preparation was performed by weighing 75 mg of the polymer in 10 ml of o-dichlorobenzene at room temperature,
Stir at 135-150 ° C for 1 hr to dissolve. After 0.5 ml of the sample solution is injected into the column at 135 ° C., the polymer is gradually cooled to 0 ° C. at 10 ° C./hr to crystallize the polymer on the surface of the filler. At that time, the amount of the polymer remaining without crystallization was defined as the soluble matter at 0 ° C. After cooling, the elution curve
-The column temperature is raised at 40 ° C./hr while dichlorobenzene is passed at 2 ml / min, and the concentration of the polymer eluted as needed is determined continuously by an infrared detector. The temperature at the peak position in the obtained elution curve was defined as the peak temperature. The column used was 4.6 mmφ × 150 mm, the packing material used was Chromosolve P, and the elution curve was adjusted using linear PE as a standard sample.
(SRM1475), and the peak temperature is adjusted to 100 ° C. (± 0.5) when eluted under the above conditions. A wavelength of 3.41 μm was used for detection.

The crystalline polypropylene of the component (i) constituting the present invention preferably has an intrinsic viscosity [η] of 0.5 to 4.0 deciliters / g measured at 135 ° C. in a tetralin solvent. . More preferably, 0.5 to
It is in the range of 3.0 deciliters / g. If it is less than 0.5 deciliter / g, the heat resistance when the resin composition is molded may decrease. 4.0 deciliter / g
If it exceeds, the rigidity when the resin composition is molded may decrease.

Next, a method for producing the above-mentioned crystalline polypropylene will be described. The crystalline polypropylene as the component (i) constituting the present invention is prepared by contacting (A) a magnesium compound and a titanium compound at a temperature of 120 to 150 ° C. in the presence of an electron-donating compound and, if necessary, a silicon compound. And then washed with an inert solvent at a temperature of 100 to 150 ° C., a catalyst comprising (B) an organoaluminum compound and, if necessary, (C) an electron-donating compound as a third component. Can be produced by polymerizing propylene or copolymerizing propylene and some α-olefin.

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 contains magnesium, titanium and an electron donor, and includes the following (a) a magnesium compound, (b) a titanium compound, (c) an electron-donating compound and It is formed from a solid catalyst component comprising a silicon compound (d), if necessary.

(A) Magnesium compound The magnesium compound is not particularly limited, but is generally
Formula (I) MgR¹R^Two... It is preferable to use a magnesium compound represented by the following formula (I).
it can. In the above general formula (I), R¹And R^Two
Is a hydrocarbon group, OR^ThreeGroup (R ^ThreeIs a hydrocarbon group) or
Indicates a halogen atom. Where R¹And R^TwoThe 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.^ThreeBase
As R^ThreeIs 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, R¹And R^TwoAre the same but different
It may be.

Specific examples of the magnesium compound represented by the above general formula (I) 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. As alcohol,
Methanol, ethanol, propanol, butanol,
Cyclohexanol, octanol and the like can be mentioned.

As another example, Mg (OR ⁴ ) ₂
In magnesium represented alkoxy compound (wherein, R ⁴
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 ⁴ , 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 is silica,
It may be supported on a support such as alumina or polystyrene. The above magnesium compounds may be used alone,
Two or more kinds may be used in combination. 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.

(B) Titanium compound The titanium compound is not particularly limited, but may have the general formula (I)
I) TiX¹ _p(OR^Five)_4-p ... Titanium compounds represented by (II) can be preferably used.
You. In the above general formula (II), X¹Is a halogen atom
And among them, a chlorine atom or a bromine atom is preferable,
A chlorine atom is particularly preferred. R^FiveIs a hydrocarbon group,
It may be a saturated or unsaturated group, and has a straight or branched chain
Or a ring,
Heteroatoms such as sulfur, nitrogen, oxygen, silicon and phosphorus
May be included. Preferably 1 to 10 carbon atoms
Hydrocarbon groups, especially alkyl groups, alkenyl groups, cyclo
Alkenyl groups, aryl groups and aralkyl groups are preferred.
Particularly preferred are linear or branched alkyl groups.
No. OR ^FiveAre the same as each other if there are multiple
But it may be different. R^FiveAs a specific example of
Group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, sec-butyl group, isobutyl group, n-pen
Tyl group, n-hexyl group, n-heptyl group, n-octyl
Group, n-decyl group, allyl group, butenyl group, cyclope
Methyl, cyclohexyl, cyclohexenyl,
Phenyl, tolyl, benzyl, phenethyl, etc.
I can do it. p shows the integer of 0-4.

Specific examples of the titanium compound represented by the general formula (II) 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.

(C) Electron-donating compound Examples of the electron-donating compound include alcohols, phenols, ketones, aldehydes, esters of organic acids and inorganic acids, and ethers such as monoether, diether and polyether. And nitrogen-containing electron donating compounds such as ammonia, 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. As dicarboxylic acids,
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. In that case,
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,
Examples thereof include 2-methylpentyl, 3-methylpentyl, 2-ethylpentyl, and 3-ethylpentyl. Among these, phthalic acid diesters are preferable, and a linear or branched aliphatic hydrocarbon having 4 or more carbon atoms in the organic group in the ester portion is preferable. Specific examples thereof include di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, and diethyl phthalate. These compounds may be used alone or in combination of two or more.

(D) Silicon compound In the preparation of the solid catalyst component, in addition to the above components (a), (b) and (c), the component (d) may optionally be represented by the following general formula (III) Si (OR) ^{_{6) q X 2 4-q}} ··· (III) (R 6 is a hydrocarbon group, X ² is a halogen atom, q is 0 to 3
Indicates an integer. ) 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, may have a linear or branched chain, or may have a cyclic structure, and furthermore, sulfur, nitrogen, oxygen, It may contain a hetero atom such as silicon or phosphorus. 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. 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, n-heptyl, Examples include n-octyl, n-decyl, allyl, butenyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, tolyl, benzyl, and phenethyl groups. 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 (A) organoaluminum compound used for producing the crystalline polypropylene of the component (i) constituting the present invention is not particularly limited, but may be an alkyl group, a halogen atom or a hydrogen atom. , Those having 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, trialkylaluminums having a lower alkyl group having 1 to 5 carbon atoms, particularly trimethylaluminum, triethylaluminum,
Tripropyl aluminum and triisobutyl aluminum are preferred. These organoaluminum compounds may be used alone or in combination of two or more.

(C) Third Component (Electron-donating Compound) In preparing the catalyst for the polymerization of crystalline polypropylene as the component (i) constituting the present invention, (C) an electron-donating compound is used as necessary. . As the (C) electron donating compound, an organosilicon compound having a Si—O—C bond, a nitrogen-containing compound, a phosphorus-containing compound, and an oxygen-containing compound can be used. Among them, from the viewpoint of polymerization activity and stereoregularity, an organosilicon compound having a Si—O—C bond,
It is preferable to use ethers and esters,
In particular, it is preferable to use an organosilicon compound having a Si-OC bond.

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-substituted 2,5-diisopropylazolidine and N-methyl 2,2,5,5-tetramethylazolidine
Substituted azolidines; substituted methylene diamines such as N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetraethylmethylenediamine; 1,3
-Dibenzylimidazolidine, 1,3-dibenzyl-2
-Substituted imidazolidines such as phenylimidazolidine;

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) magnesium compound, (b) titanium compound,
The (c) electron donor and, if necessary, the (d) silicon compound may be brought into contact by a usual method except for the temperature, 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,
Each component may be diluted with an inert solvent such as a hydrocarbon in advance and contacted. 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 5,000 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 1
Wash with an inert solvent at a temperature of 00-150 ° C, preferably 120-140 ° C. If the washing temperature is outside the above range, the effect of improving the catalytic activity and stereoregularity may not be 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 toluene and xylene, tetrachloroethane, chlorofluorocarbons and the like. Or a mixture thereof. Of these, aliphatic hydrocarbons are preferably used.

The washing method is not particularly limited, but a method such as decantation or filtration is preferred. 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. In addition,
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 for producing the crystalline polypropylene of the component (i) constituting the present invention is not particularly limited, but the solid catalyst component of the component (A) may be a titanium atom. The reaction volume is usually 0.00
An amount such that it is in the range of 005 to 1 mmol,
The organoaluminum compound as the component (B) has an aluminum / titanium atomic ratio of usually 1 to 1,000, preferably 10 to 1,000.
An amount is used such that it is in the range of ~ 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 0.01 to 2.0,
More preferably, an amount is used so as to be in the range of 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 polymerization of the crystalline propylene of the component (i) constituting the present invention, first, if necessary, after preliminarily polymerizing an olefin, from the viewpoints of polymerization activity, stereoregularity and polymer powder form, The main polymerization may be performed.
In this case, the olefin 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. At a temperature in the range of -100 ° C, pre-polymerization is carried out at normal pressure to a pressure of about 50 kg / cm ² G, and then propylene is main-polymerized in the presence of a catalyst and a pre-polymerized product.

As the olefin used for the prepolymerization, an α-olefin represented by the general formula (V) R ¹⁴ —CH ＝ CH ₂ (V) is preferable. In the general 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-
Examples thereof include 1-pentene, vinylcyclohexane, butadiene, isoprene, and piperylene. These olefins may be used alone or in combination of two or more. Among the olefins, ethylene and propylene are particularly 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. Further, it can be applied to both batch polymerization and continuous polymerization. It is applicable to two-stage polymerization and multi-stage polymerization under different conditions. Further, regarding the reaction conditions, the polymerization pressure is not particularly limited, and is usually from atmospheric pressure to 80 kg / c from the viewpoint of polymerization activity.
m ² G, preferably ^{2 to} 50 kg / cm ² G, the polymerization temperature is usually 0 to 200 ° C., preferably 20 to 90 ° C.,
More preferably, it is appropriately selected within the range of 40 to 90 ° C. The polymerization time depends on the polymerization temperature of propylene as a raw material and cannot be determined unconditionally.
0 hour, 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. Polymerization can be carried out in two or more stages under different polymerization conditions. In the polymerization for producing the crystalline polypropylene of the component (i) constituting the present invention, the catalyst component is prepared by mixing the component (A), the component (B) and the component (C) at a predetermined ratio. After mixing and contacting, propylene may be introduced immediately to carry out polymerization, or after contacting, aging may be carried out for about 0.2 to 3 hours, and then propylene may be introduced to carry out polymerization. Further, this catalyst component can be supplied by suspending in an inert solvent or propylene.

In the polymerization for producing the crystalline polypropylene of the component (i) constituting 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, to remove the olefins and the like contained in the polymer powder derived from the polymerization vessel,
It may be passed through a nitrogen stream or the like, or may be pelletized by an extruder, if desired.At that time, in order to completely deactivate the catalyst, a small amount of water, alcohol, or the like may be added. it can. 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.

In addition, in the main polymerization of propylene, as long as the produced crystalline polypropylene satisfies the relationship of the above formula (1), a small amount of ethylene, 1-
Butene, 1-pentene, 1-hexene, 1-heptene,
It may be copolymerized with an α-olefin such as 1-octene, 1-decene, 3-methyl-1-pentene and 4-methyl-1-pentene.

Next, the components (ii) and (iii) additives to be added to the crystalline polypropylene of the component (i) will be described. ( Ii) Component As the antistatic agent used as the component (ii), those conventionally used as an antistatic agent or an antistatic agent can be used without any particular limitation. For example, anionic surfactant Agents, cationic surfactants, nonionic surfactants, amphoteric surfactants and the like.

Examples of the above anionic surfactants include fatty acids or carboxylate salts such as rosin soap, N-acyl carboxylate, ether carboxylate, fatty acid amine salt; sulfosuccinate, ester sulfonate, and N-acyl. Sulfonates such as sulfonates; sulfates such as sulfated oils, sulfates, alkyl sulfates, alkyl polyoxyethylene sulfates, ether sulfates, sulfate amides, and the like; alkyl phosphates, alkyl polyphosphates Phosphate ester salts such as oxyethylene salts, phosphoric acid ether salts and phosphoric amide salts can be mentioned.

Examples of the cationic surfactant include amine salts such as alkylamine salts; alkyltrimethylammonium chloride, alkylbenzyldimethylammonium chloride, alkyldihydroxyethylmethylammonium chloride, dialkyldimethylammonium chloride, tetraalkylammonium salt, Quaternary ammonium salts such as N-di (polyoxyethylene) dialkylammonium salt and N-alkylalkanamidoammonium salt; 1-hydroxyethyl-2-alkyl-2-
Imidazoline, 1-hydroxyethyl-1-alkyl-
Alkyl imidazoline derivatives such as 2-imidazoline; and imidazolinium salts, pyridinium salts, isoquinolium salts and the like.

Examples of the nonionic activator include ether types such as alkyl polyoxyethylene ether and p-alkylphenyl polyoxyethylene ether, fatty acid sorbitan polyoxyethylene ether, fatty acid sorbitol polyoxyethylene ether, and fatty acid glycerin polyoxyethylene. Ether ester type such as ether, fatty acid polyoxyethylene ester, monoglyceride, diglyceride, sorbitan ester, sugar ester, ester type such as dihydric alcohol ester, borate ester, dialcohol alkylamine, dialcohol alkylamine ester, fatty acid alkanolamide N, N-di (polyoxyethylene) alkaneamide, alkanolamine ester, N, N-di (polyoxyethylene) alkaneamine, amine Kishido, such nitrogen-containing type such as alkyl polyethylene imine may be mentioned.

Examples of the amphoteric surfactant include amino acid types such as monoaminocarboxylic acid and polyaminocarboxylic acid;
N-alkyl-β- such as -alkylaminopropionate and N, N-di (carboxyethyl) alkylamine salt
Betaine types such as alanine type, N-alkylbetaine, N-alkylamidobetaine, N-alkylsulfobetaine, N, N-di (polyoxyethylene) alkylbetaine, imidazolinium betaine; 1-carboxymethyl-1-hydroxy Examples thereof include alkylimidazoline derivatives such as -1-hydroxyethyl-2-alkyl-2-imidazoline and 1-sulfoethyl-2-alkyl-2-imidazoline.

The surfactant is preferably a nonionic surfactant or an amphoteric surfactant. Among them, monoglyceride, diglyceride, borate ester, dialcohol alkylamine, dialcohol alkylamine ester,
Preferred are ester-type or nitrogen-containing nonionic surfactants such as amides; betaine-type amphoteric surfactants. Commercial products can also be used as the antistatic agent, for example,
Electrostripper TSS (manufactured by Kao Corporation, trademark, glycerin monostearate), Electrostripper E
A (manufactured by Kao Corporation, trademark, lauryl diethanolamine),
Denon 331P (manufactured by Marubishi Yuka Co., Ltd., trademark, stearyl diethanolamine monostearate), electrostripper EA-7 (manufactured by Kao Corporation, trademark, polyoxyethylene laurylamine caprylic ester), resist PE
-139 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trademark, monostearate & diglyceride borate), Chemistat 470
0 (Sanyo Kasei Co., Ltd., trademark, alkyl dimethyl betaine)
And the like.

These antistatic agents can be used alone or in combination. The compounding amount is preferably 0.05 to 100 parts by weight of crystalline propylene.
It is 2 parts by weight, more preferably 0.1 to 1 part by weight. When the compounding amount of the antistatic agent is within the above range, it is possible to reduce the surface specific resistance and prevent the trouble due to charging, to obtain a composition having excellent electrical properties, and to obtain the properties of crystalline propylene. For example, the tensile strength does not decrease.

( Iii) Component The antifogging agent used as the component (iii) may be a film,
A chemical compounded to prevent condensation of moisture in the air on the surface of molded products such as sheets and tubes, and to prevent the molded product from becoming cloudy.The agent makes the surface of the molded product hydrophilic and spreads the generated water droplets. There is no particular limitation as long as it has the effect of causing
Those generally used as antifogging agents can be used as they are.

Surfactants are used as such anti-fogging agents, for example, sorbitan fatty acid esters such as sorbitan monooleate, sorbitan monobehenate and sorbitan monostearate; glycerin such as glycerin monooleate and glycerin monostearate. Fatty acid esters: dixerin monooleate, diglycerin sesquilaurate, diglycerin sesquiolate, tetraglycerin monooleate, tetraglycerin monostearate,
Polyglycerin fatty acid esters such as hexaglycerin monolaurate, hexaglycerin monooleate, decaglycerin monooleate, decaglycerin monolaurate; polyoxyalkylene ethers such as polyoxyethylene lauryl ether; fatty acid amines such as lauryl diethanolamine; oleic acid amide And the like, but not limited thereto. Among them, glycerin fatty acid esters, polyglycerin fatty acid esters, polyoxyalkylene ethers, and fatty acid amines are preferable.

These antifogging agents can be used alone or in combination of two or more. When a combination of more than one kind of antifogging agent is used, there is an effect that the initial antifogging property and the antifogging durability are excellent in balance and the temperature range in which the antifogging property is developed becomes wide (particularly in a low temperature range). . Examples of the combination of two or more antifogging agents include a combination of an aliphatic amine and a glycerin fatty acid ester, and specifically, a combination of lauryl diethanolamine and glycerin monostearate. There is also a combination of an aliphatic amine, a glycerin fatty acid ester and a polyglycerin fatty acid ester, and specifically, a combination of lauryl diethanolamine, glycerin monostearate and diglycerin sesquilaurate.

The amount of the antifogging agent is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the crystalline polypropylene (i). When the compounding amount of the antifogging agent is in the above range, the antifogging effect is easily obtained, and the antifogging agent does not bleed from the surface of the molded article, has excellent transparency, and has excellent antifogging durability, mechanical properties and A molded article excellent in heat resistance can be obtained.

The molded article according to the second invention of the present application can be obtained by molding using the above-mentioned crystalline polypropylene resin composition. Examples of the molded article of the present invention include automotive interior materials, housing materials for call products, films, sheets, and the like. Examples of the molding method include an injection molding method, a compression molding method, an injection compression molding method, 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, if desired, to the crystalline polypropylene composition by adding an antiblocking agent, an antioxidant, a weathering agent, a heat stabilizer, a lubricant, a nucleating agent, a coloring agent, and a drip-free agent. The resin composition may be prepared after blending known additives such as a flame retardant, a flame retardant auxiliary, an antibacterial agent, and an inorganic or organic filler.

[0066]

[Production Example 1]

(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 octane.
0 ml was added. Heat to 40 ° C and silicon tetrachloride 24
Then, the mixture was 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 at 770 using a dropping funnel.
Milliliter was dropped. The internal temperature was set to 125 ° C., and a contact reaction was performed for 2 hours. Thereafter, washing was sufficiently performed using 125 ° C. dehydrated octane. Further, 1,220 ml of titanium tetrachloride was added, the internal temperature was set to 125 ° C., and a contact reaction was performed for 2 hours. Thereafter, the solid was thoroughly washed with 125 ° C. dehydrated octane to obtain a solid component [A].

(Preliminary polymerization) 48 parts of the solid component [A] was placed in a 1-liter three-necked flask equipped with a stirrer and purged with nitrogen.
g. Further, 400 g of dehydrated n-heptane was added.
Milliliter was added. The mixture was heated to 40 ° C., and 2.0 ml of triethylaluminum and 6.3 ml of diisopentyldimethoxysilane were added. Propylene was allowed to flow therethrough at normal pressure and reacted for 2 hours. Thereafter, the solid component was sufficiently washed with dehydrated n-heptane to obtain a catalyst component.

(Polymerization) A 10-liter volume with a stirrer
Thoroughly dry the Tenless autoclave and purge with nitrogen.
Thereafter, 6 liters of dehydrated n-heptane was added to the inside.
Was. While stirring, the temperature was raised until the internal temperature reached 80 ° C. Rise
After warming, 40.0 mmol of triethylaluminum, followed by
Add 5.0 mmol of dicyclopentyldimethoxysilane
Further, the solid catalyst component is added at 0.1 mm / Ti.
Mole, hydrogen 3.0kg / cm ^TwoAfter introducing G, the total pressure
8.0 kg / cm^TwoIntroduce propylene until it reaches G
Was. Total pressure is 8.0kg / cm^TwoIt is 1 o'clock from the time when it became G
Interpolymerization was performed. Then lower the temperature, depressurize and remove the contents
And remove the solvent with an evaporator.
A propylene powder was obtained. Its polypropylene powder
-Measurement of resin properties (structural properties) as described below
Was done. Table 2 shows the results. [Production Example 2] In Production Example 1, the amount of hydrogen introduced during polymerization was
2.8kg / cm^TwoSame as Production Example 1 except for G
To produce polypropylene. [Production Example 3] In Production Example 1, the amount of hydrogen introduced during polymerization was
1.0kg / cm^TwoSame as Production Example 1 except for G
To produce polypropylene. [Production Example 4] In Production Example 1, the amount of hydrogen introduced during polymerization was
0.5kg / cm^TwoSame as Production Example 1 except for G
To produce polypropylene. [Production Example 5] In Production Example 1, the amount of hydrogen introduced during polymerization was
0.1kg / cm^TwoSame as Production Example 1 except for G
To produce polypropylene.

[Production Example 6] (Preparation of solid catalyst component) 160 g of diethoxymagnesium was charged into a 5-necked, three-necked flask equipped with a stirrer purged with nitrogen, and 600 ml of dehydrated n-heptane was added. added. The mixture was heated to 40 ° C., added with 24 ml of silicon tetrachloride, stirred for 20 minutes, and added with 25 ml of diethyl phthalate. The temperature of the solution was raised to 80 ° C., and titanium tetrachloride was added to the solution using a dropping funnel.
0 ml was dropped. The internal temperature was 110 ° C., and the reaction was carried out for 2 hours. Thereafter, washing was sufficiently performed using dehydrated n-heptane at 90 ° C. Further, 770 ml of titanium tetrachloride was added, the internal temperature was set to 110 ° C., and a contact reaction was performed for 2 hours. Thereafter, the solid was thoroughly washed with dehydrated n-heptane at 90 ° C. to obtain a solid component [B]. (Preliminary polymerization) 48 g of the solid component [B] was placed in a 1-liter three-necked flask equipped with a stirrer and purged with nitrogen, and then 400 ml of dehydrated n-heptane was added. While maintaining the temperature at 10 ° C., 2.7 ml of triethylaluminum and 2.0 ml of cyclohexylmethyldimethoxysilane were added. Propylene was allowed to flow therethrough at normal pressure and reacted for 2 hours. Thereafter, the solid component is dehydrated.
-Fully washed with heptane to obtain a catalyst component.

(Polymerization) A stainless steel autoclave with a stirrer having an internal volume of 10 liters was sufficiently dried, and after replacement with nitrogen, 6 liters of dehydrated n-heptane was added therein. While stirring, the temperature was raised until the internal temperature reached 80 ° C. After the temperature was raised, 40.0 mmol of triethylaluminum and subsequently 5.0 mmol of cyclohexylmethyldimethoxysilane were added, and the solid catalyst component was added in an amount of 0.1 per Ti.
Mmol addition, after the introduction of hydrogen 1.1 kg / cm ² G, the total pressure was introduced propylene until 8.0kg / cm ² G. 1 from the point when the total pressure reaches 8.0 kg / cm ² G
Time polymerization was carried out. Thereafter, the temperature was lowered and the pressure was released, the contents were taken out, the solvent was removed with an evaporator, and the product was dried under vacuum to obtain polypropylene.

[Production Example 7] A polypropylene was produced in the same manner as in Production Example 6 except that the amount of hydrogen introduced during the polymerization was changed to 0.5 kg / cm ² G. [Production Example 8] A polypropylene was produced in the same manner as in Production Example 6, except that the amount of hydrogen introduced during the polymerization was changed to 0.2 kg / cm ² G. [Production Example 9] A polypropylene was produced in the same manner as in Production Example 6, except that the amount of hydrogen introduced during the polymerization was changed to 0.01 kg / cm ² G.

Examples 1 to 11 and Comparative Examples 1 to 4 Additives shown in Table 2 were added to 100 parts by weight of the polypropylene powder obtained in Production Examples 1 to 9 at the ratios shown in Table 2, and 0.1 parts by weight of calcium stearate (manufactured by NOF Corporation) as a neutralizing agent, DHT-4A
0.05 parts by weight (manufactured by Kyowa Chemical), 0.075 parts by weight of P-EPQ (manufactured by Clariant) as an antioxidant, and Irganox 1010 (Ciba Specialty Co., Ltd.)
0.15 parts by weight of Chemicals Co., Ltd.) was added, mixed well, and then melt-kneaded and granulated with a 20 mm single-screw kneading extruder to form pellets. The pellets were injection-molded and extruded to prepare various test pieces in the following manner, and the mechanical properties, electrostatic properties and anti-fogging property were evaluated. Table 2 shows the results.

(1) Test Piece for Measurement of Injection Molded Product A test piece was prepared at a resin temperature of 200 ° C. and a mold temperature of 45 ° C. using an IS100FIII type injection molding machine manufactured by Toshiba Machine Co., Ltd. (2) Test piece (film) for measuring extruded products Using an extruder manufactured by Tanabe Plastics Machine Co., Ltd., resin temperature 250 ° C., chill roll temperature 45 ° C., take-off speed 20 m /
A film having a thickness of 30 μm was formed under the conditions of min.

(Method of Measuring Structural Characteristics and Mechanical Properties) (1) Intrinsic viscosity [η] It was dissolved in tetralin and measured at 135 ° C. (2) Amount of soluble matter at 0 ° C. and peak temperature of elution curve by temperature-increased fractionation method Regarding the polypropylene powder obtained by polymerization,
It is determined by the temperature rising free separation method. Sample preparation is performed at room temperature
75m of polymer in 10ml of dichlorobenzene
g is weighed, and stirred at 135 to 150 ° C. for 1 hour to dissolve. After 0.5 ml of the sample solution is injected into the column at 135 ° C., the polymer is gradually cooled to 0 ° C. at 10 ° C./hr to crystallize the polymer on the surface of the filler. At that time, the amount of the polymer remaining without crystallization was defined as the soluble matter at 0 ° C. After cooling, the elution curve was determined by adding o-dichlorobenzene to 2 ml / m 2.
The column temperature is raised at 40 ° C./hr while flowing in, and the concentration of the polymer eluted as needed is determined by continuous measurement with an infrared detector. In the obtained elution curve, the temperature at the peak position was defined as the peak temperature. The column used was 4.6 mmφ × 150 mm, the packing material used was Chromosolve P, and the elution curve was adjusted using linear PE (SRM1475) as a standard sample. (± 0.5). A wavelength of 3.41 μm was used for detection.

(3) Measurement of Mechanical Properties of Injection Molded Product For the test piece obtained by injection molding, tensile elastic modulus, flexural elastic modulus, heat distortion temperature (HDT), Rockwell hardness (HR)
[R scale]) was changed to JIS K 7113, K
It measured according to 7203, K7207, and K7202. (4) Evaluation of Electrostatic Characteristics (Surface Resistivity) of Injection-Molded Product After a 2 mm-thick injection-molded square plate was stored in an environment of 23 ° C. and 50% RH for 7 days, it was measured according to JIS K 6911. . (5) Evaluation of anti-fogging property (adhesion area) of the film
Milliliter was added, the sample was covered with a beaker with the anti-fog side facing inside, and allowed to cool in a room at 5 ° C. for 30 minutes. And 30
After a lapse of minutes, the adhesion of water droplets to the film surface was visually observed, and a five-step evaluation was performed based on the criteria shown in Table 1 below.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

[0080]

[Table 5]

The additives used in the examples and comparative examples are as follows. Antistatic agent A: Glycerin monostearate (Electrostripper TS5, manufactured by Kao Corporation) Antistatic agent B: Stearyl diethanolamine monostearate (Denone 331P, manufactured by Marubishi Yuka Kogyo Co., Ltd.) Antifogging agent A: Lauryl diethanolamine ( Electrostripper EA, manufactured by Kao Corporation) Antifogging agent B: diglycerin sesquilaurylate (PA-5)
395, Marubishi Yuka Kogyo Co., Ltd.)

In Table 2, when comparing Example 1 and Comparative Example 1 showing almost the same [η], the crystalline polypropylene composition of the present invention showed a tensile modulus, a flexural modulus, a heat deformation temperature and a Rockwell temperature. It can be seen that the hardness is excellent. Similarly, the same can be said for the comparison between Example 2 and Comparative Example 2, the comparison between Example 3 and Comparative Example 3, and the comparison between Example 10 and Comparative Example 4. In addition, even when the elution peak is within the range of the present invention as shown in Comparative Example 2, it is clear that the physical properties are reduced when the amount of the soluble matter at 0 ° C. is large. It is clear that the use of an antistatic agent and an antifogging agent has improved the effect.

[0083]

According to the novel crystalline polypropylene resin composition of the present invention, it is possible to reduce the thickness of a molded product by increasing rigidity, to reduce the weight, and to save resources and improve productivity. . In addition, by improving rigidity and heat resistance, it is possible to substitute for applications in which polystyrene, ABS resin, and the like are conventionally used. Further, since the molded article of the present invention has excellent rigidity, heat resistance, scratch resistance, electrostatic properties and anti-fog properties, it can be suitably used for automotive interior materials, housing materials of home electric appliances, films and the like. it can.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA20 AA88 AE16 AE22 AF05 AF11 AF14 AF38 AF45 AH11 AH12 BA01 BB03 BB05 BB06 BB13 BC01 BC07 4J002 AF022 BB121 CH052 CH053 CM012 EE056 EF007 EF056 EG006 ENH006 EEG006 ENH006 EN 006 EP017 EU046 EU116 EV186 EV256 EW046 EY016 FD102 FD106 FD203 FD207 4J100 AA02Q AA03P AA04Q AA07Q AA15Q AA16Q AA17Q AA18Q AA19Q AA21Q CA01 CA04 DA09 DA40 FA09

Claims (6)

[Claims] 1. (i) Soluble content α at 0 ° C. by a temperature rising fractionation method
(% By weight) and the intrinsic viscosity [η] (deciliter / g) measured at 135 ° C. in a tetralin solvent are represented by the following formula (1) α ≦ 1.11 × [η] ^−0.42 + 1.40 (1) A crystalline polypropylene resin composition obtained by blending (ii) an antistatic agent and / or (iii) an antifogging agent with a crystalline polypropylene satisfying the following relationship: 2. The compounding amount of the component (ii) is (1)
The amount is 0.05 to 2 parts by weight based on 00 parts by weight.
The crystalline polypropylene resin composition as described in the above. 3. The compounding amount of the component (iii) is 0.1 to 5 parts by weight based on 100 parts by weight of the component (i).
Or the crystalline polypropylene resin composition according to 2. 4. The component (i) has a peak temperature T _P (° C.) of an elution curve obtained by a temperature rising fractionation method and a temperature of 1 ° C.
Intrinsic viscosity [η] measured at 35 ° C (deciliter / g)
Is a crystalline polypropylene that satisfies the following formula (2): T _P > 1.21 × [η] +116.5 (2)
4. The crystalline polypropylene resin composition according to any one of 3. 5. The component (i) has an intrinsic viscosity [η] of 0.5 to 4.0 measured at 135 ° C. in a tetralin solvent.
The crystalline polypropylene resin composition according to any one of claims 1 to 4, which is a crystalline polypropylene in a range of deciliter / g. 6. A molded product obtained by molding the crystalline polypropylene resin composition according to claim 1.