JPH11181025A - Propylene resin - Google Patents

Abstract

(57) [Problem] To provide a propylene-based resin having excellent flexibility, transparency, heat resistance, excellent moldability, and improved bleed on the surface of a molded product. The melt flow rate is 0.01 to 10 g /.
10 minutes, a propylene resin having an ethylene unit content of 10 to 30 mol% and a 1-butene unit content of 1 to 20 mol%, and a molecular weight distribution (Mw / Mn) of 6-1.
6, in the elution curve obtained by the elevated temperature elution fractionation method, the amount of the eluting component (component A) at less than 20 ° C. was 20 to
50 wt%, eluted component at 20 ° C or higher and lower than 100 ° C (B
The amount of component (A) is 25 to 75 wt%, the amount of the eluting component (C component) at 100 ° C. or higher is 5 to 50 wt%, the total of component A, component B and component C is 100 wt%, and component B and component A And the weight ratio (B / A) is 0.8 or more, and the peak top temperature of the component C is 120 ° C. or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene-based resin having excellent flexibility, transparency, heat resistance and moldability, and having improved bleeding of a low molecular weight polymer on the surface of a molded article.

[0002]

2. Description of the Related Art Olefin-based thermoplastic elastomers have an excellent balance between economy and performance, and are light and recyclable. Therefore, various industrial parts, home electric parts, and films, including automobile parts such as bumpers, etc. Widely used for sheets.

[0003] Conventionally, in the production of olefin-based thermoplastic elastomers, ethylene-propylene rubber (hereinafter referred to as EPR) has been used.
That. ) And ethylene-propylene terpolymer (hereinafter referred to as EPDM) and a thermoplastic resin such as polypropylene by an extruder, and a polymerization method in which both components are produced at once by polymerization using a highly active titanium catalyst. Are known.

[0004] Among them, thermoplastic elastomers produced by a polymerization method generally have an advantage that transparency is better than that obtained by a blending method. In the production by such a polymerization method, a two-stage polymerization method in which a polypropylene component is copolymerized in a first step and ethylene and propylene are copolymerized in a second step is generally performed.

For example, JP-A-07-118354 discloses a method for producing a thermoplastic elastomer by a polymerization method, and the resulting propylene-ethylene copolymer having a specific composition has good flexibility. , Transparency, gloss and tensile elongation.

[0006] However, the propylene-ethylene copolymer obtained by the above method has room for improvement in heat resistance when the flexibility is improved, and has a weight-average molecular weight (Mw) and a number-average molecular weight (Mw). Mn) (Mw)
/ Mn) has a molecular weight distribution of about 3, and further improvement has been desired in terms of moldability, which is affected by melt tension during extrusion molding.

On the other hand, in order to improve the heat resistance of a propylene-based copolymer, Japanese Patent Application Laid-Open No. 63-165414 discloses a copolymer obtained by carrying out three-stage polymerizations of different ethylene compositions. A method has been proposed in which a block copolymer having a specific composition is kneaded in the presence of a peroxide and a crosslinking agent to improve the balance between tensile properties, heat resistance, and workability.

However, in this method, transparency and moldability tend to decrease due to the formation of a partially crosslinked component, and the balance between flexibility, transparency, heat resistance and moldability is further increased. There was a desire for improvement.

[0009] In any of the above thermoplastic elastomers, bleeding of the low molecular weight polymer easily occurs on the surface of the molded article, and there is room for improvement in this point.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a propylene copolymer having good flexibility, transparency, heat resistance and moldability, and having improved bleed on the surface of a molded article. To provide.

[0011]

Means for Solving the Problems The present inventors have intensively studied to achieve the above object. As a result, a propylene-based resin having a specific composition and a specific molecular weight distribution and a specific composition distribution was successfully developed, and it was found that the propylene-based resin satisfies the above-mentioned object, thus completing the present invention.

That is, in the present invention, the melt flow rate is 0.01 to 10 g / 10 min, the content of ethylene unit is 10 to 30 mol%, and the content of 1-butene unit is 1 to 10 mol%.
20 mol%, a molecular weight distribution (Mw) represented by a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) measured by gel permeation chromatography (GPC).
/ Mn) is 6 to 16, and the elution is performed at a temperature lower than 20 ° C. in an elution curve in which the horizontal axis represents the elution temperature (° C.) and the vertical axis represents the integrated weight ratio of the eluted components. The amount of the component (A component) is 20 to 50% by weight, 20 ° C. or higher and 100
The amount of the eluting component (component B) below 25 ° C is 25 to 75% by weight, and the amount of the eluting component (component C) above 100 ° C is 5 to 5%.
0% by weight, the total of component A, component B and component C is 100% by weight, the weight ratio of component B to component A (B / A) is 0.8 or more, and the peak top temperature of component C is 120 ° C. The above is a propylene-based resin characterized by the above.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the propylene resin of the present invention, if the melt flow rate is less than 0.01 g / 10 minutes, molding becomes difficult. If the melt flow rate exceeds 10 g / 10 minutes, the melt tension is reduced. It is not preferable because the processability is reduced. In addition, the melt flow rate of the propylene-based resin of the present invention is approximately 10 when converted to a weight average molecular weight by gel permeation chromatography.
It is in the range of 10,000 to 1,000,000.

The propylene resin of the present invention has a content of ethylene unit of 10 to 30 mol% and a content of 1-butene unit of 1 to 20 mol%. When the content of the ethylene unit is less than 10 mol%, sufficient flexibility as a thermoplastic elastomer is not exhibited, while when it exceeds 30 mol%, a propylene-based resin having excellent heat resistance and transparency is obtained. Can not do.

On the other hand, when the content of 1-butene unit is 1 mol%
If the amount is less than the above, bleeding to the surface of the molded article increases, and as a result, the transparency of the molded article is undesirably reduced with time. On the other hand, if it exceeds 20 mol%, it is not preferable because a thermoplastic elastomer having excellent heat resistance cannot be obtained.

The balance of the content of the ethylene unit and the content of the 1-butene unit in the propylene-based resin is the remainder of the content of the propylene unit. The sum with the unit content is 40
It is preferable that the content is not more than mol% in order to maintain excellent heat resistance and the like.

The propylene-based resin of the present invention has a molecular weight distribution (Mw / Mn) represented by a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) measured by gel permeation chromatography (GPC). , 6-16,
Preferably it is 8 to 15 in order to obtain excellent moldability.

That is, when the molecular weight distribution is less than 6, the moldability decreases, and when the molecular weight distribution exceeds 16, the orientation of the resin tends to increase at the time of molding, so that the balance of physical properties of the molded article is reduced. Excellent molding processability of the propylene-based resin of the present invention, as is apparent from the examples, the melt viscosity is lower in the same melt flow rate as compared with the conventional one,
Due to the high melt tension, for example, when applied to the extrusion molding field, the extrusion speed can be increased without increasing the mechanical load.

The propylene-based resin of the present invention comprises
The butene-1 has a weight-average molecular weight (Mw) of 10,000 or less as measured by the method described above.
This is preferable because it works together with the presence of the unit to suppress the occurrence of bleeding of the molded product.

In the present invention, the elevated temperature elution fractionation method refers to, for example, Journal of Applied Pol
ymer Science; Applied Poly
mer Symposium 45, 1-24 (199
0) is described in detail. First, a high-temperature polymer solution is introduced into a column filled with diatomaceous earth filler, and the column temperature is gradually lowered to crystallize the filler surface in order from the component with the highest melting point, and then the column temperature is gradually increased. This is a method in which the components are eluted in order from the component having the lowest melting point by raising the temperature, and the eluted polymer component is collected. In the present invention, as shown in the examples, SSC-7300 type manufactured by Senshu Kagaku Co., Ltd.
-Dichlorobenzene, flow rate: 2.5 ml / min, heating rate: 4 ° C./Hr, column: values measured under conditions of 30 mm × 300 mm.

The elution component (component A) of the propylene-based resin of the present invention at a temperature lower than 20 ° C. is a component necessary for particularly exhibiting flexibility. That is, if the amount of the component A is less than 20 wt%, flexibility is impaired, and if it exceeds 50 wt%, sufficient heat resistance cannot be obtained, which is not preferable. In order to exhibit more excellent flexibility and heat resistance as a thermoplastic elastomer, the amount of the component A is particularly preferably 25 to 45 watts.
It is preferably in the range of t%. In order to improve the flexibility and the bleed component of the molded product, the content of the ethylene unit in the component A is preferably 20 to 60.
Mol%, more preferably 25 to 50 mol%.
The content of 1-butene unit in the component is preferably 5
-40 mol%, more preferably 5-35 mol%.

The propylene resin of the present invention has a temperature of not less than 20 ° C.
The component eluted at a temperature lower than 00 ° C. (component B) is a component necessary for developing a good balance between transparency, flexibility and heat resistance. That is, if the amount of the component B is less than 25 wt%, good transparency and flexibility cannot be achieved when a molded article is obtained, and if it exceeds 75%, heat resistance is insufficient. In order to express a better balance of transparency, flexibility and heat resistance, the amount of the component B is particularly preferably 30 to 60 watts.
It is preferably in the range of t%. In order to obtain better transparency, the content of the ethylene unit in the component B is less than 20 mol%, and the content of the 1-butene unit is 5 mol%.
It is preferably less than.

The elution component (component C) of the propylene-based resin of the present invention at 100 ° C. or higher is a component necessary for obtaining the excellent heat resistance characteristic of the present invention. That is, if the amount of the C component is less than 5 wt%, or if the peak top temperature of the C component is less than 120 ° C., the heat resistance of a molded article is impaired, and the amount of the C component exceeds 50 wt%. In such a case, the flexibility is impaired, which is not preferable.

In consideration of flexibility and heat resistance, the amount of the component C is particularly preferably 5 to 40% by weight. In order to obtain more excellent heat resistance, the component C is preferably a highly crystalline polypropylene component having 50% or more of an eluted component at 120 ° C. or higher. In the propylene-based resin of the present invention, the weight ratio of the component B and the component A (B /
A) is 0.8 or more, preferably 0.9 or more. When the ratio of the amount of the component B to the amount of the component A (B / A) is less than 0.8, the balance of transparency, flexibility and heat resistance, which are the characteristics of the present invention, is not sufficiently exhibited, and the object of the present invention is achieved. Not done.

The propylene-based resin of the present invention is generally constituted by a polypropylene component and a propylene-ethylene-1-butene terpolymer component. The polypropylene component is preferably a propylene homopolymer having a high stereoregularity because good heat resistance can be obtained, but a random copolymer of propylene and other α-olefins within a range satisfying the requirements of the present invention. It may be united. Other α-
As the olefin, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 3
-Methyl-1-butene, 4-methyl-1-pentene and the like.

The propylene resin of the present invention may be a so-called block copolymer in which the above-mentioned polypropylene component and propylene-ethylene-1-butene terpolymer component are arranged in one molecular chain, or Better transparency is obtained when the molecular chains of the polypropylene component and the propylene-ethylene-1-butene terpolymer component are mixed microscopically to such an extent that they cannot be achieved by mechanical mixing. Therefore, it is preferable.

The propylene-based resin of the present invention may contain, for example, 5 parts by weight in addition to the above-mentioned polypropylene component and propylene-ethylene-1-butene terpolymer component within a range not to impair the effects of the propylene-based resin of the present invention. % Or less of other α-olefin polymer as a block copolymer component.

The method for producing a propylene resin of the present invention comprises:
Although not particularly limited as long as the requirements of the present invention are satisfied, for example, it can be obtained by the following method.

The following catalyst components [A], [B], [C] and [D] [A] titanium compound [B] organoaluminum compound [C] organosilicon compound [D] selected from carboxylic acid esters or ethers After propylene is polymerized in the presence of at least one type of electron donor compound, terpolymerization of propylene, ethylene and 1-butene is performed under the following conditions.

As the titanium compound [A], a titanium compound known to be used for olefin polymerization can be used without any limitation. Among them, a titanium compound capable of obtaining a polymer having high stereoregularity at a high yield when used for the polymerization of propylene is preferable. These titanium compounds are roughly classified into a supported titanium compound and a titanium trichloride compound.
As a method for producing the supported titanium compound, a known method is employed without any limitation. For example, Japanese Patent Application Laid-Open Nos. 56-155206, 56-136806, 57-34103, and 5
8-8706, 58-83006, 58-1387
08, 58-183709, 59-206408,
59-219311, 60-81208, 60-
81209, 60-186508, 60-1927
08, 61-211309, 61-271304,
62-15209, 62-11706, 62-7
2702, 62-104810 and the like. Specifically, for example, a method of co-grinding titanium tetrachloride with a magnesium compound such as magnesium chloride, co-milling titanium halide with a magnesium compound in the presence of an electron donor such as alcohol, ether, ester, ketone or aldehyde. A method of pulverizing, or a method of contacting a titanium halide, a magnesium compound and an electron donor in a solvent may be used.

Examples of the titanium trichloride compound include known α, β, γ and δ-titanium trichloride. The methods for preparing these titanium trichloride compounds are described in, for example, JP-A-47-34478, JP-A-50-126590 and JP-A-47-44590.
0-114394, 50-93888, 50-12
3091, 50-74594, 50-10419
1, 50-98489, 51-136625, 5
2-30888 and 52-35283 are adopted.

Next, as the organoaluminum compound [B], a compound known to be used for the polymerization of olefin is employed without any limitation. For example, trialkyl aluminums such as trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, tri-i-butyl aluminum, tri-n hexyl aluminum, tri-n-octyl aluminum, tri-n-decyl aluminum; diethyl aluminum Examples thereof include diethyl aluminum monohalides such as monochloride and diethyl aluminum bromide; and alkyl aluminum halides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride and ethyl aluminum dichloride. In addition, alkoxyaluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum can be used.

Further, as the organosilicon compound [C], a compound known to be used for improving the stereoregularity of an olefin is employed without any limitation, but a chain in which an atom directly connected to a silicon atom is tertiary carbon is used. Hydrocarbon, or 2
An organosilicon compound having a bulky substituent such as a cyclic hydrocarbon which is a graded carbon is preferable because the stereoregularity of the obtained polypropylene component is further increased and good heat resistance is exhibited. Specifically, di-t-butyldimethoxysilane, t
-Butylethyldimethoxysilane, di-t-amyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylisobutyldimethoxysilane And organosilicon compounds such as cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, and cyclohexylisobutyldimethoxysilane. Among them, t-butylethyldimethoxysilane and dicyclopentyldimethoxysilane are particularly preferred. In addition, a plurality of these organosilicon compounds can be used at the same time.

Further, as the at least one kind of electron donor compound [D] selected from carboxylic acid esters or ethers, compounds known to be used for improving the stereoregularity of olefins are employed without any limitation. Specifically, methyl formate, methyl acetate, ethyl acetate, butyl acetate,
Vinyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, ethyl valerate, ethyl stearate, ethyl acrylate, methyl methacrylate,
Ethyl benzoate, methyl toluate, methyl anisate,
Carboxylic esters such as ethyl phthalate, methyl carbonate and butyrolactone; methyl ether, ethyl ether, isopropyl ether, isoamyl ether, tetrahydrofuran, anisole, diethylene glycol dimethyl ether, 2,2-diisobutyl-1,3 dimethoxypropane, 2,2- Ethers such as dicyclopentyl-1,3 dimethoxypropane, 2,2-dicyclohexyl-1,3 dimethoxypropane; Among them, carboxylic esters such as butyl acetate and methyl methacrylate are particularly preferred. It is preferable to use two or more of the above carboxylic esters or ethers at the same time in order to obtain the propylene resin having the above-mentioned specific crystallinity distribution, which is the object of the present invention.

The use of the organosilicon compound [C] in combination with at least one electron donor [D] selected from carboxylic acid esters or ethers makes it possible to obtain a wide molecular weight distribution of the propylene resin of the present invention. This is a preferred embodiment in order to satisfy the weight ratio (B / A) of the component B and the component A and the peak top temperature in the component C.

The titanium compound [A] used in the present invention,
The combination of an organoaluminum compound [B], an organosilicon compound [C] and at least one electron donor [D] selected from carboxylic acid esters or ethers is as follows: (1) supported titanium compound-trialkylaluminum- (4) Titanium trichloride compound-diethyl aluminum monohalide-organosilicon compound-electron donor (3) Titanium trichloride compound-trialkylaluminum-organosilicon compound-electron donor and (4) The combination of the supported type titanium compound-titanium trichloride compound-trialkylaluminum-organosilicon compound-electron donor is particularly preferable in order to satisfy the constitution of the propylene resin of the present invention in combination with other production conditions.

In the present invention, prior to the main polymerization in the presence of each of the above components, the titanium compound [A] is converted to the above [B] and [C], or [B] and [D],
Alternatively, the prepolymerization of the α-olefin in the presence of [B], [C] and [D] reduces the amount of low molecular weight components of the resulting propylene-based resin, and causes stickiness when a molded article is obtained. This is suitable because it is possible to suppress
Further, if necessary, an iodine compound [E] [E] iodine compound RI represented by the general formula (i) in addition to the respective combinations using the above [B], [C], and [D] (I) (where R is an iodine atom or an alkyl group having 1 to 7 carbon atoms or a phenyl group). This is a more preferable embodiment because the amount of phenol can be further reduced and stickiness in the case of a molded article can be further suppressed.

The above [A] and [B] used in the prepolymerization of the present invention, [C] and / or [D] used as needed, and further used as needed [ E] The amount of each catalyst component depends on the type of catalyst component,
Since the amount varies depending on the polymerization conditions, the optimum amount to be used may be determined in advance according to each of these conditions. An example of a range preferably used is as follows.

The proportion of the organoaluminum compound [B] used in the prepolymerization is A with respect to the titanium compound [A].
0.1 / 100 (preferably 0.1 / 100) in 1 / Ti (molar ratio).
The proportion of the organosilicon compound [C] used in the range of 1 to 20 and at least one type of electron donor [D] selected from carboxylic acid esters or ethers is used as necessary. [A] against [C]
/ Ti (molar ratio), 0.01 in [D] / Ti (molar ratio)
A range of from 100 to 100, preferably from 0.01 to 10, is suitable. Further, the proportion of the iodine compound [E] used as necessary may be I to the titanium compound [A].
/ Ti (molar ratio) of 0.1 to 100, preferably 0.5
A range of ~ 50 is preferred.

Specific examples of the iodine compound which can be suitably used in the prepolymerization of the present invention are as follows. For example,
Examples thereof include iodine, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, iodobenzene, and p-iodine toluene. Particularly, methyl iodide and ethyl iodide are preferred.

The amount of pre-polymerization of the α-olefin in the presence of the catalyst component varies depending on the pre-polymerization conditions.
Generally, a range of 0.1 to 500 g / g · Ti compound, preferably 1 to 100 g / g · Ti compound, is sufficient. The α-olefin used in the prepolymerization may be propylene alone, and may be, for example, 5 mol% or less of another α-olefin, for example, ethylene, 1-butene, or 1 mol% within a range that does not adversely affect the physical properties of the propylene resin. Mixing -pentene, 1-hexene, 4-methylpentene-1 etc. with propylene is acceptable. Further, the prepolymerization may be performed in multiple stages, and a different α-olefin monomer may be prepolymerized in each stage. It is also possible to make hydrogen coexist at each prepolymerization stage.

In the prepolymerization, slurry polymerization is usually preferably applied. As a solvent, a saturated aliphatic hydrocarbon or an aromatic hydrocarbon such as hexane, heptane, cyclohexane, benzene or toluene is used alone, or a mixed solvent thereof. Can be used. The prepolymerization temperature is-
The range of 20 to 100C, particularly 0 to 60C is preferred. The pre-polymerization time may be appropriately determined according to the pre-polymerization temperature and the amount of polymerization in the pre-polymerization. The pressure in the pre-polymerization is not limited, but in the case of slurry polymerization, it is generally from atmospheric pressure to about 5 kg / cm ² G. The prepolymerization is
Any of batch, semi-batch, and continuous methods may be used.

The main polymerization is carried out after the preliminary polymerization. In the main polymerization, propylene is firstly polymerized, and then terpolymerization of propylene-ethylene-1-butene is performed in the presence of the catalyst-containing prepolymer obtained by the above prepolymerization. The catalyst components added during the prepolymerization can be used as they are, but it is preferable to add and adjust the components other than the titanium compound during the main polymerization.

The above [A] used in the main polymerization of the present invention,
Since the amounts and polymerization conditions of each of the catalyst components (B), (C), and (D) differ depending on the type of the catalyst component, the optimal amount and polymerization conditions should be determined according to the type of the catalyst component. It may be determined in advance. Examples of the amount of the catalyst component and the polymerization conditions suitably used are as follows.

As the organoaluminum compound [B] used in the main polymerization, those described above can be used without any limitation. The amount of the organoaluminum compound used is 1 to 1 in terms of Al / Ti (molar ratio) with respect to titanium atoms in the catalyst-containing prepolymer.
000, preferably 2 to 500.

As the organosilicon compound [C] used in the main polymerization, the compounds described above are employed without any limitation. The amount of the organosilicon compound used in the main polymerization is 0.001-1000, preferably 0.1-500, in terms of Si / Ti (molar ratio), based on titanium atoms in the catalyst-containing prepolymer.

As the at least one electron donor [D] selected from carboxylic acid esters or ethers used in the main polymerization, those described above are employed without any limitation.
The amount of the at least one electron donor selected from carboxylic acid esters or ethers used in the main polymerization is 0.001 to 1000, preferably 0.1 to 1000 in terms of a molar ratio to titanium atoms in the catalyst-containing prepolymer. 500.

In the main polymerization, propylene is firstly polymerized. The polymerization of propylene may be carried out by supplying propylene alone or a mixture of propylene and another α-olefin within a range satisfying the requirements of the present invention. Taking typical conditions for propylene polymerization as an example, it is preferable to employ a polymerization temperature of 80 ° C. or less, and more preferably in the range of 20 to 70 ° C. If necessary, hydrogen can also be allowed to coexist as a molecular weight regulator. Furthermore, the polymerization may be any method such as slurry polymerization using propylene itself as a solvent, gas-phase polymerization, and solution polymerization. Considering the simplicity of the process, the reaction rate, and the particle properties of the produced copolymer, slurry polymerization using propylene itself as a solvent is a preferred embodiment. The polymerization system may be any of a batch system, a semi-batch system, and a continuous system. Further, the polymerization can be performed in two or more stages having different conditions such as hydrogen concentration and polymerization temperature.

Next, a ternary copolymerization of propylene-ethylene-1-butene is performed. In the case of slurry polymerization using propylene itself as a solvent, terpolymerization of propylene, ethylene and 1-butene is performed by charging a predetermined amount of 1-butene subsequent to the propylene polymerization and supplying ethylene gas. In the case of gas-phase polymerization, one of propylene and ethylene
-It is carried out by supplying a mixed gas of butene.

The polymerization temperature of the terpolymerization of propylene, ethylene and 1-butene is 80 ° C. or less, preferably 20 ° C.
Adopted from the range of ７０70 ° C. If necessary, hydrogen can be used as a molecular weight regulator, and the polymerization can be carried out by changing the hydrogen concentration at this time in multiple stages.

By selecting a specific catalyst in the terpolymerization of propylene, ethylene and 1-butene subsequent to the propylene polymerization, a propylene resin having a desired molecular weight distribution, crystallinity distribution, etc. is produced in one step. However, in order to obtain a wide molecular weight distribution and crystallinity distribution of the propylene-based resin of the present invention, terpolymerization is performed in multiple stages,
It can be produced by a method in which polymerization conditions such as hydrogen concentration, 1-butene charge amount, and ethylene concentration are changed at each stage. In such a multi-stage terpolymerization, the terpolymerization is carried out by appropriately adjusting the polymerization conditions so that the ratio of the component A and the component B and the ratio of the component A and the component C are adjusted.

The terpolymerization of propylene, ethylene and 1-butene may be any of a batch system, a semi-batch system and a continuous system, and the polymerization may be carried out in multiple stages. Further, the polymerization in this step may employ any method of slurry polymerization, gas phase polymerization, and solution polymerization.

After completion of the main polymerization, the propylene resin of the present invention can be obtained by evaporating the monomer from the polymerization system. This propylene-based resin can be subjected to known washing or countercurrent washing with a hydrocarbon having 7 or less carbon atoms.

The method for producing the propylene-based resin of the present invention is not limited to the above-mentioned polymerization method, but may be any other highly crystalline polypropylene and propylene-ethylene-1-butene terpolymer obtained by separate polymerization, as long as the requirements of the present invention are satisfied. Although the original copolymer may be blended, it is preferably produced by a polymerization method in order to obtain good transparency.

The propylene resin of the present invention comprises an antioxidant,
After adding and mixing a commercially available additive such as a heat stabilizer and a chlorine supplement, a pellet may be used by an extruder. Also,
An organic peroxide may be added in addition to the above additives to adjust the molecular weight within a range that satisfies the requirements of the present invention.

[0056]

The propylene resin of the present invention has flexibility,
It has excellent transparency, heat resistance, and moldability, and has improved bleeding to the surface of a molded product, and can be suitably used in various fields in which conventional thermoplastic elastomers are used. For example, in the field of injection molding, bumpers, mudguards, and lamp packings for automobile parts, and in the field of home appliances, various packings, ski shoes, grips, and roller skates. On the other hand, in the extrusion molding field, various automotive interior materials, various insulating sheets as home appliance and electric wire materials, covering materials for cords and waterproof sheets, waterproof materials, jointing materials,
It can be suitably used for a stretch film for packaging and the like.

[0057]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The measurement method used in the following examples will be described.

1) Heated Elution Fractionation Method SSC-7300 manufactured by Senshu Scientific Co., Ltd. was used under the following measurement conditions.

Solvent: O-dichlorobenzene Flow rate: 2.5 ml / min Heating rate: 4 ° C./Hr Sample concentration: 0.7 wt% Sample injection amount: 100 ml Detector: Infrared detector, wavelength 3.41 μm column; φ30mm × 300mm filler; Chromosorb P 30-6
0 mesh Column cooling rate: 2.0 ° C / Hr 2) Melt flow rate Based on ASTM D-1238.

3) Ethylene content, 1-butene content The content was measured using a 13C-NMR spectrometer using JEOL GSX-270.

4) Weight average molecular weight and molecular weight distribution P. It was measured by the C (gel permeation chromatography) method. Sensyu Science SSC-7
Using o-dichlorobenzene as solvent, 135
C. was performed. The column used was Shodex UT80.
7, 806M. The calibration curve is a standard sample having a weight average molecular weight of 950, 2900, 10,000, 50,000 and 49.8.
Were prepared using 10,000, 2.7, and 4.9 million polystyrene.

5) Flexural modulus According to ASTM D-790.

6) Tensile elongation Measured at a speed of 200 mm / min according to JIS K6301.

7) Transparency (haze value) A test piece having a thickness of 1 mm was prepared by injection molding, and was subjected to JIS.
K6714. Further, the decrease in transparency due to the bleed was evaluated by a haze value one week after molding.

8) Vicat softening temperature Measured under a load of 250 g according to JIS K7206.

9) Melt viscosity Using a Capillograph 1B manufactured by Toyo Seiki Co., Ltd., 230
The melt viscosity at 150 ° C. and a shear rate of 150 s−1 was measured.

10) Melt tension The melt tension at an orifice (L = 20 mm, D = 2 mm), 190 ° C., an extrusion speed of 5 mm / min, and a winding speed of 10 m / min was measured using a Capillograph 1B manufactured by Toyo Seiki Co., Ltd. .

Example 1 (Preliminary polymerization) A 1-liter glass autoclave reactor equipped with a stirrer was sufficiently replaced with nitrogen gas, and then 400 ml of heptane was charged. Reactor temperature 2
After keeping at 0 ° C., 0.18 mmol of butyl acetate, 22.7 mmol of ethyl iodide, 18.5 mmol of diethylaluminum chloride, and 22.7 mmol of titanium trichloride (manufactured by Marubeni Solvay Chemical Co., Ltd.) were added, and then propylene was added to 1 g of titanium trichloride. The reactor was continuously introduced into the reactor at a rate of 3 g per 30 minutes. The temperature during this period was kept at 20 ° C. After stopping the supply of propylene, the inside of the reactor was sufficiently replaced with nitrogen gas, and the obtained titanium-containing polypropylene was washed four times with purified heptane. As a result of the analysis, 2.9 g of propylene was polymerized per 1 g of titanium trichloride.

(Main Polymerization) In a 2-liter autoclave substituted with N ₂ , 430 g of liquid propylene, 0.70 mmol of diethylaluminum chloride, 0.07 mmol of butyl acetate, 0.07 mmol of dicyclopentyldimethoxysilane, and hydrogen were charged in a gas phase. Concentration of 3mol%
, And the internal temperature of the autoclave was raised to 45 ° C. 0.087 mmol of titanium-containing polypropylene obtained by pre-polymerization was added as titanium trichloride,
For 30 minutes to polymerize propylene (Step 1). Next, 20 g of 1-butene was charged so that the supply amount per hour was constant until the completion of the polymerization, and ethylene was adjusted to 3 mol% while confirming the concentration of ethylene gas in the gas phase by gas chromatography. The mixture was supplied and polymerization was performed for 60 minutes (step 2). Then, the ethylene gas concentration in the gas phase was supplied so as to be maintained at 9 mol%, and polymerization was carried out for 60 minutes (step 3).

The unreacted monomer was purged to obtain a polymer. The obtained polymer was dried at 70 ° C. for 1 hour. Next, after adding and mixing an antioxidant, a heat stabilizer and a chlorine scavenger, the mixture was extruded at 250 ° C. using a 20 mmφ extruder to obtain pellets, which were subjected to physical property measurement. The results are shown in Tables 1 and 2. FIG. 1 shows an elution curve obtained by a temperature separation method.

Example 2 In step 1 of the main polymerization in Example 1, the polymerization time of propylene was set to 60 minutes, and in step 3, ethylene was supplied so that the concentration of ethylene gas in the gas phase was maintained at 13 mol%. The same operation as in Example 1 was performed except for the above. Table 1 shows the results
And Table 2. FIG. 2 shows an elution curve obtained by the temperature-elution fractionation method.

Example 3 The same operation as in Example 1 was carried out except that the polymerization time of propylene in Step 1 of the main polymerization in Example 1 was changed to 90 minutes. The results are shown in Tables 1 and 2.

Example 4 In the main polymerization of Example 1, the charge amount of 1-butene was 50 g.
The same operation as in Example 1 was performed, except that The results are shown in Tables 1 and 2.

Example 5 In the main polymerization of Example 1, the charged amount of 1-butene was 10 g.
The same operation as in Example 1 was performed, except that The results are shown in Tables 1 and 2.

Examples 6 and 7 In step 1 of the main polymerization of Example 1, hydrogen was added so that the concentration in the gas phase became 1.5 mol% (Example 6) and 10 mol% (Example 7). The same operation as in Example 1 was performed except for the above. The results are shown in Tables 1 and 2.

Example 8 The same operation as in Example 1 was carried out except that methyl methacrylate was used instead of butyl acetate in the main polymerization of Example 1. The results are shown in Tables 1 and 2.

Example 9 The same operation as in Example 1 was performed, except that t-butylethyldimethoxysilane was used in place of dicyclopentyldimethoxysilane in the main polymerization of Example 1. The results are shown in Tables 1 and 2.

Comparative Examples 1 and 2 The procedure of Example 1 was repeated except that the amount of 1-butene was changed to 5 g (Comparative Example 1) and that 1-butene was not inserted (Comparative Example 2). The same operation as in Example 1 was performed. The results are shown in Tables 1 and 2.

Comparative Examples 3 and 4 The same procedures as in Example 1 were carried out except that dicyclopentyldimethoxysilane was not used (Comparative Example 3) and butyl acetate was not used (Comparative Example 4) in the main polymerization of Example 1. The same operation was performed. The results are shown in Tables 1 and 2.

Comparative Example 5 The procedure of Example 1 was repeated except that the polymerization time of propylene was 60 minutes in Step 1 of the main polymerization in Example 1, the polymerization in Step 2 was not performed, and the polymerization time in Step 3 was 120 minutes. The same operation as described above was performed. The results are shown in Tables 1 and 2.

Comparative Examples 6 and 7 In the main polymerization of Example 1, polymerization was carried out without using hydrogen.
In addition to the additive described in Example 1 to the obtained copolymer,
1,3-bis- (t-butylperoxyisopropyl)
-0.05% by weight of benzene (Comparative Example 6), 0.15w
Example 1 except that granulation was performed by adding t% (Comparative Example 7).
The same operation as described above was performed. The results are shown in Tables 1 and 2.

Comparative Example 8 The same operation as in Example 1 was carried out except that hydrogen was added in Step 1 of the main polymerization in Example 1 so that the concentration in the gas phase became 16 mol%. The results are shown in Tables 1 and 2.

[0083]

[Table 1]

[0084]

[Table 2]

[Brief description of the drawings]

FIG. 1 is an elution curve of a propylene-based resin of Example 1 obtained by a temperature rising elution fractionation method.

FIG. 2 is an elution curve of the propylene-based resin of Example 2 obtained by a temperature-rise elution fractionation method.

Claims (2)

[Claims] (1) a melt flow rate of 0.01 to 10 g /
10 minutes, the content of ethylene unit is 10 to 30 mol%, the content of 1-butene unit is 1 to 20 mol%, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) and Number average molecular weight (M
n) the molecular weight distribution (Mw / Mn) represented by the ratio of 6-1
6. In the elution curve, the horizontal axis of which is the elution temperature (° C.) and the vertical axis is the integrated weight ratio of the eluting components, the elution component (component A) at less than 20 ° C. Quantity 2
0 to 50% by weight, the amount of the eluted component (component B) at 20 ° C. or more and less than 100 ° C. is 25 to 75% by weight, the amount of the eluted component (component C) at 100 ° C. or more is 5 to 50% by weight, Ingredients and B
The total of the component and the component C is 100% by weight, the weight ratio of the component B and the component A (B / A) is 0.8 or more, and the peak top temperature of the component C is 120 ° C. or more. Propylene resin. 2. The amount of the eluted component at 120 ° C. or higher in the C component, which is separated by the elevated temperature elution fractionation method according to claim 1, is 5%.
The propylene-based resin according to claim 1, wherein the content is 0% by weight or more.