JPH04175317A - Butene-1 copolymer and resin composition containing same - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in impact resistance, transparency and heat sealability by mixing a specified stereoregular crystalline PP with a butene -1/propylene copolymer. CONSTITUTION:95-50 pts.wt. stereoregular crystalline PP comprising 98-80 pts.wt. propylene units, 0-18wt.% 4-12 C alpha- olefin units and 2-20wt.% ethylene units and having a melt flow index (at 230 deg.C) of 0.1-100g/10min is mixed with 5-50 pts.wt. butene -1/propylene copolymer having, when determined by <13>C-NMR spectroscopy in a 1, 2, 4- trichlorobenzene solution, an intensity of an absorption appearing at about 26.9ppm with reference to tetramethylsilane among absorptions assignable to the methylene group as a side chain of a butene -1 unit which is at least 0.3 time as strong as that of the total absorptions assignable to the methylene group as a side chain appearing at about 27.8-26.0ppm, a propylene content of 0.1-20wt.% and an intrinsic viscosity (at 135 deg.C in a tetralin solution) of 0.05 or above.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a copolymer of butene-1 and propylene, and an easy-to-use adhesive layer for heat-bonding polyolefins containing this copolymer. The present invention relates to a heat-sealable polypropylene resin composition.

[Prior Art] The existence of α-olefin polymers having a syndiotactic structure has been known for a long time, and one of them is syndiotactic polypropylene. However, syndiotactic polypropylene obtained by a method of polymerization at low temperature using a conventional catalyst consisting of a vanadium compound, an ether, and an organoaluminum compound has poor syndiotacticity and is not characterized as syndiotactic polypropylene. It was difficult to say that there existed.

J, A. and Ewen et al. showed that 13 (syndiotactic pen by NMR) was obtained by polymerizing propylene using a polymerization catalyst consisting of transition metal (Hf and Zr) compounds having asymmetric ligands and methylaluminoxane. It was discovered for the first time that polypropylene with good toughness such as a Tad fraction exceeding 0.8 can be obtained (J, Amer, Chem, Soc, 19B8°1
10.6255-6).

On the other hand, the present inventors have found that polybutene-1 having high syndiotacticity can be obtained by polymerizing butene-1 by using the above-mentioned catalyst with high purity. Although this catalyst has good activity per transition metal and the obtained polybutene has high toughness, the physical properties of the polybutene are relatively unbalanced or poor, and the transparency of molded polybutene is poor. It is enough.

Polypropylene, which has substantially q-regularity - substantially isotactic structure and substantially syndiotactic structure, has excellent rigidity, excellent appearance such as transparency and gloss, and is used for various purposes. . For the film, a copolymer of propylene and ethylene is used to improve its impact resistance and heat sealability, and propylene-ethylene-butene is used as a film with an excellent balance of rigidity, impact resistance, and heat sealability. -1 terpolymer is known.

Although these copolymers have an excellent balance of rigidity, impact resistance, and heat-sealing properties, it is desirable to further improve the heat-sealing properties in order to improve the efficiency of film utilization.

[Problems to be Solved by the Invention] An object of the present invention is to provide a copolymer of butene-1 and propylene having a substantially syndiotactic structure, which has relatively excellent impact resistance and good transparency. It is in.

Another object of the present invention is to provide a heat-sealable polypropylene resin composition which has excellent heat-sealability and other physical properties.

[Means for Solving the Problems] The copolymer of butene-1 having a substantially syndiotactic structure according to the present invention has a butene-1 copolymer having a substantially syndiotactic structure in “C-NMH” measured with a 1,2,4-1-lichlorohensen solution.
Of the absorption of the methylene group in the side chain of one unit, the absorption intensity observed at about 26.91111ffl based on tetramethylsilane is about 27.8 to 26. It is 0.3 or more of the total absorption intensity of the methylene group of the side chain observed in Oρρ−, and the content of propylene units is 0.1 wt% to 20 wt%.
%, and is characterized by having an intrinsic viscosity of 0.05 or more as measured with a tetralin solution at 135°C.

The easily heat-sealable polypropylene A4 resin composition of the present invention is a substantially stereoregular crystalline polypropylene, comprising 98 to 80 wt% of propylene units in the polymer;
α-olefin unit having 4 to 12 carbon atoms or 0 to 18 wt,
%, 2 to 20 wt% of ethylene, and the melt flow index measured at 230°C is 0.1 to 100 g.
It is characterized in that it consists of 95 to 50 wt parts of a polymer having the following properties:

The copolymer of butene-1 according to the invention having a substantially syndiotactic structure is obtained by copolymerizing butene-1 and propylene in the presence of a catalyst. Examples of polymerization catalysts include the compounds described in the above-mentioned literature by J^, Ewen et al. However, even if they have a different structure, when a propylene homopolymer is produced, the syndiotactic pentad of the resulting polymer Fraction (A, ZaLIlbel
Li et al.: Macromolecules, 6.92
5 (+97:l), 1 bid,, 8.687 (+97
5)) Any catalyst system that gives a polymer with a relatively high toughness of 0.5 or higher can be used, for example, a catalyst system consisting of a transition metal compound having an asymmetrical ligand and aluminoxane. Catalytic system is effective.

Suitable transition metal compounds for producing the copolymer of the present invention include isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride, or isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride described in the above literature.
Fluorenyl) zirconium dichloride, and those in which one or two of these chlorines are substituted with another halogen or an alkyl group having 1 to 5 carbon atoms can be mentioned.

Examples of aluminoxane include compounds represented by the formula (in the formula, R is a hydrocarbon residue having 1 to 3 carbon atoms), particularly methylaluminoxane where R is a methyl group, nf)'; 5 or more, preferably 10 It is used in areas north of this area.

The ratio of aluminoxane to the above transition metal compound is 10 to 1,000,000 times by mole, usually 50 to 5.1 times.
'100 times the mole.

The polymerization conditions are not particularly limited to II, and a known polymerization method in the presence of an inert solvent, a bulk polymerization method in a polymerization system substantially free of an inert solvent, or a gas phase method may be used. Usually 1
Polymerization temperature is -100℃~200℃, polymerization pressure is normal pressure~1
00kg/cl! It is 12-6. -100℃～100
C. and normal pressure to 50 kg/cl12-G are particularly preferred.

During polymerization, the propylene unit content in the copolymer is 0 or 0.
．． The amount of monomer introduced into the polymerization system is controlled to be 1 to 20 wt%, preferably 1 to 20 wt%, and 1 to 20 wt% of the copolymer is added.
3 (Among the absorptions of methylene groups in the side chains of butene-1 units measured by NMR, the absorption intensity observed at about 26.9pp11 with respect to tetramethylsilane is about 27.8
The monomer quantitative ratio, polymerization temperature, etc. are controlled so that the total absorption intensity of the methylene group in the side chain observed at ~26.0 ppm is 0.3 or more, preferably 04 or more, and furthermore, the monomer amount ratio, polymerization temperature, etc.
It is desirable to treat the copolymer by a method such as washing with a solvent such as a hydrocarbon of ~20%.

Examples of hydrocarbon solvents include propylene itself or saturated aliphatic hydrocarbon compounds such as propane, butane, pentane, hexane, heptane, octane, and nonane, as well as aromatic hydrocarbon compounds such as pentene, toluene, xylene, and ethylbenzene. Those in which part or all of the hydrogen is replaced with fluorine, chlorine, bromine, or iodine can also be used.

Other solvents include alcohols having 1 to 20 carbon atoms;
Ethers and esters having 2 to 20 carbon atoms and those capable of dissolving or dispersing low molecular weight atactic components can be used. There are no particular restrictions on the cleaning method, and it is usually 0°C to 1°C.
It is carried out at a temperature of 00°C.

Using a high purity catalyst, usually 90% or more, relatively low temperature,
Generally, it is also effective to carry out the polymerization at a temperature of 100° C. or lower to obtain the F copolymer.

In the copolymer of butene-1 and propylene of the present invention, the chain of butene-1 units has a substantially syndiotactic structure, which is specified as follows. That is, in l''c-NMR measured with a 1,2,4-trichlorobenzene solution, the absorption observed at about 26.9 ppm based on tetramethylsilane among the absorptions of the methylene group in the side chain of the butene-1 unit. The strength is about 27.8
The total absorption intensity of the methylene group observed in ~2
20 gastric L%, and the intrinsic viscosity measured with a tetralin solution at 135°C is 0.05 or more. Here, if the parameter specified by the C-NMR measurement result, which is a measure of syndiotacticity, is smaller than 0.3, the physical property balance will be poor.Also, the intrinsic viscosity is 0.05.
If it is less than this, the physical properties of the composition, particularly blocking when formed into a film, will be poor, which is not preferable. The upper limit of the intrinsic viscosity is about 5. Furthermore, the content of propylene units is 0
．． If it is less than 1 wt%, the effect of improving the transparency of the polymer will be small, and if it exceeds 20 wt%, the rigidity will be poor. In addition,
The number average molecular weight in terms of propylene measured by gel permeation chromatography is north of 1,000, especially 5.
,000 or more, and the ratio of weight average molecular weight to number average molecular weight (hereinafter referred to as M, /Mn -1-) is preferably 1.5 to 1O.

The substantially stereoregular crystalline polypropylene used as a component of the polypropylene resin composition of the present invention may have a substantially isotactic structure or a substantially syndiotactic structure. . This crystalline polypropylene contains 98-80 wt% propylene units, 0-18 wt% α-olefin units, and 2-20 wt% ethylene units, and has a melt flow index of 0.1 measured at 230°C. ~100g
/10n+in.

The above-mentioned polypropylene having a substantially isotactic structure means that in the 13C-NMR spectrum, the absorption mainly attributed to the methylene group of the propylene unit is about 2
1.41) Polypropylene having a substantially syndiotactic structure is observed at Dlm and the above absorption is observed at 20.2 pplO.

Polypropylene having a substantially isotactic structure can be obtained by well-known methods such as titanium trichloride or its modified products, titanium tetrachloride together with an electron-donating compound on a carrier such as magnesium chloride, or aluminum chloride. It can be produced by polymerizing propylene and ethylene together with an α-olefin having 4 to 12 carbon atoms, if desired, using an electron-donating compound if necessary. Various types of such polypropylene are available as commercial products.

On the other hand, for polypropylene having a substantially syndiotactic structure, propylene and ethylene are optionally prepared using the same catalyst as used for the polymerization of butene-1 and under the same polymerization conditions. It can be produced by copolymerizing with olefins.

Substantially stereoregular polypropylene contains 98 to 80 wt% of propylene units, θ to 18 wt% of α-olefin units having 4 to 12 carbon atoms, and 2 to 2 wt% of ethylene units.
It is necessary that the propylene content is 0wt% and the propylene degree is 80%.
If it is less than 98wt%, the rigidity of the molded product is poor.
If it exceeds this, the impact resistance is poor. Also, carbon number 4-12
If the α-olefin unit exceeds 18 wt%, the rigidity of the molded product will be poor, if the ethylene unit is less than 2 wt%, the impact resistance and heat sealing properties will be poor, and if it exceeds 20 wt%, the molded product will have poor rigidity. It is defective. Also, the melt flow index measured at 230°C from the point of the molded product is o, t.
It is necessary that ~t o Og/l 0 m1n. Melt flow index is 0.1g710m1n
Even if it is less than 100g/l 0IIlin or exceeds 100g/l 0IIlin, it becomes difficult to form it into a film.

The preferred range of each structural unit in the substantially stereoregular crystalline polypropylene is 97 to 85 w propylene units.
t%, 0 to 15 α-olefin units having 4 to 12 carbon atoms
wt%, and the ethylene unit is 3 to 15 t%. Also,
The preferred range of melt flow index is 1 to 50g.
It is 710 min.

The mixing ratio of the above-mentioned substantially stereoregular crystalline polypropylene and the copolymer of butene-1 having a substantially syndiotactic structure is 95 to 50 parts by weight of the former and 5 to 50 parts by weight of the latter. It is necessary. The former is 95
If the amount is higher than the wt part, there will be no improvement in heat sealability.
Moreover, if it is less than 50 wt, physical properties such as rigidity and blocking properties will be poor. A preferred mixing ratio is 90 to 60 parts by weight of substantially stereoregular crystalline polypropylene;
The amount is 10 to 40 parts of a substantially syndiotactic copolymer of 1-butene and propylene.

Substantially stereoregular crystalline polypropylene and butene
Various known methods can be used for mixing with the copolymer having a substantially syndiotactic structure. That is, after mixing with a Henschel mixer or the like, there are methods of melt-mixing with an extruder, methods of mixing with a roll, and methods of mixing with a Brahmender or Banbury mixer.

In addition to the above-mentioned polymer, the resin composition of the present invention also contains antioxidant I
Known additives such as L agent, ultraviolet absorber, anti-blocking agent, and slip agent may be included depending on the purpose.

The copolymer of butene-1 and propylene according to the invention can be used as a molded product such as a film. Furthermore, the polypropylene composition of the present invention is useful as a heat-sealing layer when heat-bonding polyolefins.

[Examples] Examples of the present invention are shown below, but these examples are merely illustrative of the present invention and should not be construed as limiting.

Example! In an autoclave with contents F421, isobrobylcyclopentacyenyl-I-fluorene synthesized according to a conventional method was lithiated, and this was reacted with zirconium tetrachloride. ) Zirconium dichloride 5
g of intestine and 067 g of methylaluminoxane with a degree of polymerization of about 16 manufactured by Toso Akzo ■ were dissolved in 1 u of toluene and charged. Then, add 25% of propylene at 30"C in an autoclave.
Then, 460 g of butene-1 was pressurized and polymerized for T1 hour. After polymerization, unreacted 1,000 yen was purged and 50
After adding methanol (No. 01) and filtering the mixture, the mixture was dried under reduced pressure at 80° C. to obtain 44.4 g of a copolymer.

This copolymer has an absorption intensity of about 26.9 ppm based on tetramethylsilane in 13C-NMR measured with a 1.2.4-trichlorohensen solution, but an absorption intensity of about 27.8 to 26.0 ppm. 0 of the total absorption intensity
．． 67, and propylene is 6. It contained Owt%. In addition, the intrinsic viscosity (
(hereinafter referred to as η) is 0.65, and M = /M n measured with a solution of 1.2.4 to trichlorobenzene at 135°C by gel permeation chromatography is 2.1.
Met.

This copolymer was press-molded at 210°C to produce a 1 mm sheet, and the following physical properties were measured using the methods described for each item.

・Tensile yield strength: kg/cm2 8STM [16
18 (23℃)・Elongation:% ASTM 0
618 (23℃) / Izot (notched) Impact strength: kg-cm/c +++ ASTM D256 (23
℃, -10℃)・Haze: % ASTM
D1003 tensile yield strength was 30 kg/cm2, elongation was 47%, Izod impact strength was 56.68 (23°C and -10°C, respectively) kg-col/c111, and haze was 30%.

Comparative Example 1 Polymerization without using propylene resulted in η of 0.17, syndiotactic pentad fraction of 0.89, Mw/M,
Example 1 except that a polymer with 1.5 was obtained and the physical properties were measured.
When the physical properties were measured in the same manner as above, the tensile yield strength was 1
08 kg/cm2, elongation is 38%, Izod impact strength is 48.2.8 (23℃, -10℃, respectively) kz
-cm/crn, and the haze was 68%.

From the above results, the butene-1 copolymer of the present invention is
It is clear that compared to Mobolymer No. 1, Izotsu's impact strength, strong transparency, and PJj''L are the same.

Below, methods for evaluating film physical properties in Examples and Comparative Examples of the present invention will be shown. 20/10.000 weight ratio of phenolic stabilizer to the resin composition or copolymer powder, 5/10.000 weight ratio of calcium stearate,
Lubricant 9/10,000 weight ratio and anti-blocking agent silicon dioxide fine powder 25/10.1
1011 weight ratio, and then using a 202 Henschel mixer (manufactured by Mitsui Miike Seisakusho ■), 30 to 40
Mixed for 4 minutes at °C. The mixture was kneaded into pellets using a 65 mm diameter jingle screw granulator (manufactured by Toshiba Machine ■), and then pelletized into pellets with a thickness of 30 μ and a width of 25 cm at a resin temperature of 250°C using a 40 mm diameter jingle screw film forming machine (manufactured by Osaka Seiki ■). A T-tie film was prepared and its physical properties were evaluated. The method for measuring each physical property is as follows.

・Haze (%): ASTM 1003-53° ・Blocking (%): Place two 200 mm x 200 ml films on top of each other on a flat iron plate, and place 20011! as a weight on top of it. IX 2001111 market 2kg
After placing a steel plate on the surface and keeping it at 50℃ for 24 hours, it is calculated as a percentage of the adhesion area.

・Young's modulus (kg/mm2): 20 mm x 2
Measured using an Instron universal tensile compression tester using a 20 am film.

- Embossing: Determined visually after holding the film at 50°C for 30 days.

・Heat-sealing temperature: Measured using a Toyo Seiki thermal gradient tester (heat-sealing is performed at a pressure of 2 kg/cm2,
The heat-sealing strength of the sample was heat-sealed for 1 second and was measured using an Instron universal tensile compression tester)
.

・Hot tack property: Uses a heat seal tester manufactured by Tester Sangyo ■. Heat sealing pressure 1 kg/c+m2
Pressure is applied for seconds and measured as the lowest temperature at which peeling does not occur under a peeling load of 45 g.

・Melt flow rate ・ASTM 01238-657
Measured at a temperature of 230℃ and a load of 2.15kg.

Example 2 Bladder vine pH A vibratory mill equipped with four grinding pots of M4.9 containing 9 kg of steel balls with a diameter of 12 mm was prepared. Add 300 g of magnesium chloride, 1151 g of diisobutyl phthalate, and 601 g of titanium tetrachloride to each pot in a nitrogen atmosphere.
Time crushed.

5 g of the above co-pulverized product was placed in a 2001 flask, 1001 g of toluene was added thereto, stirred at 114° C. for 30 minutes, and then left to stand to remove the supernatant liquid. Then Rehebutane 100
Wash the solid content three times at 20°C using m1, and then
1 was dispersed in n-heptane to prepare a transition metal catalyst slurry. The obtained transition metal catalyst contained 1.8 wt% titanium and 18 wt% and 8 wt% diisobutyl phthalate.

25 kg of propylene and 13.4 kg of butene were charged into a jacketed autoclave, which had been purged with N100 Il of sufficiently dry nitrogen, and then replaced with propylene. I prepared.

Meanwhile, 500 ml of n-hebutane was added to the IIL flask.
Triethylaluminum 4.71, cyclohexylmethyldimethoxysilane 2.3011 and the above catalyst j! The solid content of the transition metal catalyst obtained by I.I. : 15μ was mixed and press-fitted into the prepared autoclave containing M100U. Next, after charging 30 g of hydrogen and 300 g of ethylene, hot water was poured into the jacket at an internal temperature of 65° C. so that the gas phase concentration of each component was 2.3 mol% hydrogen, ethylene 1.
Hydrogen, ethylene, and butene were charged to maintain the concentration of 5 mol% and 13,5 mol% of propylene, respectively.
The polymerization was carried out by continuously charging the reactor at a rate of kg/h, and after 3 hours, 3,51 liters of thiethylene glycol monoisobrobyl ether was introduced under pressure, and the polymerization was completed by further stirring at 60° C. for 30 minutes.

The obtained copolymer slurry was heated to a diameter of 15 cm at the thin part.
m, the inner diameter of the thick part at the top is 30 cm, the length of the thin part is 5 m, and the length of the thick part at the top is 1 m.
50 kg/h was introduced into the F part, and from the lower part, 100 kg of a cleaning solution having a composition of 89 mol% propylene, 5 mol% propane, 1 mol% ethylene, and 15 mol% butene was introduced.
/h, and 110 kg/h from the north of the flow washing tower.
Washing solution of h, the copolymer slurry washed from below was added to 4
Take out at 0 kg/h. The copolymer slurry taken out was placed in an outer tube with an inner diameter of 20 cm and a length of 60 m at a weight of 1 kg/
The powder was then discharged into a cyclone maintained at atmospheric pressure through a double tube heated through C1112 gauge steam, and the resulting powder was further dried at 50°C and 60 mmHg for 10 hours to yield 13.0 kg of copolymer. Obtained.

The ethylene content of this propylene copolymer is 2.1 wt%
, butene was 1.6 wt%, intrinsic viscosity was 1.63, and melt flow index was 5.7. The physical properties measured for the resulting film were haze 2.0, blocking 10%, Young's modulus 69 kg/am2, heat seal temperature 132.8°C, no embossment, and hot tack temperature f42.5°C. Ta.

ヱヱ->(!-Part 13) Isopropylcyclopentadienyl-1-fluorene synthesized according to a conventional method in a 112 fl autoclave was lithiated, and this was reacted with zirconium tetrachloride, and then specially prepared. The obtained isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride 5
11 g and 0.67 g of methylaluminoxane with a degree of polymerization of about 16 manufactured by Tow Akzo ■ were dissolved in toluene lβ and charged, 30 g of propylene was added at 30°C, and then 460 g of butene-1 was pressurized to 1 liter. Polymerized for hours. After the polymerization, unreacted particles were purged, a large amount of methanol was added, the mixture was filtered, and the mixture was dried under reduced pressure at 80° C. to obtain 46.8 g of a copolymer.

This copolymer has an absorption intensity of about 27.8 to 26.0 ppm, which is observed at about 25.9 ppm based on tetramethylsilane in 13C-NMR measured with a 1,2.4-trichlorohenzene solution. It had a strength of 0.67 and contained 9.5 wt% of propylene. Moreover, its η was 0o68, and M 2 and /M n were 2.1.

80 wt parts of the above propylene copolymer and the above butene-1
A film was formed by mixing 20 wt parts of a copolymer of propylene and propylene, and the physical properties were measured. The haze was 2.1%, the blocking was 10%, and the Young's modulus was 68 kg/ll! 12. Heat sealing temperature was 122.6°C, no embossing, hot tack temperature was 128.0°C.

Comparative Example 2 As a propylene-butene-1 copolymer, the isotactic structure obtained by polymerizing using the catalyst supported on magnesium chloride of Example 2 was used.

This copolymer has almost no absorption at about 26.9 ppm, the maximum intensity (about 0.7 of the absorption intensity of all methylene groups) is observed at about 27.8 ppm, and the content of propylene units is 10.8 ppm.
5 wt%, η was 0.7. When evaluated in the same manner as in Example 2 except that this copolymer was used, the haze was 2.
．． 2. Blocking 10%, Young's modulus 63 kg/mo
b2, the heat seal temperature was 128.5°C, there was no embossment, and the hot tack temperature was 130.0°C.

Young's modulus decreases significantly and hot tack properties are slightly inferior.

Comparative Example 3 Example 2 except that the gas phase concentration of ethylene was 3.6 mol%
Adding a propylene-butene-1 copolymer using a propylene copolymer containing 4.5 L% ethylene units and 1.5 at% butene-1 units obtained in the same manner as in the production of a propylene copolymer. When the physical properties were measured by forming the film as it was, the haze was 1.7, the blocking was 10%, the Young's modulus was 50 kg/m112, and the heat sealing temperature was 124.6.
°C, there was no floating, and the hot tack temperature was 135.0 °C. By increasing the ethylene content, heat sealing properties similar to those of Example 2 were exhibited, but the Young's modulus was significantly reduced and the hot tack properties were poor.

Example 3 A copolymer of butene-1-propylene with a propylene content of +7.2 wt% was obtained in the same manner as in Example 1 except that the amount of propylene used was 50 g. η is o, 82, approximately 26.9pp
The absorption intensity observed at m is approximately 27.8 to 26.0 pp
The absorption intensity of m was 0.62. A resin composition obtained in the same manner as in Example 1 except for using this copolymer was formed into a film, and its physical properties were measured. Blocking was 15%, Young's modulus was 67 kg/am2, heat sealing temperature was 118.5°C, there was no floating, and hot tack temperature was 119.5°C.

Example 4 Using the catalyst used in Example 1, content $211
100 g of propylene, butene-
15 g and 2 g of ethylene were press-injected and the mixture was heated to 1.
Polymerization was carried out in the same manner as in Example 1, so that the content of ethylene degree was 1.8% and the content of butene-1 unit was 2%.
．． A 5% propylene-ethylene-butene copolymer was obtained.

This copolymer has an η of 1.25 and a melt flow index of 7.2, and in C-NMR, the absorption intensity observed at about 20.2 ppm based on tetramethylsilane is due to the methyl group of the propylene unit. was obtained in the same manner as in Example 2 using this copolymer, which had a total absorption intensity of 0.75 or more and which had a substantially syndiotactic structure. 5
When the 4If1 composition was formed into a film and the physical properties of the obtained film were measured, the haze was 15% and the blocking was 2.
0%, Young's modulus: 48 kg/+m2, heat seal temperature: 95°C, no floating, hot tack temperature: 98°C
Met.

[Effects of the Invention] The copolymer of butene-1 and propylene according to the present invention having a substantially syndiotactic structure has relatively excellent impact resistance and good transparency. Moreover, the polypropylene resin composition according to the present invention has excellent heat sealability,
It also has good physical properties and is useful as a heat-sealing layer for heat-bonding polyolefins.

Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] Measured with 1,1,2,4-trichlorobenzene solution^
In 1^3C-NMR, the absorption intensity observed at about 26.9 ppm based on tetramethylsilane among the absorption of the methylene group of the side chain of the butene-1 unit is about 27.8
It is 0.3 or more of the total absorption intensity of the methylene group of the side chain observed at ~26.0 ppm, the content of propylene units is 0.1 wt% ~ 20 wt%, and the limit measured in a tetralin solution at 135 ° C. A copolymer of butene-1 and propylene having a viscosity of 0.05 or more. 2. The copolymer according to claim 1, wherein the content of propylene units is 1 wt% to 20 wt%. 3. The copolymer according to claim 1, which has a number average molecular weight in terms of propylene measured by gel permeation chromatography of 1,000 or more. 4. The ratio of weight average molecular weight to number average molecular weight is 1.5 to 1.
The copolymer according to claim 1, wherein the copolymer has a molecular weight of 0. 5. Stereoregular crystalline polypropylene, the propylene unit in the polymer is 98 to 80 wt%, and the number of carbon atoms is 4.
~12 α-olefin units are 0 to 18 wt%, ethylene units are 2 to 20 wt%, and the melt flow index measured at 230°C is 0.1 to 100 g/10 min.
In the ^1^3C-NMR measured with 95 to 50 wt parts of the polymer and 1,2,4-trichlorobenzene solution, the absorption of the methylene group of the side chain of the butene-1 unit is based on tetramethylsilane. The absorption intensity observed at about 26.9 ppm is 0.3 or more of the total absorption intensity of methylene groups observed at about 27.8 to 26.0 ppm, and the content of propylene units is 0.1 to 20 wt%. Yes, 13
Copolymer of butene-1 and propylene 5 to 50w having an intrinsic viscosity of 0.05 or more as measured in a tetralin solution at 5°C
An easily heat-sealable polypropylene resin composition comprising part t. 6. Stereoregular crystalline polypropylene 90-60wt
6. The resin composition according to claim 5, comprising 10 to 40 parts by weight of the butene-1 copolymer. 7. The resin composition according to claim 5, wherein the stereoregular crystalline polypropylene has a substantially isotactic structure. 8. The resin composition according to claim 5, wherein the stereoregular crystalline polypropylene has a substantially syndiotactic structure.