JP2002226650A - Poly 1-butene resin composition and usage of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide poly 1-butene resin composition which prevents from gum formation upon extrusion molding and of which pipes easily piled up with an excellent anti-cracking property are produced, pipes made of the same and joints for the pipes which can be easily piled up with an excellent anti-cracking property. SOLUTION: This poly 1-butene resin composition has a static friction coefficient of less than 4.3 and/or a dynamic friction coefficient of less than 2.3. In more detail, the poly 1-butene resin composition can be produced by (co) polymerization of 1-butene of 80-100 mol% and a 2-10C α-olefin except 1-butene, of 0-20 mol%. The composition includes poly 1-butene resin (A) of 97-99.999 mol% having MFR of 0.01-50 g/10 min, fluoro elastomer (B) of 0.001-3 wt.% and/or fluororesin (C) of 0.001-3 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a poly-1-butene resin composition and its use, for example, a pipe for fluid transportation such as a pipe for water supply and hot water supply and a pipe joint therefor.

[0002]

BACKGROUND OF THE INVENTION Poly 1-butene resin is excellent in creep characteristics at high temperatures and stress cracking resistance, and is flexible and has very good workability, so that hot water pipes such as water supply and hot water supply pipes are used. Used for fluid transport pipes and pipe fittings. In order to satisfy the long-term creep properties of such a pipe,
It is necessary to use a poly-1-butene resin having a relatively high molecular weight. When the molecular weight of the poly 1-butene resin increases, the melt flow rate decreases, that is, the flowability decreases, and there is no problem in extrusion molding at a low speed. However, at a molding speed such that the linear velocity exceeds 1 m / min, Melt fracture occurs, and the smoothness of the entire surface of the pipe is reduced, or a pipe having a partially poor surface state is obtained. In particular, when the surface condition of the inner surface is poor, the flow resistance increases, and excessive energy is required for transporting the fluid. In addition, when extruding a poly 1-butene resin having a high melt flow rate at a high linear velocity, a die is generated at the exit of the die at the time of molding, and it is necessary to frequently clean the die. There is a problem of sticking to the pipe.

[0003] Furthermore, pipes made of poly 1-butene resin have problems that the scratch resistance is not always sufficient, and that the pipes are difficult to bundle due to the rough surface. Therefore, it is possible to suppress the occurrence of die build-up during extrusion molding, and it is excellent in scratch resistance,
There is a demand for a poly 1-butene resin composition capable of preparing pipes that can be easily bundled, and for the appearance of pipes and pipe joints having excellent scratch resistance.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above. It is an object of the present invention to provide a poly 1-butene resin composition capable of preparing a pipe that can be easily bundled, and a pipe and a pipe joint having excellent scratch resistance.

[0005]

SUMMARY OF THE INVENTION The poly-1-butene resin composition according to the present invention is characterized in that the coefficient of static friction is 4.3 or less and / or the coefficient of dynamic friction is 2.3 or less. Specifically, the poly 1-butene resin composition according to the present invention contains 80 to 100 mol% of 1-butene and 0 to 20 mol% of α-olefins other than 1-butene having 2 to 10 carbon atoms (co-olefin). ) Obtained by polymerization and having a melt flow rate (MFR; ASTM D 123).
97-99.999% by weight of poly 1-butene resin (A) having a weight of 8,50 ° C and a load of 2.16 kg) of 0.01 to 50 g / 10 min.
And fluorine-based elastomer (B) 0.001 to 3% by weight
And / or 0.001 to 3% by weight of a fluororesin (C).

Melt flow rate of the poly 1-butene resin (A) (MFR; ASTM D 1238, 190 ° C, 2.16 kg load)
Is preferably 0.05 to 30 g / 10 min, and the isotactic index (mmmm%) measured by NMR is preferably 90 or more. This poly 1-butene resin (A)
May be composed of one kind of poly 1-butene resin or a mixture of two or more kinds of poly 1-butene resins, for example, a mixture of 1-butene / propylene copolymer and 1-butene homopolymer. is there.

The poly 1-butene resin (A) includes a melt flow rate (MFR; ASTM D 1238, 190 ° C, 2.16).
kg load) is 0.01 to 5 g / 10 min, the molecular weight distribution (Mw / Mn) determined by the GPC method is 6 or less, and the isotactic index (mmmm%) measured by NMR is 90. The above poly 1-butene resin (a1) is contained in an amount of 60 to 95% by weight and a melt flow rate (MFR; ASTM D 1238, 190 ° C, 2.16 kg load).
20 times or more the MFR value of the 1-butene resin (a1),
5-40 weight% of poly 1-butene resin (a2) having a molecular weight distribution (Mw / Mn) determined by GPC method of 6 or less and an isotactic index (mmmm%) measured by NMR of 90 or more 1-butene resin (a) consisting of 80% to 100% by mole of 1-butene and α-olefin other than 1-butene having 2 to 10 carbon atoms
２０20 mol% obtained by (co) polymerization, has an isotactic index (mmmm%) of at least 90 measured by NMR, and has a molecular weight distribution (Mw) determined by the GPC method.
/ Mn) is 3 or more, and the amount of the residual catalyst represented by titanium metal is 50 ppm or less.

The above-mentioned poly 1-butene resin composition according to the present invention is suitable for use in pipes and pipe joints. A pipe and a pipe joint according to the present invention are characterized by being composed of the above-described poly-1-butene resin composition according to the present invention.

[0009]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a poly-1-butene resin composition according to the present invention, a pipe made of the composition, and a pipe joint will be described in detail. The poly 1-butene resin composition according to the present invention contains a poly 1-butene resin (A) and a fluorinated elastomer (B) and / or a fluorinated resin (C). First, these components will be described.

Poly 1-butene resin (A) The poly 1-butene resin (A) used in the present invention is composed of 80 to 100 mol% of 1-butene and an α-olefin other than 1-butene having 2 to 10 carbon atoms. And (co) polymerization of
It is a homopolymer of butene or a 1-butene / α-olefin copolymer. Α other than 1-butene having 2 to 10 carbon atoms
-Specific examples of the olefin include ethylene, propylene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like. These α-olefins may be used alone or in combination of two or more.

The content of structural units derived from α-olefins other than 1-butene in the 1-butene / α-olefin copolymer is 20 mol% or less, preferably 10 mol% or less. The content of the derived structural unit is
It is at least 80 mol%, preferably at least 90 mol%. 1-
The above composition of the butene / α-olefin copolymer is usually 1
A ¹³ C-NMR spectrum of a sample obtained by uniformly dissolving about 200 mg of a 1-butene-α-olefin copolymer in 1 ml of hexachlorobutadiene in a 0 mmφ sample tube was measured at a measurement temperature of 120 ° C., a measurement frequency of 25.05 MHz, It is determined by measuring under the conditions of a spectrum width of 1500 Hz, a pulse repetition time of 4.2 sec., And a pulse width of 6 μsec.

The poly-1-butene resin (A) used in the present invention has a melt flow rate (MFR; ASTM D 1238,1).
90 ° C., 2.16 kg load) is 0.01 to 50 g / 10 min, preferably 0.05 to 30 g / 10 min, more preferably 0.1 to 30 g / 10 min, particularly preferably 0.2 to 10 g.
g / 10 minutes. The poly 1-butene resin (A) having a melt flow rate within the above range is flexible and has excellent creep resistance, impact resistance, abrasion resistance, chemical resistance, stress cracking resistance, and the like. ing.

The poly 1-butene resin (A) as described above is
Conventionally known production methods, for example, polymerization of 1-butene alone or copolymerization of 1-butene with α-olefins other than 1-butene such as ethylene and propylene in the presence of Ziegler-Natta catalyst or metallocene catalyst Can be prepared. Further, in the present invention, poly 1-
For the production of the butene resin (A), a titanium catalyst such as the following solid titanium catalyst component (a), and further a titanium catalyst containing an organoaluminum compound catalyst component (b) and an organosilicon compound catalyst component (c) is used. be able to.

In the present invention, the solid titanium catalyst component (a) can be produced by contacting a magnesium compound (or metallic magnesium) and a titanium compound, and preferably an electron donor. In order to produce the solid titanium catalyst component (a), a known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and an electron donor can be employed. The above-mentioned components may be brought into contact in the presence of another reaction reagent such as silicon, phosphorus and aluminum.

The method for producing the solid titanium catalyst component (a) will be briefly described below with several examples. (1) A method in which a magnesium compound or a complex compound comprising a magnesium compound and an electron donor is reacted with a titanium compound in a liquid phase. This reaction may be performed in the presence of a grinding aid or the like. Further, when reacting as described above, the solid compound may be pulverized. (2) a liquid magnesium compound having no reducing property;
A method in which a liquid titanium compound is reacted in the presence of an electron donor to precipitate a solid titanium composite agent.

This method is disclosed, for example, in Japanese Patent Application Laid-Open No. 58-830.
No. 06 publication. (3) A method of further reacting the reaction product obtained in (2) with a titanium compound. (4) The reaction product obtained in (1) or (2)
A method in which an electron donor and a titanium compound are further reacted. (5) A solid compound obtained by pulverizing a magnesium compound or a complex compound comprising a magnesium compound and an electron donor in the presence of a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. how to.

In this method, a magnesium compound or a complex compound comprising a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Alternatively, a magnesium compound or a complex compound comprising a magnesium compound and an electron donor may be pulverized in the presence of a titanium compound, pre-treated with a reaction aid, and then treated with a halogen or the like. In addition, examples of the reaction assistant include an organic aluminum compound and a halogen-containing silicon compound. (6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound or an aromatic hydrocarbon. (7) A method of contacting a reaction product of a metal acid compound, dihydrocarbylmagnesium and a halogen-containing alcohol with an electron donor and a titanium compound. (8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium is reacted with an electron donor, a titanium compound and / or a halogen-containing hydrocarbon. (9) In an organic liquid medium containing 0.1 to 40% by weight of a siloxane and / or an organic liquid medium containing a surfactant,
A method of supporting a titanium compound on a solid support obtained by solidifying complex particles from a suspension containing complex particles of a magnesium halide and an active hydrogen compound in a molten state.

This carrier is described, for example, in JP-B-60-378.
No. 04 and JP-B-60-37805. In the solid titanium catalyst component (a) obtained by the methods (1) to (9), (b) an organoaluminum compound catalyst component is usually used at the same time. Also, if necessary, (c) SiR ¹ R ² _m (OR ³ ) _3-m [wherein
m is 0 ≦ m <3, R ¹ is a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or a derivative thereof, and R ² and R ³ are each a hydrocarbon group]. The organosilicon compound catalyst component may be used simultaneously.

The poly 1-butene resin (A) preferably used in the present invention includes a melt flow rate (MFR; AS
TM D 1238, 190 ℃, 2.16kg load) 0.01-5g / 1
0-minute, poly 1-butene resin (a1) 60-95 having a molecular weight distribution (Mw / Mn) of 6 or less and an isotactic index (mmmm%) of 90 or more measured by NMR method. Wt% and melt flow rate (MFR; ASTM D 1238, 190 ° C, 2.16 kg load)
20 times or more the MFR value of the 1-butene resin (a1),
A polymer having a molecular weight distribution (Mw / Mn) of 6 or less and an isotactic index (mmmm%) of 90 or more
Poly 1-butene resin (a) comprising 5 to 40% by weight of 1-butene resin (a2) is exemplified.

The poly-1-butene resin (a1) is a 1-butene homopolymer or 1-butene having a content of structural units derived from 1-butene of 80 to 100 mol% and 2 to 10 carbon atoms. 1-butene-α-olefin copolymer with α-olefin other than 1-butene, whose melt flow rate (MFR; ASTM D 1238, 190 ° C, 2.16 kg load)
Is from 0.01 to 5 g / 10 min, preferably from 0.1 to 2 g / 10 min, in that the obtained poly 1-butene resin (a) composition has good extrusion moldability.

The poly 1-butene resin (a1)
The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) representing the molecular weight distribution is 6 or less, and the resulting poly 1-butene resin (a) composition has excellent impact resistance. And it is preferably 5 or less. This Mw and Mn
(Mw / Mn) is measured by the following method.

(I) Using standard polystyrene having a known molecular weight (monodispersed polystyrene, manufactured by Tosoh Corporation), polystyrenes having different molecular weights were subjected to GPC (gel permeation chromatography) analysis under the following measurement conditions to obtain a molecular weight M And a calibration curve of EV value (Elution Volume). <Measurement conditions> Apparatus: ALC / GPC150-C type, manufactured by Water Column: TSK _gel GMH _HR- H (S) H, manufactured by Tosoh Corporation
T × 2 + TSK _gel GMH ₆ -HTL × 1 (7.
(8 mmφ × 300 mm, 7.5 mmφ × 600 mm) Temperature: 140 ° C. Flow rate: 1 ml / min (ii) Preparation of sample A polymer sample whose molecular weight is to be measured and a solvent o-dichlorobenzene are put in a flask, and 30 mg of the polymer is added. A solution of 20 ml of solvent is prepared.

In the obtained polymer solution, 2,2 was added as a stabilizer.
6-Di-t-butylcresol is added to a concentration of 0.1% by weight. The solution was stirred at 145 ° C. for 1 hour,
Allow the polymer and stabilizer to completely dissolve. Next, 14
Filter the solution through a 0.45 μm filter at a temperature of 5 ° C. The obtained filtrate was subjected to GPC analysis under the same measurement conditions as in the above (i), and from the obtained EV value, the number average molecular weight (Mn = Mn) was obtained from the calibration curve prepared in the above (i).
ΣMi ² Ni / ΣNi) and weight average molecular weight (Mw =
ΣMi ² Ni / ΣMiNi) is calculated, and Mw / Mn is calculated.

Further, NMR of the poly 1-butene resin (a1)
Index (mmmm
%) Is 90 or more, and is preferably 93 or more, particularly 93 to 98, from the viewpoint that the obtained poly 1-butene resin (a) composition has excellent rigidity, heat resistance and creep resistance. The poly 1-butene resin (a2) is, like the poly 1-butene resin (a1), a 1-butene homopolymer or
It is a 1-butene / α-olefin copolymer of 1-butene and an α-olefin other than 1-butene having 2 to 10 carbon atoms.

The melt flow rate (MFR; ASTM D 1238, 190 ° C., 2.16 kg load) of this poly 1-butene resin (a2) is such that the obtained poly 1-butene resin (a) composition has good extrusion moldability. In that the poly 1-butene resin (a
It is 20 times or more, preferably 50 to 1,000 times the melt flow rate value of 1). The poly 1-butene resin (a2) has a molecular weight distribution (Mw / Mn) of 6 or less determined by the GPC method, and is excellent in impact resistance of the obtained poly 1-butene resin (a) composition. It is preferably 5 or less.

Further, the NM of the poly-1-butene resin (a2)
Isotactic index (mmmm
%) Is 90 or more, and is preferably 93 or more, particularly 93 to 98, from the viewpoint that the obtained poly 1-butene resin (a) composition has excellent rigidity, heat resistance and creep resistance. Such poly 1-butene resin (a1) and poly 1-butene
In the poly 1-butene resin composition containing the poly 1-butene resin (A) comprising the butene resin (a2), the melt tension of the molten parison of the resulting poly 1-butene resin (a) composition is increased, so that molding is performed. Workability is improved, and it is possible to form a pipe at high speed. In addition, from the viewpoint that a molded article excellent in excellent impact resistance is obtained, the mixing ratio of the poly 1-butene resin (a1) and the poly 1-butene resin (a2) is determined by the weight ratio [(a1) / (a2) ] 60 / 40-95
/ 5, preferably 90/10 to 70/30.

The poly 1-butene resin (a1)
Poly 1-butene resin (a) consisting of 1-butene resin (a2)
The production example of is described in JP-A-5-9352. Further, as the other poly 1-butene resin (A) preferably used in the present invention, 80 to 100 mol% of 1-butene and 0 to 20 mol% of α-olefin other than 1-butene having 2 to 10 carbon atoms are used. The isotactic index (mmmm%) obtained by (co) polymerization and measured by NMR method is 9
0 or more, the molecular weight distribution (Mw / Mn) determined by the GPC method is 3 or more, and the residual amount of the catalyst represented by titanium metal is 50 ppm or less.
1-butene resin (b).

Such a poly-1-butene resin (b) and a method for producing the same are described in WO 99/45043. Poly 1-butene resin (A)
97 to 99.999% by weight, preferably 98 to 99.999% by weight, more preferably 99 to 99.999% by weight, based on 100% by weight of the total amount of the butene resin (A) and the fluoroelastomer (B). Used in the ratio of

Fluorine-based elastomer (B) The fluorine-based elastomer (B) used in the present invention contains a fluorine atom in the molecule and has at least 2% of its length at any temperature from -18 ° C to 66 ° C. It is a synthetic elastomer that can quickly recover elasticity to its original length after stretching to double its length.

The fluorine-based elastomer (B) used in the present invention may be, for example, a copolymer of a fluorine-based monomer, a binary copolymer of vinylidene fluoride and hexafluoropropylene, or a copolymer of the two. It may be one containing polyethylene glycol. In this case, the mixing ratio of the polyethylene glycol is preferably 70% by weight or less based on the binary copolymer. Furthermore, a terpolymer of this binary copolymer and ethylene tetrafluoride, a copolymer of tetrafluoroethylene and propylene, a copolymer of ethylene trifluoride and vinylidene fluoride, and a copolymer of vinylidene fluoride A copolymer of propylene and hexafluoropropylene can also be used as the fluoroelastomer (B). Among them, a binary copolymer of vinylidene fluoride and hexafluoropropylene is preferable.

The fluoroelastomer (B) is used in an amount of 0.001 to 3% by weight, preferably 0.001 to 1% by weight, based on 100% by weight of the total of the poly-1-butene resin (A) and the fluoroelastomer (B). 2% by weight, more preferably 0.
It is used at a ratio of 001 to 1% by weight. In the present invention, when the fluoroelastomer (B) is used in the above ratio, the resulting poly 1-butene resin composition has sufficient effects of improving smoothness and scratch resistance, and suppressing the generation of die build-up during extrusion molding. And is economically advantageous. Moreover, pipes obtained from this composition are easy to bundle.

In the present invention, the fluoroelastomer (B) can be used in combination with the fluororesin (C). Fluorine-based resin (C) Examples of the fluorine-based resin (C) used in the present invention include tetrafluoroethylene resin, trifluoride-ethylene chloride resin, tetrafluoroethylene-hexafluoropropylene resin (fluoroethylene-propylene resin). ), Vinylidene fluoride resin and the like.

The fluororesin (C) is 100% by weight in total of the poly-1-butene resin (A) and the fluororesin (C).
0.001 to 3% by weight, preferably 0.00
1-2% by weight, more preferably 0.001-1% by weight
Used in the ratio of In the present invention, when the fluoroelastomer (B) is used in the above ratio, the resulting poly 1-butene resin composition has sufficient effects of improving smoothness and scratch resistance, and suppressing the generation of die build-up during extrusion molding. And is economically advantageous. Moreover, pipes obtained from this composition are easy to bundle.

In the present invention, the fluororesin (C)
Can be used in combination with the above-mentioned fluorine-based elastomer (B). Preparation of Poly 1-Butene Resin Composition The poly 1-butene resin composition according to the present invention comprises, for example, a poly 1-butene resin (A) and a fluoroelastomer (B) and / or a fluororesin (C). Can be prepared by melt-kneading at a specific ratio.

The above-mentioned kneading can be carried out using a kneading device such as a single-screw extruder, a twin-screw extruder, a twin-screw kneader or a Banbury mixer. A master batch comprising a poly-1-butene resin (A) and a fluoroelastomer (B) and / or a fluororesin (C);
The poly-1-butene resin composition according to the present invention can also be prepared by melt-kneading the butene resin (A). In the present invention, the method of preparing the poly 1-butene resin composition according to the present invention using such a masterbatch is preferred from the viewpoint of cost reduction by rationalization.

In the present invention, a nucleating agent, a heat stabilizer, a weathering stabilizer, an antistatic agent, a fungicide, a rust inhibitor, a lubricant, a filler, a pigment may be optionally added to the poly-1-butene resin composition. Such additives as described above can be blended within a range that does not impair the purpose of the present invention. Examples of the nucleating agent include polyethylene wax, polypropylene wax, polyethylene,
Polypropylene, polystyrene, nylon (polyamide), polycaprolactone, talc, titanium oxide, 1,8-
Naphthalimide, phthalimide, alizarin, quinizarin, 1,5-dihydroxy-9,10-anthraquinone, quinalizarin, sodium 2-anthraquinonesulfonate, 2-methyl-9,10-anthroquinone, anthrone, 9-methylanthracene, anthracene, 9,10-dihydroanthracene,
1,4-naphthoquinone, 1,1-dinaphthyl, stearic acid, calcium stearate, sodium stearate, potassium stearate, zinc oxide, hydroquinone, anthranilic acid, ethylenebisstearylamide, sorbitol derivatives, and further JP-A-8-48838 Japanese Patent Application Laid-Open Publication No. HEI-5-260, Japanese Patent Application Publication No.
And a vinylcycloalkane polymer described in JP-A-58019.

These nucleating agents include poly 1-butene resin (A)
And the fluorine-based elastomer (B) and / or the fluorine-based resin (C) in a total amount of 100 parts by weight,
It is used in a proportion of 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight. In the present invention, when the nucleating agent is used in the above ratio, the solidification rate of the molten resin extruded during pipe molding is increased, so that more stable high-speed moldability is obtained, and the molten resin is solidified. After poly
It promotes the rate of crystal transition unique to 1-butene resin and further improves rigidity.

Pipe The pipe according to the present invention is the same as the above-described poly 1- according to the present invention.
It is made of a butene resin composition, and its shape is not particularly limited, and its cross-sectional shape may be circular, polygonal, or any other shape. Although the size of the pipe varies depending on the application, for example, a pipe used as a water distribution pipe usually has an inner diameter of 3 to 1400 mm and an outer diameter of 5 to 160 mm.
0 mm and a wall thickness of 1 to 100 mm.

The pipe according to the present invention can be prepared by a conventionally known extrusion molding method. The pipe joint according to the present invention is made of the above-described poly-1-butene resin composition according to the present invention, and the shape thereof is not particularly limited. This pipe joint is used for connecting the pipes according to the present invention as described above.

The pipe joint according to the present invention can be prepared by a conventionally known injection molding method.

[0041]

According to the present invention, it is possible to suppress the occurrence of die build-up at the time of extrusion molding, and furthermore, it is possible to prepare a pipe which is excellent in scratch resistance and easy to bundle.
It is possible to provide a 1-butene resin composition, a pipe thereof, and a pipe joint excellent in scratch resistance and easy to bundle.

The pipe according to the present invention is suitable for a fluid transport pipe such as a water supply / hot water supply pipe, and the pipe joint according to the present invention is suitable as a joint for these fluid transport pipes.

[0043]

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0044]

[Production Example 1] [Preparation of solid titanium catalyst component (1)] Anhydrous magnesium chloride 6.0 kg (63 mol), decane 2
6.6 liters and 2-ethylhexyl alcohol 2
9.2 liters (189 moles) were heated and reacted at 140 ° C. for 4 hours to form a homogeneous solution. Thereafter, 1.59 kg (7.88 mol) of 2-ethylisopropyl-2-isobutyl-1,3-dimethoxypropane was added to this solution,
And further stirred for 1 hour to obtain a homogeneous solution.

After cooling the obtained homogeneous solution to room temperature,
37.0 kg of the homogeneous solution was added dropwise to 120 liters (1080 mol) of titanium tetrachloride kept at -24 ° C over 2.5 hours. Thereafter, the temperature of the resulting solution was increased over 6 hours, and when it reached 110 ° C., 2-isopropyl-2-isobutyl-1,3-dimethoxypropane 0.68
kg (3.37 mol) was added.

Further, the solution was stirred at 110 ° C. for 2 hours to be reacted. Thereafter, a solid was collected from the reaction mixture by hot filtration, and the solid was added with 132 liters of titanium tetrachloride, reslurried, and then the slurry was again heated at 110 ° C. for 2 hours.
Heated and reacted. Thereafter, a solid portion was collected again from the reaction mixture by hot filtration, and washed with decane and hexane at 90 ° C. When the titanium compound is no longer detected in the cleaning solution, the cleaning is stopped and the solid titanium catalyst component (1)
I got

A portion of the hexane slurry of the solid titanium catalyst component (1) was collected and dried, and the dried product was analyzed. The mass composition of the solid titanium catalyst component (1) is as follows: titanium 3.0%, chlorine 57%, magnesium 17%, and 2-isopropyl-2-isobutyl-1,3-dimethoxypropane 1
8.0%. [Preparation of poly-1-butene resin (b-1)] In a continuous polymerization vessel having an internal volume of 200 liters, hexane was supplied at 73 liters / hour, 1-butene was supplied at 16 kg / hour, and propylene was supplied at 0.0 hours / hour.
7 kg, 10 Nl / h of hydrogen, 0.38 mmol / h of the solid titanium catalyst component (1) in terms of titanium atom, 19 mmol / h of triethylaluminum (TEA) and 0.95 mmol / h of cyclohexylmethyldimethoxysilane While doing so, 1-butene and propylene were copolymerized to obtain 4.8 kg / h of a poly-1-butene resin (b-1). The copolymerization temperature was 60 ° C., the residence time was 1 hour, and the total pressure was 3.5 kg / cm ² .

Table 1 shows the physical properties of the obtained poly-1-butene resin (b-1). The intrinsic viscosity [η] is 135 ° C.
Measured in decalin.

[0049]

[Production Example 2] [Preparation of solid titanium catalyst component (2)] 4.28 kg (45 mol) of anhydrous magnesium chloride, decane 2
6.6 liters and 2-ethylhexyl alcohol 2
1.1 liter (135 mol) was heated and reacted at 140 ° C. for 5 hours to obtain a homogeneous solution. To this solution, 1 kg (6.78 mol) of phthalic anhydride was added,
The mixture was stirred and mixed for an hour, and phthalic anhydride was dissolved to form a homogeneous solution.

After cooling the thus obtained homogeneous solution to room temperature, titanium tetrachloride 12 kept at -20.degree.
It was added dropwise to 0 liter (1080 mol) over 2 hours. The temperature of the resulting solution was raised over 4 hours and 11
When 0 ° C. is reached, 3.02 of diisobutyl phthalate
One liter (11.3 mol) was added. Further, this solution was stirred at 110 ° C. for 2 hours to be reacted. Thereafter, a solid was collected from the reaction mixture by hot filtration,
Put in liter of titanium tetrachloride. The slurry thus obtained was heated and reacted at 110 ° C. for 2 hours. Thereafter, a solid was collected again from the reaction mixture by hot filtration,
Washed with decane and hexane at 110 ° C. When no more titanium was detected in the washing solution, washing was stopped to obtain a solid titanium catalyst component (2).

A portion of the hexane slurry of the solid titanium catalyst component (2) was collected and dried, and the dried product was analyzed. The composition of the solid titanium catalyst component (2) was 2.5% by weight of titanium, 58% by weight of chlorine, 18% by weight of magnesium, and 13.8% by weight of diisobutyl phthalate. [Preparation of poly 1-butene resin (b-2)] Copolymerization of Production Example 1 under the polymerization conditions shown in Table 1 using dicyclopentyldimethoxysilane instead of cyclohexylmethyldimethoxysilane as the organosilicon compound catalyst component Was repeated to prepare a 1-butene-propylene copolymer (poly 1-butene resin (b-2)).

Table 1 shows the physical properties of the obtained poly-1-butene resin (b-2).

[0053]

[Production Example 3] [Preparation of poly 1-butene resin (b-3)]
Without using propylene as a copolymerization component, triethylaluminum (TEA) as an organometallic compound catalyst component
Using triisobutylaluminum (TIBA) in place of dicyclopentyldimethoxysilane and cyclohexylmethyldimethoxysilane in place of dicyclopentyldimethoxysilane
The polymerization of Production Example 2 was repeated under the polymerization conditions shown in the table.
A butene resin (b-3) was prepared.

Table 1 shows the physical properties of the obtained poly 1-butene resin (b-3).

[0055]

[Production Example 4] [Preparation of poly 1-butene resin (b-4)] In the preparation of poly 1-butene resin (b-3) of Production Example 3,
The supply amount of hydrogen was adjusted so that the molar ratio of hydrogen / 1-butene in the gas phase portion of the reactor was 0.5, and the polymerization of Production Example 3 was repeated under the polymerization conditions shown in Table 1 to obtain poly-1- A butene resin (b-4) was prepared.

Table 1 shows the physical properties of the obtained poly 1-butene resin (b-4).

[0057]

[Table 1]

[0058]

Example 1 The poly-1-butene resin (b) obtained in Production Example 1
-1) 79.8 parts by weight, 19.9 parts by weight of the poly 1-butene resin (b-4) obtained in Production Example 4, and Dynomer FX-5911X (trade name) manufactured by Dyneon as a fluorine-based resin. 3 parts by weight, and a high-density polyethylene [HDPE; density (ASTM D 1505) = 0.965 g /
cm ³ , MFR (ASTM D 1238, load 2.16 kg, 190 ° C) =
13 g / 10 min] was melt-blended with a 40 mmφ single screw extruder to obtain a pelletized poly-1-butene resin composition.

Next, an outer diameter of 17 mm was obtained from the poly 1-butene resin composition under the conditions of a set temperature of 180 ° C., a cooling water temperature of 11 ° C., and a molding speed of 10 m / min.
A 2 mm thick pipe was extruded. This pipe is 10
m, and while pulling it on a concrete floor for 30 seconds while walking at a slow pace (80 m / min) while holding one end, check the scratched state (number of scratches, depth) on the pipe surface. It was determined visually.

The length of a pipe manufactured in the same manner as described above was adjusted to a length of 1 m, and the time required for bundling 20 pipes to bind a person was measured five times. It was a measure of ease. The shorter the average time, the easier it is to bundle the pipes. Table 2 shows the results.
The melt flow rate (MFR; ASTM D 1238, 190 ° C.) of a mixture of 79.8 parts by weight of poly 1-butene resin (b-1) and 19.9 parts by weight of poly 1-butene resin (b-4) 2.
Table 2 shows the isotactic index and the isotactic index.

The isotactic index of this mixture (I
I, mmmm%), and poly 1-
The isotactic index (II, mmmm%) of the butene resins (b-1) to (b-4) was measured by the following method. Nuclear magnetic resonance apparatus (NMR; GSX manufactured by JEOL Ltd.)
-400 type) into a sample tube, sample polybutene resin) 50
mg was added, and 0.5 ml of a solvent, hexachlorobutadiene, was added. The mixture was sonicated for 30 minutes, and then placed in a heating furnace at 110 ° C. to dissolve the sample. When almost all of the sample was dissolved, 0.2 ml of deuterated benzene was added, and the sample was further uniformly heated and dissolved. At the time of uniform dissolution, the sample tube was sealed and used as a measurement sample. This sample was measured using NMR under the following conditions.

Measurement nucleus: ¹³ C Observation frequency: 100.4 MHz Pulse interval: 4.5 seconds Pulse width: 45 ° Measurement temperature: 118 ° C. Chemical shift standard: Butene unit side chain methylene (m
mm) = 27.50 ppm isotactic index (II,
mmmm%) was determined by the following formula.

II of 1-butene homopolymer II (mmmm%) = [(S2 + S3) / S1] × 10
0% II of 1-butene / propylene copolymer II (mmmm%) = (S2 / S1) × 100% 1-butene homopolymer and 1-butene / propylene copolymer
In the II II (mmmm%) of the mixture = (S2 / S1) × 100 % The calculation formula, S1 is the total area of 26.1~28.2ppm the side chain methylene carbon of the butene unit, the S2 , 27.36 to 28.2 ppm, and S3 is the satellite peak area on the low magnetic field side of the mmmm peak.

Further, the poly-1-butene resin composition obtained as described above was press-molded at 190 ° C. for 5 minutes to produce a sheet having a thickness of 2 mm. Next, the static friction coefficient and the dynamic friction coefficient of this sheet were measured according to the following measurement methods. <Measurement method of static and dynamic friction coefficient> 1. Apparatus and instrument-Tester: Intesco MODEL2005 type universal material testing machine, Intesco Co. slip jig-Load: 100 g (6.35 cm × 6.35 cm, made of metal) 2. Test Method 2-1 A sample having the following shape was collected from a sheet prepared by press-molding a test piece .

Incidentally, five test pieces were prepared and tested at n = 5. Load side test piece: 12 cm × 12 cm × 2 mm Plate side test piece: 13 cm × 25 cm × 2 mm 2-2 Outline of Test Apparatus The outline of the test apparatus is shown in FIGS. 1 and 2. FIG. 1 is a front view schematically showing a test apparatus, and FIG. 2 is a plan view thereof.

2-3 Test Method 1) Plate-side test piece 1 was placed on plate 2 as shown in FIG.
Set on top. 2) The load side test piece 3 is set on the plate side test piece 1 as shown in FIG. 3) One end of the load-side test piece 3 is adhered to the jig 4 with a double-sided tape (not shown) as shown in FIG.
1 and 2 are connected to the load cell 6 as shown in FIG. 1 and FIG. At this time, the thread 5 is hung on a pulley 7 as shown in FIG.

4) As shown in FIGS. 1 and 2, a load 8 is placed at the center of the load-side test piece 3 and in parallel with the load moving direction. 5) The load side test piece 3 is moved at a test speed of 200 ± 10 mm / min, and the relationship between the distance over which the load 8 has slipped and the force observed by the load cell is determined by a chart as shown in FIG.

6) The static friction coefficient and the dynamic friction coefficient are obtained by the following equations. Static friction coefficient = static friction force (g) / load (g) Dynamic friction coefficient = dynamic friction force (g) / load (g)

[0069]

Comparative Example 1 A pellet-like poly-1-butene resin composition was obtained in the same manner as in Example 1 except that the fluorine-based resin was not used. Hereinafter, using this composition, it carried out similarly to Example 1. The results are shown in Table 2.

[0070]

Example 2 In Example 1, the poly 1-butene resin (b
In the same manner as in Example 1 except that the poly-1-butene resin (b-2) obtained in Production Example 2 was used instead of -1),
A poly-1-butene resin composition in the form of a pellet was obtained. Hereinafter, using this composition, it carried out similarly to Example 1. The results are shown in Table 2.

[0071]

Comparative Example 2 In Example 1, the poly 1-butene resin (b
Instead of -1), the poly (1-butene) resin (b-2) obtained in Production Example 2 was used, and the pellet-like poly (1) was prepared in the same manner as in Example 1 except that the fluororesin was not used. -A butene resin composition was obtained. Hereinafter, using this composition, Example 1
Was performed in the same manner as described above. The results are shown in Table 2.

[0072]

Example 3 In Example 1, the poly 1-butene resin (b
In the same manner as in Example 1 except that the poly-1-butene resin (b-3) obtained in Production Example 3 was used instead of -1),
A poly-1-butene resin composition in the form of a pellet was obtained. Hereinafter, using this composition, it carried out similarly to Example 1. The results are shown in Table 2.

[0073]

Comparative Example 3 In Example 1, the poly 1-butene resin (b
Instead of -1), the poly 1-butene resin (b-3) obtained in Production Example 3 was used, and a pellet-shaped poly 1 -A butene resin composition was obtained. Hereinafter, using this composition, Example 1
Was performed in the same manner as described above. The results are shown in Table 2.

[0074]

Example 4 In Example 1, the poly-1-butene resin (b
-1) was replaced with the poly-1-butene resin (b-3) obtained in Production Example 3, and instead of 0.2 parts by weight of high-density polyethylene (HDPE) as a nucleating agent, ethylene bisstearylamide ( EBSA) A pellet-form poly-1-butene resin composition was obtained in the same manner as in Example 1 except that 0.05 parts by weight of EBSA) was used.

Thereafter, the same procedure as in Example 1 was carried out using this composition. The results are shown in Table 2.

[0076]

Comparative Example 4 In Example 1, the poly 1-butene resin (b
-1) was replaced with the poly-1-butene resin (b-3) obtained in Production Example 3, and instead of 0.2 parts by weight of high-density polyethylene (HDPE) as a nucleating agent, ethylene bisstearylamide ( EBSA) A pellet-like poly-1-butene resin composition was obtained in the same manner as in Example 1 except that 0.05 parts by weight of EBSA) was used and no fluororesin was used.

Hereinafter, this composition was used, and the same procedure as in Example 1 was carried out. The results are shown in Table 2.

[0078]

Example 5 In Example 1, the poly 1-butene resin (b
Instead of -1), the poly 1-butene resin (b-3) obtained in Production Example 3 was used, and instead of 0.3 part by weight of the fluororesin, a fluoroelastomer [manufactured by Dupont Dow Elastomer Co., Ltd. Name Viton Free Flow SC PW]
A pellet-like poly-1-butene resin composition was obtained in the same manner as in Example 1 except that 0.3 parts by weight was used.

Hereinafter, this composition was used, and the same procedure as in Example 1 was carried out. The results are shown in Table 2.

[0080]

[Table 2]

[Brief description of the drawings]

FIG. 1 is a front view schematically showing a test apparatus for explaining a method for measuring static and dynamic friction coefficients.

FIG. 2 is a partial plan view of FIG. 1 showing an outline of a test apparatus for explaining a method for measuring static and dynamic friction coefficients.

FIG. 3 is a chart for explaining a method of measuring static and dynamic friction coefficients, and is a chart showing a relationship between a distance in which a load has slipped and a force observed by a load cell.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Plate side test piece 2 ... Plate 3 ... Load side test piece 4 ... Jig 5 ... Thread 6 ... Load cell 7 ... Pulley 8 ... Load

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3H111 AA01 BA15 BA34 CB02 DA26 DB03 EA04 4F071 AA21 AA26 AH05 EA01 4J002 BB033 BB123 BB171 BC033 BD122 BD152 BD162 CL003 CL013 DE106 DE136 DJ046 EA066 EC056 EE056 EF0206 EF0206 EF0206 EF0206

Claims (10)

[Claims] 1. A poly-1-butene resin composition having a coefficient of static friction of 4.3 or less and / or a coefficient of dynamic friction of 2.3 or less. 2. The poly-1-butene resin composition comprises 80 to 100 mol% of 1-butene and 2 to 10 carbon atoms.
Of α-olefins other than 1-butene by (co) polymerization, and a melt flow rate (MFR;
ASTM D 1238, 190 ℃, 2.16kg load) 0.01 ~ 50g
Poly-1-butene resin (A) 97-99.9
2. The composition according to claim 1, comprising 99% by weight, 0.001 to 3% by weight of a fluoroelastomer (B) and / or 0.001 to 3% by weight of a fluororesin (C). 3. Poly
1-butene resin composition. 3. A melt flow rate (MFR; ASTM D 1238, 190 ° C., 2.16 kg load) of the poly-1-butene resin (A).
The poly-1-butene resin composition according to claim 2, wherein the isotactic index (mmmm%) measured by NMR is 90 or more. 4. The poly-1-butene resin (A) has a melt flow rate (MFR; ASTM D 1238, 190 ° C., 2.
16 kg load) is 0.01 to 5 g / 10 min, the molecular weight distribution (Mw / Mn) determined by the GPC method is 6 or less, and the isotactic index (mmmm%) measured by NMR is 90. The above poly 1-butene resin (a1) is contained in an amount of 60 to 95% by weight and a melt flow rate (MFR; ASTM D 1238, 190 ° C, 2.16 kg load).
20 times or more the MFR value of the 1-butene resin (a1),
5-40 weight% of poly 1-butene resin (a2) having a molecular weight distribution (Mw / Mn) determined by GPC method of 6 or less and an isotactic index (mmmm%) measured by NMR of 90 or more % Of the poly 1-butene resin (a). 5. The poly-1-butene resin (A) (co) polymerizes 80 to 100 mol% of 1-butene and 0 to 20 mol% of α-olefins other than 1-butene having 2 to 10 carbon atoms. Having an isotactic index (mmmm%) of 90 or more as measured by NMR, a molecular weight distribution (Mw / Mn) of 3 or more as determined by a GPC method, and a metal represented by titanium metal 50p remaining
3. The poly-1-butene resin composition according to claim 2, which is a poly-1-butene resin (b) having a pm or less. 6. The poly-1-butene resin composition according to claim 2, further comprising a nucleating agent. 7. The method according to claim 1, wherein the pipe is used for a pipe.
7. The poly-1-butene resin composition according to any one of items 1 to 6. 8. The poly-1-butene resin composition according to claim 1, which is used for pipe joints. 9. A pipe comprising the poly-1-butene resin composition according to claim 1. 10. The poly-1- according to claim 1, wherein
A pipe joint comprising a butene resin composition.