JPH09252803A - Polypropylene resin for ski boots - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene resin for ski boots excellent in mechanical strength, flexibility at a low temperature, shock resistance, and scar resistance, having heat resistance and a high gloss, capable of being manufactured by injection molding with high productivity, and excellent in fashionability. SOLUTION: This polypropylene resin for ski boots is composed of (A) 10020wt.% of a resin made of a copolymer containing a propylene single polymer and/or another olefin olefin unit of 4wt.% or below and having (a) the pentad percentage rrrr/(1-mmmm)×100 of 15-60% of 4wt.% or below and having (a) the pentad percentage rrrr/(1-mmmm)×100 of 15-60% in the isotopic carbon unclear magnetic resonance spectrum (<13> C-NMR) and (b) the fused enthalpy (ΔH) of 10-100J/g measured by DSC and (B) 0-80wt.% of a propylene copolymer containing the olefin unit of 10-80wt.% other than propylene.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polypropylene resin for ski boots, and in particular, it is excellent in mechanical strength, low temperature impact resistance, heat resistance and scratch resistance, as well as excellent in colorability, gloss and fashionability. And a polypropylene resin for ski boots.

[0002]

2. Description of the Related Art In recent years, various thermoplastic resins have been used for sporting goods because of their moldability, colorability and lightness. Above all, ski boots have recently been drawing attention because they can be colored to give them a lustrous color. As a resin for such ski boots,
(1) Organopolysiloxane is added to 100 parts by weight of a thermoplastic resin in order to improve scratch resistance and mold releasability during molding.
Elastic ski shoes mixed with 1 to 5 parts by weight (JP-A-62-60)
No. 501). (2) A composition for ski boots containing 50 to 90% by weight of a polyamide resin, 2 to 40% by weight of a modified polyolefin-containing resin composition, and 2 to 40% by weight of a modified olefin-based elastomer-containing elastomer composition (Japanese Patent Laid-Open Publication No. HEI-6 (1999)). No. 46901). (3) Polyamide resin 55 to 90% by weight, modified polyolefin-containing resin mixture 2 to 25% by weight, and modified olefin elastomer-containing elastomer mixture 2 to 40% by weight in total 100
Potassium titanate whiskers 0.01 to 5 parts by weight
Ski boot composition containing 1 part by weight and 0.01 to 1 part by weight of a phosphorus compound (JP-A-6-133801)
There is. Virtually all of these are resin compositions containing a polyamide resin as a main component and a modified polyolefin resin added thereto. However, these ski boot resin compositions have tried to improve the water absorption, flexibility at low temperature, and impact resistance of the polyamide resin by adding a polyolefin resin, but the polyamide resin is the main component. No essential solution has been reached.

On the other hand, when a polyolefin resin is used, (4) the content of ethylene polymerized by a specific catalyst is 85 to 95 mol%, and the density is 0.86 to 0.91.
Ski shoes have been proposed which have a polyolefin composition consisting of 60 to 85% by weight of a g / cm ³ ethylene / 1-butene random copolymer and 40 to 15% by weight of polypropylene (Japanese Patent Publication No. 59-13202). Issue). However, in this composition, since general polypropylene is used, the heat resistance is high, but polypropylene itself is not flexible.
There is a problem in obtaining uniform properties because there is a large difference in properties from the 1-butene random copolymer.

[0004]

Under the above circumstances, the present invention is directed to mechanical strength, low temperature impact resistance, heat resistance, hardness,
An object of the present invention is to provide a polypropylene resin for ski boots, which has good scratch resistance and can be manufactured with good productivity by injection molding ski boots excellent in fashionability such as coloring and surface gloss.

[0005]

Means for Solving the Problems As a result of intensive studies to develop a resin satisfying many characteristics required for the ski boots, the present inventors have found that a specific soft polypropylene resin is It has been found that it can meet the purpose. The present invention has been completed based on such findings.

That is, the present invention provides (a) a melting peak temperature (Tm) measured by a differential scanning calorimeter (DSC).
Is 150 ° C or higher, (b) tensile modulus is 20 to 500MP
a) a polypropylene resin for ski boots, which comprises a soft polypropylene resin which is a, in particular, such a soft polypropylene resin has a pentad fraction based on (A) (c) isotope carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR) , Rrrr / (1-mmmm) × 100 is 15 to 6
0%, (d) Containing a propylene homopolymer having a melting enthalpy (ΔH) of 10 to 100 J / g as measured by a differential scanning calorimeter (DSC) and / or other olefin units of 4% by weight or less. 100 to 20% by weight of the copolymer, and (B) olefin units other than propylene 10 to 8
A polypropylene resin for ski boots, which is a polypropylene resin composed of 0 to 80% by weight of a propylene copolymer containing 0% by weight.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the polypropylene resin for ski boots of the present invention, (a) the melting peak temperature (Tm) measured by a differential scanning calorimeter (DSC) is 15
There is no particular limitation as long as it is a soft polypropylene resin having a tensile modulus of 20 to 500 MPa at 0 ° C. or higher, and it is a homopolymer of propylene, a copolymer of propylene and another olefin, or a mixture thereof. Good. As such a resin component, (A) a propylene homopolymer and / or a copolymer containing 4% by weight or less of other olefin units may be used, and the resin of the (A) component, (B) 10 to 8 olefin units other than propylene
A composition comprising a propylene-based copolymer containing 0% by weight may be used.

However, it is particularly preferable that the soft polypropylene resin is (A) in addition to (A) the melting peak temperature and (B) tensile modulus, and (C) an isotope carbon nuclear magnetic resonance spectrum ( ¹³ C). In the pentad fraction by -NMR), rrrr / (1-mmmm) x 100 is 1
5-60%, (d) Melting enthalpy (ΔH) measured by differential scanning calorimetry (DSC) is 10-100 J /
g of propylene homopolymer and / or copolymer containing 4% by weight or less of other olefin units 100 to 2
0% by weight and (B) olefin units other than propylene 1
Propylene-based copolymer containing 0 to 80% by weight 0 to 8
It is a polypropylene resin composed of 0% by weight.

Hereinafter, desirable properties related to the soft polypropylene resin in the present invention will be described. First, regarding the soft polypropylene-based resin, it is necessary that (a) the melting peak temperature (Tm) measured by a differential scanning calorimeter (DSC) is 150 ° C. or higher. Tm
Is less than 150 ° C, sufficient heat resistance cannot be obtained. This T
m is usually in the range of 150 to 165 ° C. The T
m is a value determined as a melting peak temperature in accordance with JIS K7121 by measuring using DSC-7 manufactured by Perkin-Elmer.

Next, the soft polypropylene resin (b) has a tensile elastic modulus of 20 to 500 MPa, preferably 30 to 400 MPa. When it is less than 20 MPa, strength and rigidity are insufficient, and when it exceeds 500 MPa, flexibility and low temperature impact resistance are insufficient. The tensile elastic modulus is a value determined according to JIS K6760. Also,
(A) Component propylene homopolymer and 4% by weight
Regarding the copolymers containing the following other olefin units, (C) isotope carbon nuclear magnetic resonance spectrum ( ¹³ C-N
In the pentad fraction by MR, rrrr / (1
-Mmmm) × 100 is preferably in the range of 15 to 60%. If this value is less than 15%, the heat resistance is insufficient, and if it exceeds 60%, the flexibility is insufficient. From these aspects, preferable rrrr / (1-mmmm) ×
100 is in the range of 20 to 55%. Here, rrrr is a three-dimensional structure in which five methyl groups, which are side chains, are alternately located in opposite directions with respect to the main chain formed by carbon-carbon bonds composed of arbitrary continuous five propylene units, or a ratio thereof. The term "mmmm" means a three-dimensional structure in which all five methyl groups as side chains are located in the same direction with respect to the main chain formed by carbon-carbon bonds composed of arbitrary continuous five propylene units, or the ratio thereof. Means

Note that this rrrr / (1-mmmm) ×
100 is a value measured as follows. That is,
Using JNM-FX-200 (manufactured by JEOL Ltd., ¹³ C-nuclear resonance frequency 50.1 MHz), measurement mode: complete proton decoupling method, pulse width: 6.9 μs (45 °), pulse repetition time: 3 s, Accumulation number: 10,000 times, solvent: 1,2,4-trichlorobenzene / deuterated benzene (9
0/10% by volume), sample concentration 250 mg / 2.5 ml solvent, measurement temperature: 130 ° C., ¹³ C-NM
R measurement was performed, and the pentad fraction was measured by the difference in chemical shift due to the stereoregularity of the methyl group, that is, from the area intensity ratio of each peak of mmmm to mrrm appearing in the 22.5 to 19.5 ppm region, and rrrr was measured. / (1-mm
The value of (mm) × 100 was determined.

Mmmm: 21.86 ppm mmmr: 21.62 ppm mmrr: 21.08 ppm mmrm + rrmr: 20.89 ppm rrrr: 20.36 ppm mrrm: 19.97 ppm Further, the above (A) component was measured by (d) DSC. Melting enthalpy (ΔH) is 10-100 J / g
It is desirable that: If ΔH exceeds 100 J / g, the flexibility may be impaired and the object of the present invention may not be achieved. This ΔH is usually in the range of 20 to 100 J / g. The ΔH was measured using DSC-7 manufactured by Perkin-Elmer, and was measured according to JIS K-712.
This is a value determined as the total heat energy absorbed during melting of the crystal in accordance with No. 2. In addition, Tm, ΔH by DSC
The rate of temperature increase / decrease in the measurement of is 10.degree. C./min.

The propylene homopolymer of component (A) and the copolymer containing 4% by weight or less of other olefin units have a boiling n-heptane insoluble content of 40 to 95%.
Those in the range of weight% are preferred. When the boiling n-heptane insoluble content exceeds 95% by weight, flexibility may be impaired, and when it is less than 40% by weight, sufficient mechanical strength tends to be not obtained. From the viewpoint of the balance between flexibility and mechanical strength, a more preferable boiling n-heptane insoluble content is in the range of 50 to 93% by weight. In addition, the boiling n-heptane insoluble content is a value obtained by using a Soxhlet extraction tester and calculating from the extraction residual amount after extraction with boiling n-heptane for 6 hours.

Further, in the propylene homopolymer and the copolymer containing 4% by weight or less of other olefin units, carbon having a side chain methyl group is usually adjacently arranged in the propylene chain. There is nothing, that is, there is no reverse coupling, and every other is neatly arranged.
That is, in the present invention, each propylene unit is linked by a head-tail bond, and
There are virtually no ead) or tail-tail bonds.

In the propylene copolymer containing 4% by weight or less of other olefin units, the comonomer olefins forming the other olefin units include, for example, ethylene; butene-1; pentene-1; 4
-Methyl-1-pentene; hexene-1; heptene-
1; octene-1, nonene-1, decene-1 and other α-
Olefins can be mentioned. Of these, ethylene is preferred. These olefins may be used alone or in combination of two or more. Further, it is necessary to use the olefins of these comonomers such that the content of the units derived from the olefins in the obtained propylene copolymer is 4% by weight or less.

In the flexible polypropylene resin of the present invention, a resin comprising the resin of the above-mentioned component (A) and a propylene-based copolymer containing (B) 10 to 80% by weight of an olefin unit other than propylene may be used as the resin. Can be used. Here, examples of the olefin of the comonomer that forms an olefin unit other than propylene include ethylene; butene-1; pentene-1; 4-methyl-1-
Pentene; hexene-1; heptene-1; octene-
1; α-olefins such as nonene-1 and decene-1, and dienes such as butadiene, dicyclopentadiene and tricyclopentadiene. The olefins of these comonomers may be used alone or in combination of two or more.

In the present invention, when the propylene copolymer of the above component (B) is used as the soft polypropylene resin component, the content of the component (B) in the resin component is 8%.
0% by weight or less. If this content exceeds 80% by weight, it is not preferable in terms of strength, elastic modulus and heat resistance. The preferred content of the component (B) is 70% by weight or less, particularly 60% by weight.
% By weight or less is preferred.

In the resin of the present invention, the polypropylene resin used as the component (A) preferably has a melt index (MI) in the range of 1 to 200 g / 10 minutes. If this MI is less than 1 g / 10 min, molding is difficult, and if it exceeds 200 g / 10 min, the mechanical properties of the molded product obtained are insufficient. More preferable MI in terms of balance between moldability and mechanical properties of molded products.
Is in the range of 5 to 100 g / 10 minutes. Note that this MI
Is a value measured under the conditions of a load of 2.16 kgf and a temperature of 230 ° C.

The soft polypropylene resin comprising the component (A) or the component (A) + (B) in the resin of the present invention is, for example, a gas phase one-step polymerization method, a slurry one-step polymerization method, a gas phase multi-step polymerization method, a slurry multi-step polymerization method. It can be manufactured by a legal method or a blend method. For example, when it is produced by a polymerization method, it is composed of (W) (i) a solid catalyst component composed of magnesium, titanium, a halogen atom and an electron donor, and (ii) a crystalline polyolefin which is optionally used. Homopolymerization of propylene in the presence of a catalyst system comprising a solid component, (X) an organoaluminum compound, (Y) an alkoxy group-containing aromatic compound, and (Z) an electron-donating compound optionally used, or Propylene and other olefins may be copolymerized.

The above-mentioned (W) solid component comprises (i) a solid catalyst component comprising magnesium, titanium, a halogen atom and an electron donor, and (ii) a crystalline polyolefin as necessary. Have been. The solid catalyst component of the component (i) is magnesium, titanium,
It has a halogen atom and an electron donor as essential components, and can be prepared by contacting a magnesium compound, a titanium compound and an electron donor. In this case, the halogen atom is included as a halide in the magnesium compound and / or the titanium compound.

Examples of the magnesium compound include magnesium dihalides such as magnesium chloride, magnesium oxide, magnesium hydroxide, hydrotalcite, carboxylates of magnesium, alkoxy magnesium such as diethoxy magnesium, allyloxy magnesium, alkoxy magnesium halides. , Alkyl magnesium such as allyloxy magnesium halide and ethyl butyl magnesium, alkyl magnesium halide, or organomagnesium compound and electron donor,
Examples thereof include reaction products with halosilanes, alkoxysilanes, silanols, aluminum compounds, and the like, and among these, magnesium halides, alkoxymagnesiums, alkylmagnesiums, and alkylmagnesium halides are preferable. These magnesium compounds may be used alone or in combination of two or more.

Further, as the magnesium compound, a reaction product of metallic magnesium, a halogen and an alcohol can be used. The metallic magnesium used at this time is not particularly limited, and metallic magnesium having an arbitrary particle size, for example, granular, ribbon-like, powder-like or the like can be used. Further, the surface state of the magnesium metal is not particularly limited, but it is preferable that the surface of the surface is not coated with magnesium oxide.

Further, any alcohol can be used, but it is preferable to use a lower alcohol having 1 to 6 carbon atoms. In particular, ethanol gives a solid catalyst component which remarkably improves the expression of catalytic performance. It is suitable. The purity and the water content of the alcohol are not limited, but when an alcohol having a high water content is used, magnesium hydroxide is formed on the surface of metal magnesium. Therefore, it is preferable to use an alcohol having a water content of 1% by weight or less, particularly 2000 ppm or less. Preferably, the lower the water content, the more advantageous.

The type of halogen and / or halogen-containing compound is not limited, and any compound containing a halogen atom in its molecule can be used as the halogen-containing compound. In this case, the type of halogen atom is not particularly limited, but chlorine, bromine or iodine, particularly iodine is preferably used. Among the halogen-containing compounds, halogen-containing metal compounds are particularly preferable. The state, shape, particle size, etc. are not particularly limited and may be arbitrary, for example, alcohol solvent (eg, ethanol).
It can be used in the form of a solution in.

The amount of the alcohol used is selected in the range of 2 to 100 mol, preferably 5 to 50 mol, per 1 mol of metallic magnesium. If the amount of alcohol is too large, it tends to be difficult to obtain a magnesium compound having a good morphology, and if it is too small, the reaction with metallic magnesium may not be carried out smoothly. The halogen and / or the halogen-containing compound is usually 0.000 as a halogen atom per 1 gram atom of metallic magnesium.
It is used in a proportion of 1 gram atom or more, preferably 0.0005 gram atom or more, and more preferably 0.001 gram atom or more. If it is less than 0.0001 gram atom, when the obtained magnesium compound is used without being crushed, the carried amount, activity, stereoregularity, morphology of the produced polymer and the like are lowered, and the crushing treatment becomes indispensable, which is not preferable. Further, by appropriately selecting the amount of halogen and / or the halogen-containing compound used, the particle size of the obtained magnesium compound can be arbitrarily controlled.

The reaction itself between the metal magnesium, the alcohol and the halogen and / or the halogen-containing compound can be carried out by a known method. For example, it is a method of obtaining a desired magnesium compound by reacting metallic magnesium, an alcohol, a halogen and / or a halogen-containing compound under reflux, usually for about 20 to 30 hours until generation of hydrogen gas is not observed. Specifically, for example, when iodine is used as the halogen, a method in which metallic magnesium and solid iodine are put into an alcohol and then heated and refluxed, and an alcohol solution of metallic magnesium and iodine is dropped into the alcohol and then added. Examples thereof include a method of heating and refluxing, a method of dropping an alcohol solution of iodine while heating an alcohol solution containing metallic magnesium, and the like. Both methods are preferably carried out in an inert gas atmosphere such as nitrogen gas or argon gas, optionally using an inert organic solvent (for example, saturated hydrocarbon such as n-hexane). Metal magnesium,
Regarding the introduction of the alcohol, the halogen and / or the halogen-containing compound, it is not necessary to add the entire amount to the reaction tank from the beginning, and it may be added in a divided manner. A particularly preferred form is a method in which the alcohol is charged in its entirety from the beginning, and the magnesium metal is divided and charged several times.

In this case, it is possible to prevent a temporary large amount of hydrogen gas from being generated, which is very desirable in terms of safety. Also, the size of the reaction tank can be reduced. Furthermore, it becomes possible to prevent the entrainment of alcohol, halogen and / or halogen-containing compound caused by the temporary large generation of hydrogen gas. The number of divisions is
It may be determined in consideration of the scale of the reaction tank, and usually 5 to 10 times is preferable considering the complexity of the operation. Further, it goes without saying that the reaction itself may be a batch type or a continuous type. Furthermore, as a modified method, a small amount of metallic magnesium is first added to the alcohol that has been entirely added from the beginning, the product produced by the reaction is separated and removed in another tank, and then a small amount of metallic magnesium is added again. It is also possible to repeat.

When the magnesium compound thus obtained is used for the next preparation of the solid catalyst component, it may be used after being dried, or may be washed with an inert solvent such as heptane after filtration. . In each case,
The obtained magnesium compound can be used in the next step without pulverization or classification operation for adjusting the particle size distribution.

Further, as the titanium compound, for example, tetramethoxytitanium, tetraethoxytitanium, tetra-titanium
n-propoxytitanium, tetraisopropoxytitanium,
Tetra-n-butoxytitanium, tetraisobutoxytitanium, tetracyclohexyloxytitanium, tetraphenoxytitanium and other tetraalkoxytitaniums, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and other tetrahalogenated titanium, and methoxytitanium trichloride. , Ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, ethoxytitanium tribromide and other halogenated alkoxytitanium, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride , Dialkoxytitanium dialkoxytitanium such as diethoxytitanium dibromide, trimethoxytitanium chloride, triethoxytitanium Rorido, tripropoxy titanium chloride, but such monohalogenated trialkoxy titanium and tri -n- butoxy titanium chloride and the like, high halogen-containing titanium compound Among these, particularly titanium tetrachloride is preferred. These titanium compounds may be used alone or in combination of two or more.

As the electron donor, those exemplified later as the electron donating compound of the component (Z) can be used. The solid catalyst component (i) can be prepared by a known method (JP-A-53-43094, JP-A-55-135).
102, JP-A-55-135103, JP-A-56-18606, JP-A-56-166205.
JP-A-57-63309, JP-A-57-63309
190004, JP-A-57-300407, JP-A-58-47003).

The composition of the solid catalyst component (i) thus prepared usually has a magnesium / titanium atomic ratio of 2 to 2.
100, the halogen / titanium atomic ratio is in the range of 5 to 100, and the electron donor / titanium molar ratio is in the range of 0.1 to 10. Also,
Examples of the crystalline polyolefin as the component (ii) used as necessary in the preparation of the solid component (W) include, for example:
Polyethylene, polypropylene, polybutene, poly 4-
A crystalline polyolefin obtained from an α-olefin having 2 to 10 carbon atoms such as methyl-1-pentene can be mentioned. This crystalline polyolefin is (1) a method of prepolymerizing an olefin in the presence of (1) a combination of the solid catalyst component, an organoaluminum compound and an electron-donating compound used as necessary (preliminary polymerization method). ), (2) In the crystalline powder such as crystalline polyethylene or polypropylene having a uniform particle size, (i) the solid catalyst component and an organoaluminum compound and an electron donating compound (melting point 100 ° C. or higher) optionally used. Can be obtained by using a method of dispersing and (dispersion method), (3) a method of combining the method of (1) and the method of (2), and the like.

In the prepolymerization method (1), the aluminum / titanium atomic ratio is usually selected in the range of 0.1 to 100, preferably 0.5 to 5, and the electron donor compound / titanium molar ratio is set. It is selected in the range of 0 to 50, preferably 0.1 to 2. Regarding the ratio of (i) solid catalyst component and (ii) crystalline polyolefin in (W) solid component,
The weight ratio of component (ii) to component (i) is usually 0.33.
To 200, preferably 0.1 to 50.

The organoaluminum compound used as the component (X) is, for example, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, diisopropyl. Dialkylaluminum monohalides such as aluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum monochloride, and alkylaluminum sesquihalides such as ethylaluminum sesquichloride can be preferably used. These aluminum compounds may be used alone or in combination of two or more.

In the catalyst system for obtaining the flexible polypropylene resin in the present invention, an alkoxy group-containing aromatic compound as the component (Y) is used. Specific examples of the alkoxy group-containing aromatic compound include m-methoxytoluene;
o-methoxyphenol; m-methoxyphenol; 2
-Methoxy-4-methylphenol; vinylanisole; p- (1-propenyl) anisole; p-allylanisole; 1,3-bis (p-methoxyphenyl) -1
-Pentene; 5-allyl-2-methoxyphenol; 4
-Hydroxy-3-methoxybenzyl alcohol; methoxybenzyl alcohol; nitroanisole; monoalkoxy compounds such as nitrophenetole; o-dimethoxybenzene; m-dimethoxybenzene; p-dimethoxybenzene; 3,4-dimethoxytoluene; 2,6 -Dimethoxyphenol; dialkoxy compounds such as 1-allyl-3,4-dimethoxybenzene, 1,3,5-trimethoxybenzene; 5-allyl-1,2,3-trimethoxybenzene; 5-allyl-1, 2,4-trimethoxybenzene; 1,2,3-trimethoxy-5- (1-propenyl) benzene; 1,2,4-trimethoxy-5- (1
-Propenyl) benzene; 1,2,3-trimethoxybenzene; trialkoxy compounds such as 1,2,4-trimethoxybenzene, and the like, and among these, dialkoxy compounds and trialkoxy compounds are preferable. . These alkoxy group-containing aromatic compounds may be used alone or in combination of two or more.

Further, in the catalyst, an electron-donating compound is used as a component (Z) if necessary. The electron donating compound is a compound containing oxygen, nitrogen, phosphorus, sulfur, silicon, and the like. Basically, a compound having a performance of improving regularity in propylene polymerization is considered.
Examples of such electron-donating compounds include organosilicon compounds, esters, thioesters, amines,
Ketones, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, acid amides,
Examples thereof include aldehydes, organic acids and azo compounds.

For example, diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane. , Phenyltriethoxysilane, benzyltrimethoxysilane, cyclohexylmethyldimethoxysilane and other organosilicon compounds, monomethylphthalate, monoethylphthalate, monopropylphthalate, monobutylphthalate, monoisobutylphthalate, monoamylphthalate, monoisoamylphthalate, monomethylterephthalate , Monoethyl terephthalate, monopropyl terephthalate, monobutyl terephthalate, Roh isobutyl terephthalate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, methyl ethyl phthalate, methyl isobutyl phthalate,
Methyl propyl phthalate, ethyl butyl phthalate,
Ethyl isobutyl phthalate, ethyl propyl phthalate, propyl isobutyl phthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methyl isobutyl terephthalate, methyl propyl terephthalate, ethyl butyl terephthalate, ethyl isobutyl terephthalate, ethyl propyl terephthalate, propyl Isobutyl terephthalate,
Dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, diisobutyl isophthalate, methyl ethyl isophthalate, methyl isobutyl isophthalate, methyl propyl isophthalate, ethyl butyl isophthalate, ethyl isobutyl isophthalate, ethyl propyl isophthalate, propyl isobutyl isophthalate Aromatic dicarboxylic acid ester such as phthalate,
Methyl formate, ethyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, Ethyl crotonate, ethyl bivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, toluyl Methyl acid, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate,
Monoesters such as ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate and ethyl naphthoate, γ-butyrolactone,
δ-valerolactone, coumarin, phthalide, esters such as ethylene carbonate, benzoic acid, organic acids such as p-oxybenzoic acid, succinic anhydride, benzoic anhydride, p-anhydride
Acid anhydrides such as toluic acid, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone and other ketones, acetaldehyde, propionaldehyde, octyl aldehyde,
Aldehydes such as tolaldehyde, benzaldedo, and naphthylaldehyde, acetyl chloride, acetyl bromide, propionyl chloride, butyryl chloride, isobutyryl chloride, 2-methylpropionyl chloride,
Valeryl chloride, isovaleryl chloride, hexanoyl chloride, methylhexanoyl chloride, 2-ethylhexanoyl chloride, octanoyl chloride, decanoyl chloride, undecanoyl chloride, hexadecanoyl chloride, octadecanoyl chloride, henzyl Carbonyl chloride, dichlorohexane carbonyl chloride, malonyl dichloride, succinyl dichloride, pentanedioleyl dichloride, hexanedioleyl dichloride, dichlorohexanedicarbonyldichloride, benzoyl chloride, benzoyl bromide, methylbenzoyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthalyl chloride Phthaloyl chloride, benzene-1,2,4-
Acid halides such as tricarbonyl trichloride,
Methyl ether, ethyl ether, isopropyl ether, n-butyl ether, isopropyl methyl ether, isopropyl ethyl ether, t-butyl ethyl ether, t-butyl-n-propyl ether, t-butyl-n-butyl ether, t-amyl methyl ether,
Ethers such as t-amyl ethyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol butyl ether, acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, tributylamine, N, N′-dimethylpiperazine, Amine such as tribenzylamine, aniline, pyridine, pyrroline, tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile, tolunitrile, 2,2′-azobis (2-methylpropane), 2,2′-azobis (2 -Ethyl propane),
An azo compound in which a sterically hindering substituent is bonded to an azo bond such as 2,2′-azobis (2-methylpentane) is exemplified.

Of these, organosilicon compounds, esters, ketones, ethers, thioethers, acid anhydrides, and acid halides are preferable, and diphenyldimethoxysilane, phenyltriethoxysilane, cyclohexylmethyldimethoxysilane and the like are particularly preferable. An organosilicon compound,
Aromatic dicarboxylic acid diesters such as di-n-butyl phthalate and diisobutyl phthalate, and alkyl esters of aromatic monocarboxylic acids such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid and toluic acid are preferable. These electron donating compounds may be used alone or in combination of two or more.

With respect to the amount of each component of the catalyst system,
The solid component (W) is used in an amount in the range of 0.0005 to 1 mol per liter of reaction volume in terms of titanium atom. The (X) organoaluminum compound has an aluminum / titanium atom ratio of usually 1 to 30.
An amount of 00, preferably 40 to 800 is used, and if the amount deviates from the above range, the catalytic activity may be insufficient. Further, the (Y) alkoxy group-containing aromatic compound is used in such a proportion that the molar ratio to the titanium atom in the (W) solid component is usually 0.01 to 500, preferably 1 to 300. If it is less than 0.01, the physical properties of the polymer produced may be deteriorated, and if it exceeds 500, the catalytic activity may be insufficient.

In the case where a homopolymer of propylene as the component (A) and / or a copolymer containing 4% by weight or less of other olefin units is used as the soft polypropylene resin in the present invention, the presence of the catalyst system Below, for example, by homopolymerization of propylene or copolymerization of propylene with a small amount of another olefin by a one-stage polymerization method, (A)
The resin of the component may be manufactured. When a resin comprising the resin (A) and the propylene copolymer (B) is used, for example, in a multistage polymerization in the presence of the catalyst system, the first polymerization (the first polymerization) )), A resin of the component (A) is produced in the same manner as described above, and then propylene and another olefin are copolymerized in the second and subsequent stages to obtain a resin (B)
A propylene-based copolymer as a component may be produced.

The polymerization system is not particularly limited, and slurry polymerization, gas phase polymerization, bulk polymerization, solution polymerization, suspension polymerization and the like can be used. When polymerizing by gas phase polymerization,
With regard to the production or the production stage of the resin (A), the polymerization pressure is usually 10 to 45 kg / cm ² , preferably 20 to 45 kg / cm ² .
The polymerization temperature is 30 kg / cm ² , and the polymerization temperature is usually selected in the range of 40 to 90 ° C, preferably 60 to 75 ° C. Also,
Regarding the production stage of the propylene copolymer (B), the polymerization pressure is usually 5 to 30 kg / cm ² , preferably 10 to 20 kg / cm ² , and the polymerization temperature is usually 20 to 90.
C, preferably selected in the range of 40 to 60C. At any stage, the molecular weight of the polymer can be adjusted by known means, for example, adjusting the hydrogen concentration in the polymerization vessel. It can also be adjusted by producing a (co) polymer having a relatively high molecular weight in the polymerization step and melt-kneading the obtained (co) polymer in the presence of an organic peroxide. The polymerization time is appropriately selected from about 5 minutes to 10 hours.

In the polymerization, the components constituting the catalyst system, that is, the components (W) to (Z) are mixed at a predetermined ratio and brought into contact with each other.
The polymerization may be started, or the raw material monomer may be introduced after aging for about 0.2 to 3 hours after the contact. further,
This catalyst component can be supplied by suspending it in an inert solvent or an olefin as a raw material monomer.

Post-treatment after the polymerization can be carried out by a conventional method. That is, in the gas phase polymerization method, after the polymerization, a nitrogen stream or the like may be passed through the polymer powder discharged from the polymerization vessel in order to remove unreacted monomers and the like contained therein. If desired, pelletizing may be carried out by an extruder, and in this case, a small amount of water, alcohol or the like may be added in order to completely deactivate the catalyst. In the bulk polymerization method, after polymerization, the unreacted monomer may be completely separated from the polymer discharged from the polymerization vessel, and then pelletized.

Further, as a soft polypropylene resin,
In the case of using a resin consisting of the components (A) and (B), the resin of the component (A) and the resin of the component (B) are separately manufactured, and these are prepared by a known method (for example, dry blending,
It can also be prepared by blending at a predetermined ratio by solution blending or kneading. If desired, the soft polypropylene resin of the present invention may include other resins and various additive components such as thermoplastic elastomers, thermoplastic resins, modified polyolefins, various stabilizers, inorganic or organic fillers, further antistatic agents, and chlorine. Scavenger, anti-blocking agent, anti-fog agent, organic flame retardant, flame retardant aid, dye,
Pigments, natural oils, synthetic oils, waxes, etc. can be added.

Examples of the thermoplastic elastomer include ethylene-α-olefin copolymer elastomer having 3 or more carbon atoms, ethylene-α-olefin having 3 or more carbon atoms.
A diene copolymer elastomer and a hydrogenated product thereof,
Examples thereof include a styrene-diene copolymer elastomer, a hydrogenated product thereof, and an acrylonitrile copolymer elastomer. Further, examples of the thermoplastic resin include low density polyethylene, high density polyethylene, and linear low density polyethylene copolymer. Here, the compounding ratio of these resins is not particularly limited. For example, when a thermoplastic elastomer is compounded, the thermoplastic elastomer 2 to 100 parts by weight of the soft polypropylene resin is added.
It is added in an amount of 100 parts by weight, preferably 5 to 60 parts by weight.

As the above-mentioned various stabilizers, conventionally known ones, for example, phenolic stabilizers, organic phosphite stabilizers, thioether stabilizers, hindered amine stabilizers, etc. can be used. Phenolic stabilizers include 2,6-di-t-butyl-4-methylphenol, stearyl-β- (4-hydroxy-3,5-di-
t-butylphenol) propionate, 2,2'-ethylidenebis (4,6-di-t-butylphenol),
There is tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, and an organic phosphite stabilizer is tris (2,4-di-t-butylphenyl). There are phosphite, tris (nonylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphite, etc., and as an organic thioether stabilizer, dilaurylthiodiprophyl Peonate,
There are distearyl thiodipropionate, pentaerythritol tetralauryl thiopropionate, and the like, and hindered amine stabilizers include bis (2,2,6,
6-tetramethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate of succinate and the like.

Examples of the inorganic fillers include spherical fillers, plate fillers, fibrous fillers and inorganic flame retardants. Examples of the spherical filler include calcium carbonate, kaolin (aluminum silicate), silica,
Sericite, diatomaceous earth, calcium sulfite, calcined alumina, calcium silicate, crystalline zeolite, amorphous zeolite and the like, plate fillers such as talc and mica, and fibrous fillers such as wollastonite. Such as needle-like ones, magnesium oxysulfate, potassium titanate fibers, fibrous ones such as fibrous calcium carbonate, and even completely fibrous ones such as glass fibers, etc. Examples of the flammable agent include hydrated aluminum, hydrated gypsum, zinc borate, barium borate, borax, kaolin, clay, calcium carbonate, alumite, basic magnesium carbonate, calcium hydroxide, magnesium hydroxide and the like. To be

The polypropylene resin for ski boots of the present invention comprises a tumbler blender, a Henschel mixer, a Banbury mixer, an extrusion kneading molding, if necessary, by adding various additives such as a thermoplastic elastomer, a stabilizer and a colorant to the polypropylene resin. Ski boots can be manufactured by pelletizing using a machine or the like, and then usually by injection molding.

[0048]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The characteristics of the resin were evaluated according to the methods described below. (1) Surface hardness According to JIS K7215 Shore hardness D. (2) Tensile properties According to JIS K6760. (3) Impact strength Conforms to JIS K7110. Izod impact strength (notched, -30 ° C). Example 1 Production of Soft Propylene Block Copolymer (1) Preparation of Magnesium Compound A glass reactor equipped with a stirrer having an internal volume of about 6 liters was sufficiently replaced with nitrogen gas, and then ethanol was added to about 2,430 of the same.
g, 20 g of iodine and 160 g of metallic magnesium were charged, heated with stirring, and reacted under reflux conditions until hydrogen gas was not generated from the inside of the system to obtain a solid reaction product. The reaction liquid containing this solid reaction product was dried under reduced pressure to obtain a magnesium compound.

Preparation of solid catalyst component (W) In a glass reactor having an internal volume of 5 liters which was sufficiently replaced with nitrogen gas, 160 g of the magnesium compound (not crushed) obtained above, 800 ml of purified heptane, 24 ml of silicon tetrachloride and 23 ml of diethyl phthalate were charged, the temperature of the system was kept at 80 ° C., 770 ml of titanium tetrachloride was added with stirring and reacted at 110 ° C. for 2 hours, and then the solid component was separated to 90 It was washed with purified heptane at ℃. Further, 1,220 ml of titanium tetrachloride was added, and the mixture was reacted at 110 ° C. for 2 hours and then thoroughly washed with purified heptane to obtain a solid catalyst component (W).

Gas Phase Polymerization In a polymerization tank having an internal volume of 200 liters, 6.0 g / hour of the solid catalyst component (W) obtained above, 0.2 mol / hour of triisobutylaluminum (TIBA), 1-allyl-3 ，
4-dimethoxybenzene (ADMB) 0.006 mol / hour, cyclohexylmethyldimethoxysilane (CHMD
MS) was supplied at 0.03 mol / hour and 43 kg / hour of propylene, and polymerization was carried out at 70 ° C. and 28 kg / cm ² G.
The amount of polymer produced was 30 kg / hour.

The polymer obtained by this polymerization is a propylene homopolymer, and its intrinsic viscosity [η] (135
(° C, in decalin) was 5.04 deciliter / g. The amount of the boiling n-heptane insoluble component of the homopolymer was 88.2% by weight, [η] of the boiling n-heptane insoluble component was 5.42 deciliter / g, and the boiling n-heptane-soluble component [ η] was 2.07 deciliter / g.

On the other hand, the pentad fraction rrrr / (1-m calculated from the ¹³ C-NMR spectrum of the homopolymer
mmm) × 100 was 24.2%, the melting peak temperature (Tm) measured by DSC was 158.7 ° C., and the melting enthalpy (ΔH) was 80.7 J / g. In addition, no reverse bond was observed in the head-to-tail bond of propylene.

The propylene homopolymer obtained by the above gas phase polymerization was continuously transferred to the subsequent polymerization tank, and ethylene was added to
Polymer powder of 7.5 kg / hour and 13 kg / hour of propylene, polymerized at 52 ° C. and 14 kg / cm ² G, ethylene unit content of 13.0 wt%, reaction ratio of 43.0% in the latter stage Got This polymer is a propylene block copolymer composed of a mixture of propylene homopolymer and ethylene-propylene random copolymer, and has an intrinsic viscosity [η] (135 ° C, in decalin) of 4.89.
It was deciliter / g.

2.5-dimethyl-2, was added to the obtained powder.
5-di- (t-butylperoxy) -hexane is mixed, and an antioxidant, a stabilizer, and a chlorine scavenger are further added and mixed therewith, and the mixture is extruded at 40 mmφ and melt index (MI, 230 ° C, 2.16kgf) is 5.1g / 1
A 0 minute pellet was obtained. Although the above polymer was decomposed with peroxide to have a low molecular weight, there was no change in the above-mentioned Pendad fraction, melting peak temperature and melting enthalpy even with this low molecular weight polymer. The tensile modulus of elasticity of the obtained resin was 320 MPa.

100 parts by weight of the obtained soft propylene block copolymer (1) was added to an ethylene-propylene copolymer elastomer [Nippon Synthetic Rubber Co., Ltd., JSR EP.
57P Mooney viscosity (ML _{1 + 4} 100 ° C.): 76, propylene content 28% by weight] 10 parts by weight were added and mixed by a single-screw kneader to obtain a soft polypropylene resin. This polypropylene resin had a tensile elastic modulus of 220 MPa, an Izod impact strength of 70 kj / m ² , and a hardness (Shore D) of 53. A ski boot was molded by injection molding using a raw material obtained by adding a red dye to this resin. It was bright and glossy and comfortable to wear.

Example 2 Production of Soft Propylene Block Copolymer (2) After preparing a magnesium compound in the same manner as in Example 1, a solid catalyst component (W) was prepared. Next, the internal volume 20
In a 0 liter polymerization tank, the above solid catalyst component (W) 6.0
g / h, triisobutylaluminum (TIBA) 0.
2 mol / hour, 1-allyl-3,4-dimethoxybenzene (ADMB) 0.008 mol / hour, cyclohexylmethyldimethoxysilane (CHMDMS) 0.01 mol / hour, and propylene 43 kg / hour were supplied at 70 ° C. 28
Polymerization was performed at kg / cm ² G. Polymer production is 3
It was 0 kg / hour.

The polymer obtained by this polymerization is a propylene homopolymer, and its intrinsic viscosity [η] (135
(° C, in decalin) was 5.00 deciliters / g. The amount of the boiling n-heptane-insoluble component of the homopolymer was 82.2% by weight, [η] of the boiling n-heptane-insoluble component was 5.3 deciliter / g, and the boiling n-heptane-soluble component [ η] was 2.10 deciliters / g.

On the other hand, the pentad fraction rrrr / (1-m calculated from the ¹³ C-NMR spectrum of the homopolymer
mmm) × 100 was 24.4%, the melting peak temperature (Tm) measured by DSC was 160.0 ° C., and the melting enthalpy (ΔH) was 75.0 J / g. In addition, no reverse bond was observed in the head-to-tail bond of propylene.

Next, this polymer was continuously transferred to the subsequent polymerization tank, ethylene was supplied at 17.5 kg / hour and propylene at 13 kg / hour, and the temperature was 50 ° C. and 13 kg / c.
Polymerization was carried out with m ² G to obtain a polymer powder having an ethylene unit content of 15.6% by weight and a reaction ratio of 43.2% in the latter stage. This polymer is a propylene-based block copolymer composed of a mixture of a propylene homopolymer and an ethylene-propylene random copolymer, and has an intrinsic viscosity [η] (1
35 ° C. in decalin) was 4.90 deciliter / g.

2.5-dimethyl-2, was added to the obtained powder.
5-di- (t-butylperoxy) -hexane is mixed, and an antioxidant, a stabilizer, and a chlorine scavenger are further added and mixed therewith, and the mixture is extruded at 40 mmφ and melt index (MI, 230 ° C, 2.16kgf) is 5.2g / 1
A 0 minute pellet was obtained. Although the above polymer was decomposed with peroxide to have a low molecular weight, there was no change in the above-mentioned Pendad fraction, melting peak temperature and melting enthalpy even with this low molecular weight polymer. The tensile modulus of elasticity of the obtained resin was 300 MPa.

100 parts by weight of the obtained soft propylene block copolymer (2) was added to an ethylene-propylene copolymer elastomer [Nippon Synthetic Rubber Co., Ltd., JSR EP5.
7P Mooney viscosity (ML _{1 + 4} 100 ° C.): 76, propylene content 28% by weight] 20 parts by weight was added and mixed with a Banbury mixer to obtain a soft polypropylene resin. This polypropylene resin has a tensile modulus of elasticity: 137MP
a, Izod impact strength: 84 kj / m ² , hardness (Shore D): 51. A ski boot was molded by injection molding using a raw material obtained by adding a red dye to this resin. It was bright and glossy and comfortable to wear.

[0062]

The ski boot molded from the polypropylene resin for ski boots of the present invention has excellent functions as a ski boot such as flexibility, hardness, low temperature impact resistance, and heat resistance, and at the same time, has a resin coloring property and gloss. It is possible to manufacture ski boots that are highly fashionable and have good productivity.

Claims (3)

[Claims] (1) a melting peak temperature (Tm) measured by a differential scanning calorimeter (DSC) is 150 ° C. or more;
(B) A polypropylene resin for ski boots made of a soft polypropylene resin having a tensile elastic modulus of 20 to 500 MPa. 2. The method according to claim 1, wherein the soft polypropylene resin is (A) or (C).
In pentad fraction by isotope carbon nuclear magnetic resonance spectrum ( ^13C -NMR), rrrr / (1-mmm
m) × 100 is 15 to 60%, (d) a propylene homopolymer having a melting enthalpy (ΔH) of 10 to 100 J / g measured by a differential scanning calorimeter (DSC) and / or 4% by weight or less. Polypropylene resin comprising 100 to 20% by weight of a copolymer containing other olefin units and (B) 0 to 80% by weight of a propylene copolymer containing 10 to 80% by weight of olefin units other than propylene. The polypropylene-based resin for ski boots according to claim 1. 3. The polypropylene resin for ski boots according to claim 1, wherein 2 to 100 parts by weight of the thermoplastic copolymer elastomer is mixed with 100 parts by weight of the soft polypropylene resin.