JPH11240987A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in flexibility and heat resistance, capable of suppressing the bleeding of low-molecular weight substances after molding and processing and excellent in transparency. SOLUTION: This resin composition is obtained by compounding a low- crystalline polypropylene having 1-20 g/10 min melt flow rate and 5-35 wt.% amount of an eluted component (component A) at a temperature below 20 deg.C, 10-40 wt.% amount of an eluted component (component B) at >=20C and <100 deg.C and 40-80 wt.% amount of an eluted component (component C) at >=100 deg.C in which the sum total of the components A and B is 100 wt.% at >=0.6 weight ratio (B/A) of the components B to A and the peak top temperature in the component C is >=115 deg.C in an elution curve determined by a temperature rising elution fractionating method and representing the abcsissa axis by the elution temperature ( deg.C) and the ordinate axis by the cumulative weight ratio (wt.%) of the eluted component with a copolymer containing 5-25 wt.% of an aromatic vinyl compound unit and 95-75 wt.% of at least a partially hydrogenated conjugated diene compound unit.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which is excellent in flexibility and heat resistance, suppresses bleeding of a low molecular weight product after molding, and is excellent in transparency.

[0002]

2. Description of the Related Art Polypropylene is widely used for industrial parts, sheets, films and the like because of its excellent moldability, rigidity and heat resistance. However, conventionally used so-called isotactic polypropylene having high crystallinity is excellent in rigidity and heat resistance, but has a disadvantage that it is inferior in flexibility and transparency.

As a method for improving the flexibility of polypropylene, ethylene-propylene copolymer rubber, ethylene-butene copolymer rubber, low-density polyethylene, linear low-density polyethylene, etc. are added to crystalline polypropylene as a modifier. The method of doing so is generally known.

However, in the composition containing the above-mentioned modifier, transparency is remarkably impaired, and it is difficult to simultaneously satisfy flexibility and transparency.

On the other hand, as the improvement by the polymerization method, a method of randomly copolymerizing propylene and another α-olefin, a method of randomly copolymerizing propylene and ethylene after propylene homopolymerization to obtain a block copolymer, and There is known a method of improving transparency and flexibility by a method of reducing regularity and the like.

However, in the case of a random copolymer, transparency and flexibility are improved, but the melting point is remarkably lowered and heat resistance is impaired. In this case, flexibility and heat resistance were excellent, but it was difficult to satisfy transparency. Further, as a method for lowering the stereoregularity, JP-A-59-122506 proposes a polypropylene having a relatively high melting point and a low stereoregularity having flexibility. The method still leaves room for improvement in the balance between flexibility and heat resistance.

Further, the above-mentioned polymer having improved flexibility has a problem that a low-molecular-weight product is uniformly present in the polymer and the low-molecular-weight product bleeds after molding.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a resin composition having excellent transparency, excellent balance between flexibility and heat resistance, and suppressing bleeding of a low molecular weight product after molding. To provide things.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, low-crystalline polypropylene having a specific molecular weight distribution and crystallinity distribution has been found to be flexible and transparent. Excellent in heat resistance and heat resistance. By blending it with a copolymer of a specific aromatic vinyl compound and a hydrogenated aliphatic conjugated diene compound, the transparency is maintained or further improved, and molding processing is performed. The present inventors have found that a resin composition excellent in balance between flexibility and heat resistance in which bleeding of a low-molecular-weight substance later is suppressed can be obtained, and the present invention has been completed.

That is, the present invention relates to (1) a propylene homopolymer or a copolymer of propylene and an α-olefin having a content of α-olefin units other than propylene of 5 mol% or less; Melt flow rate is 0.1 ~
20 g / 10 min. (II) In the elution curve obtained by the elevated temperature elution fractionation method, the horizontal axis represents the elution temperature (° C.), and the vertical axis represents the integrated weight ratio (% by weight) of the eluted components. 5 to 35% by weight of eluted component (component A) below 20 ° C, 20 ° C
The amount of the eluted component (component B) at a temperature of 100 ° C. or less is 10 to
40% by weight, eluted component (C component) at 100 ° C or higher is 4
0 to 80% by weight, the total of the A component, the B component and the C component is 100% by weight, the weight ratio (B / A) of the B component and the A component is 0.6 or more, and the peak in the C component 100 parts by weight of a low-crystalline polypropylene characterized in that the top temperature is 115 ° C. or higher. (2) 5 to 25% by weight of an aromatic vinyl compound unit and an aliphatic conjugated diene compound unit at least partially hydrogenated From 100 to 95% by weight
A resin composition comprising parts by weight.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The (1) low-crystalline polypropylene in the present invention is a polypropylene homopolymer or a copolymer of propylene and an α-olefin having an α-olefin other than propylene of 5 mol% or less (hereinafter referred to as a copolymer). , Propylene-α-olefin copolymer).

In the present invention, α-olefins other than propylene include, for example, ethylene, 1-butene,
-Pentene, 1-hexene, 1-heptene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene and the like. When the α-olefin content in the propylene-α-olefin copolymer exceeds 5 mol%, heat resistance is impaired due to a decrease in melting point, which is not preferable.

In the low crystallinity polypropylene of the present invention, if the melt flow rate is less than 0.1, the molding processability is difficult, and if it exceeds 20, the molding processability in extrusion molding is undesirably reduced.

The melt flow rate of the low crystalline polypropylene of the present invention is approximately 200,000 when converted to a weight average molecular weight by gel permeation chromatography.
The range is one million.

In the low-crystalline polypropylene of the present invention, the amount of the component of 10,000 or less in the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 3% by weight or less. It is preferable for suppressing stickiness, and has a weight average molecular weight (Mw).
And the molecular weight distribution (M
(w / Mn) is preferably 4 to 15 in consideration of moldability and mechanical properties of the obtained molded body.

In the present invention, the elevated temperature elution fractionation method is, for example, Journal of Applied Poly.
mer Science; Applied Polym
erSymposium 45, 1-24 (1990)
The method is described in detail in FIG. First, a high-temperature polymer solution is introduced into a packed column using diatomaceous earth as a filler, and the temperature of the column is gradually decreased to crystallize the filler surface in order from the component with the higher melting point, and then the column temperature is gradually increased. In this method, the components are eluted in order from the component having the lowest melting point to separate the eluted polymer components. 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 the conditions of 30 mm × 300 mm.

20 ° C. of the low crystalline polypropylene of the present invention
The eluted component (A component) with less than the above is a component necessary especially for developing flexibility. That is, if the amount of the component A is less than 5% by weight, flexibility is impaired, and if it exceeds 35% by weight, sufficient heat resistance cannot be obtained, which is not preferable.
In order to exhibit more excellent flexibility and heat resistance, the amount of the component A is particularly preferably in the range of 10 to 30% by weight.

20 ° C. of the low crystalline polypropylene of the present invention
The eluted component (component B) at a temperature of less than 100 ° C. is a component necessary to express a good balance between transparency, flexibility and heat resistance. That is, the amount of the component B is 10% by weight.
If the amount is less than 40%, good transparency and flexibility cannot be achieved when a molded article is obtained. If the amount exceeds 40% by weight, heat resistance is insufficient. In order to develop a better balance between transparency, flexibility and heat resistance, the amount of the B component is particularly preferably from 10 to
Preferably it is in the range of 30% by weight.

The eluting 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 40% by weight or the peak top temperature of the C component is less than 115 ° C., the heat resistance of a molded article is impaired, and the amount of the C component exceeds 80% by weight. In such a case, it is not preferable because flexibility is impaired. In consideration of flexibility and heat resistance, the amount of the component C is preferably more than 50% by weight and 70% by weight or less. Further, in order to obtain more excellent heat resistance, the component C is preferably a highly crystalline polypropylene component having 60% by weight or more of an eluted component of 115 ° C. or more and a peak top temperature of 120 ° C. or more.

The weight ratio (B / A) of the component B to the component A of the low crystalline polypropylene of the present invention is 0.6 or more;
Preferably it is 0.7 or more. When the weight ratio (B / A) of the component B and the component A (B / A) is less than 0.6, 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 low crystalline polypropylene of the present invention has a melting point of 150 as measured by differential scanning calorimetry (DSC).
It is preferable that the heat of fusion be 100 ° C. or higher and 100 J / g or lower. When the melting point is lower than 150 ° C., sufficient heat resistance cannot be obtained, and when the heat of fusion exceeds 100 J / g, flexibility is impaired, which is not preferable.

The method for producing the low-crystalline polypropylene of the present invention is 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 [i], [ii], [iii] [i] titanium compound [ii] general formula R1nAlX3-n (where R1 is a saturated hydrocarbon group having 1 to 10 carbon atoms, and X is a halogen atom) , N is an integer of 0 to 3) [iii] Formula (1) R2n / 2Al (OR3) 3-n / 2 (where R2 and R3 are the same or different and have 1 to 1 carbon atoms) 10 saturated hydrocarbon groups, n is an integer of 1 to 4) or a general formula (m)

[0024]

Embedded image

(Where R4 is an alkyl group, an aryl group or a halogen atom, R5, R6 and R7 are a hydrogen atom, an alkyl group or an aryl group, and n is 0 <n <
3. In the presence of the organoalkoxyaluminum compound represented by the formula (1), firstly, homopolymerization of propylene or copolymerization of propylene with another α-olefin is carried out in the absence or presence of hydrogen in the first step. As a step, in the presence of the components [i], [ii], and [iii], an electron donor compound [iv] is further added to carry out a second-stage polymerization. This is a method for increasing the hydrogen concentration.

As the titanium compound [i], a titanium compound known to be used for polymerization of an olefin is used without any limitation. 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 and 56
-136806, 57-34103, 58-870
6, 58-83006, 58-138708, 5
8-183709, 59-206408, 59-2
19311, 60-81208, 60-8120
9, 60-186508, 60-192708, 61-211309, 61-271304, 62-
15209, 62-11706, 62-7270
2, the methods shown in 62-104810 and the like are adopted.

More specifically, for example, a method of co-grinding titanium tetrachloride with a magnesium compound such as magnesium chloride, a method in which a titanium halide is mixed with a magnesium compound in the presence of an electron donor such as alcohol, ether, ester, ketone or aldehyde. And a method of contacting a titanium halide, a magnesium compound and an electron donor in a solvent. Examples of the titanium trichloride compound include known α, β, γ, and δ-titanium trichloride. Methods for preparing these titanium trichloride compounds are described, for example, in JP-A-47-34478,
126590, 50-114394, 50-938
88, 50-123091, 50-74594, 50-104191, 50-98489, 51-1
36625, 52-30888, 52-35283
Etc. are adopted.

Next, as the organoaluminum compound [ii], a compound known to be used for the polymerization of olefin is employed without any limitation. For example, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-i-
Butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, trialkyl aluminums such as tri-n-decyl aluminum or diethyl aluminum monochloride, diethyl aluminum monohalides such as diethyl aluminum bromide or methyl aluminum sesquichloride, Examples thereof include alkyl aluminum halides such as ethyl aluminum sesquichloride and ethyl aluminum dichloride. The organic alkoxyaluminum compound [iii] is a reaction product of an alkylaluminum or an alkylaluminum halide and an alcohol, and the organic alkoxyaluminum compound represented by the general formula (l) or (m) is employed without any limitation. You.

Examples of the organic alkoxyaluminum compound represented by the general formula (l) include dimethylaluminum methoxide, dimethylaluminum ethoxide, dimethylaluminum isopropoxide, diethylaluminum methoxide, diethylaluminum ethoxide,
Examples thereof include diethylaluminum-n-butoxide, methylaluminum sesquimethoxide, methylaluminum sesquiethoxide, ethylaluminum sesquiethoxide, ethylaluminum diethoxide, diisobutylaluminum ethoxide, and ethylaluminum chloride monoethoxide.

The organic alkoxyaluminum compound represented by the general formula (m) includes, for example, dimethylaluminum phenoxide, dimethylaluminum (2-
Methylphenoxide), dimethylaluminum (2,4
-Dimethylphenoxide), dimethylaluminum (2,6-dimethylphenoxide), dimethylaluminum (2,4,6-trimethylphenoxide), dimethylaluminum (2,6-diisopropylphenoxide), dimethylaluminum (2,6-di-t) -Butylphenoxide), dimethylaluminum (2,6-diphenylphenoxide), diethylaluminum phenoxide, diethylaluminum (2-methylphenoxide), diethylaluminum (2,4-dimethylphenoxide), diethylaluminum (2,6-dimethylphenoxide) , Diethylaluminum (2,4,6-trimethylphenoxide), diethylaluminum (2,4,6-trimethylphenoxide)
6-diisopropylphenoxide), diethyl aluminum (2-isobutyl phenoxide), diethyl aluminum (2-t-butyl phenoxide), diethyl aluminum (2,6-di-t-butyl phenoxide), diethyl aluminum (2,6-di- t-butyl-4-methylphenoxide), diethylaluminum (2,6-
Diphenylphenoxide) and the like.

Further, as the electron donor compound [iV], a compound known to be used for improving the stereoregularity of an olefin is employed without any limitation. For example, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, isopropyl alcohol,
Alcohols such as isoamyl alcohol, phenol,
Phenols such as cresol, cumylphenol, xylenol and naphthol; ketones such as acetone, methyl ethyl ketone, acetophenone and benzophenone; aldehydes such as acetaldehyde, propionaldehyde and benzaldehyde; methyl formate, methyl acetate, ethyl acetate, butyl acetate and acetic acid Organic acids such as vinyl, methyl propionate, ethyl propionate, ethyl valerate, ethyl stearate, ethyl acrylate, methyl methacrylate, ethyl benzoate, methyl toluate, methyl anisate, ethyl phthalate, methyl carbonate, butyrolactone Esters, methyl ether, ethyl ether, isopropyl ether, isoamyl ether, tetrahydrofuran, anisole, ethers such as diethylene glycol dimethyl ether, vinegar Amide, amide benzoate, acid amides such as maleic acid amide, methylamine, ethylamine, piperidine, pyridine, amines such as aniline,
Acetonitrile, nitriles such as benzonitrile, dimethyldimethoxysilane, diethyldimethoxysilane, ethyl silicate, divinyldimethoxysilane, diallyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, methyltriethoxysilane,
Ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, isopropyltriethoxysilane, cyclohexylmethyldimethoxysilane, di-t-butyldimethoxysilane, t-butylethyldimethoxysilane, di-t-amyldimethoxysilane , Dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexyl Examples of organosilicon compounds such as isobutyldimethoxysilane It is possible. Further, a plurality of these electron donor compounds can be used at the same time.

The titanium compound [i] used in the present invention,
The combination of the organoaluminum compound [ii], the organoalkoxyaluminum compound [iii] and the electron donor [iv] is as follows: (1) supported titanium compound-trialkylaluminum-organoalkoxyaluminum compound-electron donor (2) trichloride Titanium compound-diethylaluminum monohalide-organoalkoxyaluminum compound-electron donor (3) titanium trichloride compound-trialkylaluminum-organoalkoxyaluminum compound-electron donor; and (4) supported titanium compound-titanium trichloride compound The combination of -trialkylaluminum-organoalkoxyaluminum compound-electron donor is particularly preferred in order to satisfy the constitution of the low crystalline polypropylene 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-mentioned components, the pre-polymerization of propylene in the presence of the same components is carried out so that the particle properties of the obtained polymer powder are high fluidity. It is preferable because it can be performed.

In the prepolymerization, the above [i] and [i
i), and if necessary, in addition to the system using (iii), an iodine compound represented by the following general formula for the purpose of reducing the amount of low molecular weight components of the low stereoregularity polypropylene obtained by the main polymerization. It is also possible to add [v].

[V] Iodine compound General formula RI (where R is an iodine atom or an alkyl group having 1 to 7 carbon atoms or a phenyl group.) The amount of each of these components used in the prepolymerization depends on the amount of the catalyst. Type,
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 generally preferred range is as follows.

That is, the ratio of the organoaluminum compound [ii] used in the prepolymerization is 0.1 to 100, preferably 0.1 to 20 in terms of Al / Ti (molar ratio) with respect to the titanium compound [i]. And the organoalkoxyaluminum compound [iii] used as necessary may be 0.01 to [iii] / Ti (molar ratio) with respect to the titanium compound [i].
-100, preferably in the range of 0.01-10,
The use ratio of the electron donor compound [iv] is 0.01 to 1 in terms of [iv] / Ti (molar ratio) with respect to the titanium compound [i].
00, preferably in the range of 0.01 to 10, respectively. The proportion of the iodine compound [v] used as required is in the range of 0.1 to 100, preferably 0.5 to 50 in terms of the iodine compound / Ti (molar ratio) with respect to the titanium compound [i]. It is.

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

The prepolymerization amount for polymerizing the α-olefin in the presence of the catalyst component varies depending on the prepolymerization 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 other α-olefins, for example, ethylene, 1-butene, 1-pentene, 1-hexene, and so on as long as the physical properties of the polymerization powder are not adversely affected. 4-methylpentene-1 or the like may be mixed with propylene. 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 such as hexane, heptane, cyclohexane, benzene, toluene or an aromatic hydrocarbon alone or a mixed solvent thereof is used. Can be used.

The prepolymerization temperature is preferably in the range of -20 to 100 ° C, particularly preferably 0 to 60 ° C. The pre-polymerization time may be appropriately determined according to the pre-polymerization temperature and the amount of polymerization in the pre-polymerization, and the pressure in the pre-polymerization is not limited, but in the case of slurry polymerization, generally, the pressure is from atmospheric pressure to 5 kg / c.
It is about m2G. The prepolymerization may be performed in any of batch, semi-batch, and continuous methods.

Following the preliminary polymerization, the main polymerization is carried out. In the main polymerization of the low crystalline polypropylene of the present invention, it is preferable to perform the main polymerization by multistage polymerization of two or more stages under different conditions in order to satisfy a specific molecular weight distribution and crystallinity distribution.

The amount of the organoaluminum compound [ii] used in the first stage of the main polymerization is Al / Ti (molar ratio) based on titanium atoms in the titanium compound-containing prepolymer.
In the range of 1 to 1000, preferably 2 to 500. Further, an organic alkoxy aluminum compound (iii)
Is used in an amount of 0.01 to 10 mol, preferably 0.1 to 10 mol, per 1 mol of the organoaluminum compound [ii].
Is a mole. Further, the electron donor [iv] used in the second stage of the main polymerization is 0.001 to 10 mol based on 1 mol of the organoaluminum compound [ii] used in the first stage,
Preferably it is in the range of 0.01 to 1 mol.

In the first stage polymerization, the titanium compound-containing prepolymer obtained by the prepolymerization and the above-mentioned [ii], [ii]
The order of addition of i) to the polymerization system is not particularly limited, and those in which the respective components are mixed in advance can also be used.

The polymerization of propylene in the first step is carried out in the absence or presence of hydrogen by supplying propylene alone or a mixture of propylene and another α-olefin within a range satisfying the requirements of the present invention. Subsequently, the second stage polymerization may be carried out by adding the electron donor compound [iv] and hydrogen.

In the method for producing a low-crystalline polypropylene of the present invention, it is important to carry out the polymerization in the first stage and the second stage under different hydrogen concentrations. That is, in the second stage polymerization, by increasing the hydrogen concentration more than in the first stage, a component having a lower molecular weight than the polymer polymerized in the first stage is polymerized. In addition, the electron donor added in the second stage can reduce the crystallinity of the polymer polymerized in the second stage to the first.
From the above effects, a low stereoregularity polypropylene that satisfies the specific molecular weight distribution and crystallinity distribution of the present invention can be obtained.

In the present invention, when the first stage polymerization is carried out in the presence of hydrogen, the weight of the polymer to be polymerized in the first stage is reduced in order to reduce the fluidity and low molecular weight components of the obtained low crystalline polypropylene. It is preferable to set the hydrogen concentration so that the average molecular weight is 700,000 or more.

Illustrative typical conditions for the propylene polymerization in the first and second stages are as follows.
Further, it is preferable to adopt from a range of 20 to 70 ° C. Further, the polymerization may be any method such as slurry polymerization using propylene itself as a solvent, gas phase polymerization, solution polymerization and the like. Considering the simplicity of the process, the reaction rate, and the particle properties of the produced polymer powder, 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.

After completion of the main polymerization, the monomer is evaporated from the polymerization system to obtain the low crystalline polypropylene of the present invention. This low-crystalline polypropylene can be subjected to known washing or countercurrent washing with a hydrocarbon having 7 or less carbon atoms.

The method for producing low-crystallinity propylene of the present invention is not limited to the above-mentioned polymerization method, but may be obtained by blending a high-crystalline polypropylene and a low-crystalline polypropylene obtained by separate polymerization as long as the requirements of the present invention are satisfied. However, in order to obtain good transparency, it is a preferable embodiment to produce by a polymerization method.

The low-crystalline polypropylene of the present invention is prepared by adding commercially available additives such as an antioxidant, a heat stabilizer, a chlorine scavenger, a light stabilizer, a lubricant, an antiblocking agent, a nucleating agent and an antistatic agent. After mixing, pellets may be used with an extruder. Further, a known organic peroxide may be added in addition to the above additives to adjust the molecular weight within a range satisfying the requirements of the present invention.

It is preferable to add a nucleating agent to the low-crystalline polypropylene of the present invention because transparency can be improved without significantly impairing the flexibility of the low-crystalline polypropylene. As the nucleating agent to be used, a known nucleating agent used for the purpose of improving rigidity, heat resistance, and transparency of polypropylene can be used without any limitation.

The crystal nucleating agent in the present invention is important in the effect of making the spherulite of the low-crystalline polypropylene fine. The nucleating agent used in the present invention preferably raises the crystallization temperature of the low-crystalline polypropylene of the present invention by 5 ° C or more, and more preferably raises the crystallization temperature by 10 ° C or more.

Examples of the crystal nucleating agent suitably used in the present invention include organic phosphorus compounds, dibenzylidene sorbitol compounds, metal benzoates, rosin compounds and the like. Specific examples of these organic crystal nucleating agents include organic phosphorus compounds such as sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate and sodium-2 , 2'-
Ethylidene-bis (4,6-di-t-butylphenyl)
Phosphate, lithium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidene-bis (4,6-di-t
-Butylphenyl) phosphate, calcium-bis-
[2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis-
[2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris-
[2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], bis (2,4,8,10-
Tetra-t-butyl-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphin-6-oxide) aluminum hydroxide, 2,2′-methylenebis (4,6-di-t) -Butylphenyl) phosphate basic aluminum salt and the like.

Examples of the dibenzylidene sorbitol compounds include 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, and di (p-ethylbenzylidene) sorbitol , Di (dimethylbenzylidene) sorbitol,
Mono (p-methylbenzylidene) sorbitol, 1.3
-P-chlorobenzylidene 2.4-p-methylsorbitol and the like.

Examples of the metal benzoate include aluminum hydroxy-pt-butyl benzoate and sodium benzoate.

Examples of the rosin compound include dehydroabietic acid, sodium dehydroabietic acid, potassium dehydroabietic acid, magnesium dehydroabietic acid, aluminum dehydroabietic acid, dihydroabietic acid, sodium dihydroabietic acid, potassium dihydroabietic acid, Examples thereof include magnesium dihydroabietic acid and aluminum dihydroabietic acid.

As the crystal nucleating agent suitably used in the present invention, a polymer crystal nucleating agent can be used in addition to the above-mentioned organic crystal nucleating agent. For example, poly-3-methyl-1-butene, poly-
3-methyl-1-pentene, poly-4-methyl-1-pentene, poly-4,4-dimethylpentene, poly-4,
Examples thereof include 4-dimethylhexene, polycyclopentene, polyvinylcyclohexane, polyallyltrimethylsilane, and polyvinylpyridine. Among them, poly-3-methyl-1-butene and polyvinylcyclohexane are particularly preferable for improving impact resistance.

The method of adding the high molecular weight nucleating agent in the present invention is not particularly limited.
A method in which these monomers are polymerized as an olefin or in place of an α-olefin, or a method in which these monomers are separately polymerized and added separately, are generally used.

The compounding amount of the crystal nucleating agent used in the present invention is 1 part by weight or less based on 100 parts by weight of the low crystalline polypropylene. If the amount exceeds 1 part by weight, the effect of improving the physical properties corresponding to the compounding amount is not sufficiently exhibited, which is not preferable. Further, as the nucleating agent, one kind or / and a plurality of nucleating agents may be used simultaneously.

In the present invention, the content of the aromatic vinyl compound unit is 5 to 25 in the low crystalline polypropylene.
Incorporation of a copolymer having a content of 95 to 75% by weight of an aliphatic conjugated diene compound unit which is at least partially hydrogenated, particularly while maintaining the transparency of the low-crystalline polypropylene, Excellent flexibility and heat resistance,
It is important to obtain a resin composition having an excellent effect of suppressing bleeding of a low molecular weight product after molding as described later.

Incidentally, JP-A-3-168233 discloses that
A thermoplastic elastomer composition in which a soft elastomer is blended with a soft polypropylene is described. However, in the above-mentioned literature, not only the transparent resin is not conscious at all as the soft polypropylene to be added, but also the addition of the soft elastomer to the resin has the problem of weather resistance, low temperature impact resistance, injection moldability. Is to improve.

On the other hand, the present invention is directed to a transparent resin made of a low-crystalline polypropylene, and the transparency is increased by adding a specific amount of a specific copolymer containing an aromatic vinyl compound to the transparent resin. While maintaining, flexibility, excellent heat resistance, or to obtain a resin composition excellent in the effect of suppressing the bleeding of low molecular weight material after molding, the technical idea of the present invention, and a configuration based on this, The effect was first found by the present invention.

The content of the aromatic vinyl compound unit in the polymer is preferably 8 to 20% by weight, more preferably 8 to 18% by weight, whereas the content of the aliphatic conjugated diene compound unit is 8 to 20% by weight. Preferably, it is 92 to 80% by weight, more preferably 92 to 82% by weight. When the content of the aromatic vinyl compound unit is less than 5% by weight, the composition of the present invention has insufficient heat resistance. On the other hand, when the content of the aromatic vinyl compound unit exceeds 25% by weight, not only the transparency is lowered but also the effect of improving the flexibility is lowered, which is not preferable.

It is necessary that at least a part of the double bond part of the conjugated diene part of the present polymer is hydrogenated. Further, if the hydrogenation is not sufficient, the compatibility with the low-crystalline polypropylene component of the resin composition of the present invention is poor and the transparency is impaired, which is not preferable. In consideration of transparency, it is preferable that 80% or more be hydrogenated and saturated.

In the resin composition of the present invention, based on 100 parts by weight of the low-crystalline polypropylene component (1),
The copolymer component of (2) is 1 to 100 parts by weight, preferably 3 to 100 parts by weight.
８０80 parts by weight. If the copolymer component (2) is less than 1 part by weight, the effect of improving transparency and flexibility is not sufficient, and if it exceeds 100 parts by weight, heat resistance is undesirably reduced.

The vinyl aromatic compounds include styrene, o-methylstyrene, p-methylstyrene and p-methylstyrene.
Examples include at least one kind of alkyl styrene such as tertiary butyl styrene, paramethoxy styrene, vinyl naphthalene and the like, and styrene is particularly preferable. Examples of the conjugated diene compound include butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, and 3,4.
One or more of -dimethyl-1,3-hexadiene, 4,5-dimethyl-1,3-octadiene and the like can be mentioned, and butadiene and isoprene are particularly preferable.

Further, in the resin composition of the present invention,
The copolymerization form of the aromatic vinyl compound of the copolymer component (2) and the hydrogenated conjugated diene is required to suppress bleeding of a low-molecular-weight material after molding and maintain transparency. The copolymers shown are preferred.

That is, it has a structure of any one of (aba) and (ab) (where a is a polymer block based on an aromatic vinyl compound, and b is a hydrogenated aliphatic conjugate). It is preferable to use a block copolymer which is a polymer block based on a diene compound) or a mixture thereof (hereinafter, (a-ba) is a triblock type,
(Ab) is abbreviated as diblock type).

In order to obtain particularly excellent transparency of the resin composition of the present invention, the copolymer form of the aromatic vinyl compound of the copolymer component (2) and the hydrogenated conjugated diene must be as follows. Is preferred.

That is, (ac-a), (ac), (a)
-C-d) (where a is a polymer block based on an aromatic vinyl compound, c is a random copolymer block of a hydrogenated aliphatic conjugated diene compound and an aromatic vinyl compound) , D is preferably a block copolymer of an aromatic vinyl compound and a hydrogenated aliphatic conjugated diene compound in which the aromatic vinyl compound is gradually increased) or a mixture thereof (hereinafter, (ac) -A), (ac) or (ac-)
d) is abbreviated as a random block).

In the present invention, as the copolymer component (2), those having a melt flow rate measured at 230 ° C. under a load of 2.16 kg of 0.1 to 20 g / 10 minutes are preferably used.

The resin composition of the present invention may contain known additives such as an antioxidant, a light stabilizer, an antistatic agent, a lubricant, a copper damage inhibitor and a flame retardant. Further, other resins can be added within the scope of the present invention.

In the present invention, the resin composition used is
It is obtained by mixing and melt-kneading after blending the above raw materials and the like as necessary. The method of melt-kneading is not particularly limited. For example, using a screw extruder, a Banbury mixer, a mixing roll, or the like,
It is good to carry out at a temperature of 300 ° C., preferably 180 to 270 ° C. The melt-kneading can also be performed under a stream of an inert gas such as nitrogen gas. Prior to melt-kneading, a known mixing device such as a tumbler or a Henschel mixer can be used without any limitation.

Further, in the present invention, a molded article may be obtained by mixing the respective components of the above resin composition if necessary, mixing the components, and then directly putting the mixture into a molding machine and molding. It is possible.

[0075]

According to the present invention, the addition of the aromatic vinyl compound-hydrogenated aliphatic conjugated diene compound copolymer makes it clear that the mechanism of the transparency and the improvement effect of suppressing the bleeding of the low molecular weight product after the molding process are clear. This is probably because the compatibility between the low-crystalline polypropylene and the aromatic vinyl compound-hydrogenated aliphatic conjugated diene compound copolymer is good. In particular, in the case of having an (ab-a) or (ab) structure, it is considered that these bleeds are suppressed because they have good compatibility with the low molecular weight atactic component to bleed. Also, (ac-a), (ad), (ac)
-D) in the case of having a structure, it is considered to be finely dispersed in the low-crystalline polypropylene, so that excellent transparency,
It is considered that it can have flexibility and heat resistance.

The resin composition of the present invention has appropriate flexibility, excellent heat resistance, excellent transparency after molding, and is effective in bleeding low molecular weight components after molding. 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, home appliances and electric wire materials, various insulation sheets, covering materials for cords and waterproof sheets, waterproof materials, jointing materials, packaging stretch films, adhesive tapes, masking tapes in the civil engineering and construction materials field. It can be suitably used for films, agricultural sheets, desk mats, sealant films, and the like.

[0077]

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) Elevated Temperature 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 (hereinafter abbreviated as MI) Based on ASTM D-1238.

(3) Flexural modulus According to ASTM D-790.

(4) Transparency (Haze Value) A test piece having a thickness of 1 mm was prepared by injection molding and subjected to JIS.
K6714.

(5) Vigat softening temperature Based on JIS K7206.

Production Example 1 (Preliminary Polymerization) A 1-liter glass autoclave reactor equipped with a stirrer was sufficiently replaced with nitrogen gas, and 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 n-hexane. 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, 1 liter of liquid propylene, 0.70 mmol of diethyl aluminum chloride, ethyl aluminum sesquiethoxide (Et 1.5 Al (OE
t) 1.5) 0.70 mmol was added, and the internal temperature of the autoclave was raised to 70 ° C. The titanium compound-containing polypropylene obtained by the prepolymerization was converted to titanium trichloride by 0.08.
7 mmol was added, and propylene was polymerized at 70 ° C. for 2 hours (first stage). Next, butyl acetate 0.014mmo
1 was added, hydrogen was inserted so that the concentration in the gas phase became 2 mol%, and polymerization was performed for 1 hour (second stage).

Unreacted monomers were purged to obtain a polymer. The obtained polymer was dried under reduced pressure 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 30 mmφ extruder to form a pellet, which was subjected to physical property measurement (granulation step). The results are shown in Table 1. FIG. 1 shows an elution curve obtained by a temperature separation method.

Production Example 2 The same operation as in Production Example 1 was carried out except that the addition amount of ethyl aluminum sesquiethoxide was changed to 0.35 in the main polymerization of Production Example 1. The results are shown in Table 1.

Production Example 3 In the second stage of the main polymerization of Production Example 1, the polymerization time was set at 40
The same operation as in Production Example 1 was performed except that the amount was changed to minutes. The results are shown in Table 1.

Production Example 4 The same operation as in Production Example 1 was carried out except that the amount of butyl acetate used in the second stage of the main polymerization was changed to 0.14 mmol. The results are shown in Table 1.

Production Examples 5 and 6 The amount of butyl acetate used in the second stage of the main polymerization in Production Example 1 was 0.14 mmol, and 1,3-bis (t-
Butyl peroxyisopropyl) benzene at 0.006
The same operation as in Production Example 1 was performed except that the weight% (Production Example 4) and 0.01% by weight were used. The results are shown in Table 1.

Production Example 7 In the main polymerization of Production Example 1, the polymerization time of the first stage was 90
And the amount of butyl acetate used in the second stage is 0.14
The same operation as in Production Example 1 was performed except that the amount was changed to mmol.
The results are shown in Table 1.

Production Example 8 In the main polymerization of Production Example 1, the first stage polymerization was carried out at a hydrogen concentration of 0.2 mol%, and the second stage polymerization was carried out at a hydrogen concentration of 5 m
The same operation as in Production Example 1 was performed, except that ol% was used. The results are shown in Table 1.

Production Example 9 In the second stage of the main polymerization of Production Example 1, polymerization was carried out without using hydrogen, and 1,3-bis (t-butylperoxyisopropyl) benzene was used in an amount of 0.1% by weight during granulation. The same operation as in Production Example 1 was carried out except for the above. The results are shown in Table 1.

Production Example 10 In the granulation step of Production Example 1, organic crystal nucleating agents 1, 3,
The same operation as in Production Example 1 was performed except that 0.25% by weight of 2,4-di (p-methylbenzylidene) sorbitol was added. The results are shown in Table 1.

Production Example 11 In the prepolymerization of Production Example 1, instead of propylene, 3
The same operation as in Production Example 1 was performed, except that -methyl-1-butene was introduced in an amount of 2 g per 1 g of titanium trichloride. The results are shown in Table 1.

Production Example 12 In the main polymerization of Production Example 1, the same operation as in Production Example 1 was carried out except that the polymerization time in the first stage was 1 hour and the amount of butyl acetate used was 0.0035 mmol. The results are shown in Table 1.

Comparative Production Example 1 In the main polymerization of Production Example 1, the same operation as in Production Example 1 was carried out except that ethylaluminum sesquiethoxide was not used. The results are shown in Table 1.

Comparative Production Example 2 In the main polymerization of Production Example 1, the amount of butyl acetate was changed to 0.0
The same operation as in Production Example 1 was performed except that the amount was changed to 07 mmol. The results are shown in Table 1.

Comparative Production Example 3 In the main polymerization of Production Example 1, the polymerization time of the second stage was 20
And the same operation as in Production Example 1 was performed except that 1,3-bis (t-butylperoxyisopropyl) benzene was used in an amount of 0.005% by weight during granulation. The results are shown in Table 1.

Comparative Production Example 4 In the main polymerization of Production Example 1, the same operation as in Production Example 1 was performed except that the polymerization time in the first stage was 1 hour and the amount of butyl acetate used was 0.0005 mmol. . The results are shown in Table 1.

Comparative Production Example 5 In the main polymerization of Production Example 1, the same operation as in Production Example 1 was carried out except that 0.014 mmol of butyl acetate was used in the polymerization in the first stage. The results are shown in Table 1.

Comparative Production Example 6 In the main polymerization of Production Example 1, ethyl aluminum sesquiethoxide was not used, the polymerization time in the first step was 30 minutes, and the amount of butyl acetate used in the second step was 0.14 mm.
The same operation as in Production Example 1 was performed except that the amount was changed to ol. The results are shown in Table 1.

[0102]

[Table 1]

Example 1 The low-crystalline polypropylene pellets obtained in Production Example 1 were mixed with styrene-hydrogenated isoprene copolymer, Septon 2043, manufactured by Kuraray (trade name: isoprene hydrogenation rate of 90% or more, styrene content 13wt%, triblock, diblock type Melt flow rate 4g / 10
After mixing at a ratio shown in Table 2, the mixture was melted and kneaded with a φ30 mm extruder, and then subjected to a cylinder temperature of 2 with a 15 t injection molding machine.
Under the condition of 30 ° C. and mold temperature of 40 ° C., a bending test piece, 1 mm
A flat plate for measuring haze was prepared. The bleed rating is
The evaluation was made by measuring the external haze value of the plate immediately after molding and the external haze of the plate aged at 40 ° C. for one week. Table 2 shows the results.

Example 2 Using the low-crystalline polypropylene obtained in Production Example 2,
The same operation as in Example 1 was performed except that the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at the ratio shown in Table 2. Table 2 shows the results.

Example 3 Using the low-crystalline polypropylene obtained in Production Example 3,
The same operation as in Example 1 was performed except that the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at the ratio shown in Table 2. Table 2 shows the results.

Example 4 Using the low crystalline polypropylene obtained in Production Example 4,
The same operation as in Example 1 was performed except that the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at the ratio shown in Table 2. Table 2 shows the results.

Example 5 Using the low crystalline polypropylene obtained in Production Example 5,
The same operation as in Example 1 was performed except that the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at the ratio shown in Table 2. Table 2 shows the results.

Example 6 Using the low-crystalline polypropylene obtained in Production Example 6,
The same operation as in Example 1 was performed except that the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at the ratio shown in Table 2. Table 2 shows the results.

Example 7 Using the low-crystalline polypropylene obtained in Production Example 7,
The same operation as in Example 1 was performed except that the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at the ratio shown in Table 2. Table 2 shows the results.

Example 8 Using the low-crystalline polypropylene obtained in Production Example 8,
The same operation as in Example 1 was performed except that the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at the ratio shown in Table 2. Table 2 shows the results.

Example 9 Using the low-crystalline polypropylene obtained in Production Example 9,
The same operation as in Example 1 was performed except that the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at the ratio shown in Table 2. Table 2 shows the results.

Example 10 Example 1 was repeated except that the low-crystalline polypropylene obtained in Production Example 10 was mixed with the styrene-hydrogenated isoprene copolymer used in Example 1 at the ratio shown in Table 2.
The same operation as described above was performed. Table 2 shows the results.

Example 11 Example 1 was repeated except that the low-crystalline polypropylene obtained in Production Example 11 was mixed with the styrene-hydrogenated isoprene copolymer used in Example 1 at a ratio shown in Table 2.
The same operation as described above was performed. Table 2 shows the results.

Example 12 Example 1 was repeated except that the low-crystalline polypropylene obtained in Production Example 12 was mixed with the styrene-hydrogenated isoprene copolymer used in Example 1 at the ratio shown in Table 2.
The same operation as described above was performed. Table 2 shows the results.

Example 13 The low-crystalline polypropylene pellets obtained in Production Example 1 and Clayton G1657 made by Shell, a styrene-hydrogenated butadiene copolymer (trade name: hydrogenation rate of butadiene 90% or more (rubber structure : Ethylene-butylene),
The same operation as in Example 1 was performed except that the styrene content was 13 wt%, the triblock and diblock type melt flow rates were 8 g / 10 min) at the ratios shown in Table 2. Table 2 shows the results.

Example 14 Pellets of the low-crystalline polypropylene obtained in Production Example 1 and Dynalon 1320P made by Nippon Synthetic Rubber, a styrene-hydrogenated butadiene copolymer (trade name: hydrogenation rate of butadiene of 90% or more, Styrene content 10wt%, random block type melt flow rate 3.5g /
Example 1 except that 10 minutes) were mixed at the ratios shown in Table 2.
The same operation as described above was performed. Table 2 shows the results.

Example 15 The low-crystalline polypropylene pellets obtained in Production Example 9 and DYNARON 1320P made by Nippon Synthetic Rubber, a styrene-hydrogenated butadiene copolymer (trade name: hydrogenation rate of butadiene of 90% or more, Styrene content 10wt%, random block type melt flow rate 3.5g /
Example 1 except that 10 minutes) were mixed at the ratios shown in Table 2.
The same operation as described above was performed. Table 2 shows the results.

Example 16 The low-crystalline polypropylene pellets obtained in Production Example 10 and DYNARON 1320P made by Nippon Synthetic Rubber, a styrene-butadiene copolymer (trade name: butadiene, hydrogenation rate of 90% or more, styrene content 10wt%, random block type melt flow rate 3.5g / 10min)
Was carried out in the same manner as in Example 1 except that was mixed at the ratio shown in Table 2. Table 2 shows the results.

[0119]

[Table 2]

Comparative Example 1 The same procedure as in Example 1 was carried out except that the low-crystalline polypropylene obtained in Comparative Production Example 1 was mixed with the styrene-hydrogenated isoprene copolymer used in Example 1 at a ratio shown in Table 3. 1
The same operation as described above was performed. Table 3 shows the results.

Comparative Example 2 The procedure of Example 1 was repeated except that the low-crystalline polypropylene obtained in Comparative Production Example 1 was mixed with the styrene-hydrogenated butadiene copolymer used in Example 13 at the ratio shown in Table 3. The same operation as in Example 1 was performed. Table 3 shows the results.

Comparative Example 3 The procedure of Example 2 was repeated except that the low-crystalline polypropylene obtained in Comparative Production Example 2 was mixed with the styrene-hydrogenated isoprene copolymer used in Example 1 at the ratio shown in Table 3. 1
The same operation as described above was performed. Table 3 shows the results.

Comparative Example 4 The procedure of Example 1 was repeated except that the low-crystalline polypropylene obtained in Comparative Production Example 3 was mixed with the styrene-hydrogenated isoprene copolymer used in Example 1 at the ratio shown in Table 3. 1
The same operation as described above was performed. Table 3 shows the results.

Comparative Example 5 The procedure of Example 1 was repeated except that the low-crystalline polypropylene obtained in Comparative Production Example 4 was mixed with the styrene-hydrogenated isoprene copolymer used in Example 1 at the ratio shown in Table 3. 1
The same operation as described above was performed. Table 3 shows the results.

Comparative Example 6 The procedure of Example 1 was repeated except that the low-crystalline polypropylene obtained in Comparative Production Example 5 was mixed with the styrene-hydrogenated isoprene copolymer used in Example 1 at the ratio shown in Table 3. 1
The same operation as described above was performed. Table 3 shows the results.

Comparative Example 7 The procedure of Example 1 was repeated except that the low-crystalline polypropylene obtained in Comparative Production Example 6 was mixed with the styrene-hydrogenated isoprene copolymer used in Example 1 at the ratio shown in Table 3. 1
The same operation as described above was performed. Table 3 shows the results.

Comparative Example 8 Using the low-crystalline polypropylene obtained in Production Example 1,
The same operation as in Example 1 was performed except that the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at a ratio shown in Table 3. Table 3 shows the results.

Comparative Example 9 Using the low crystalline polypropylene obtained in Production Example 1,
The same operation as in Example 1 was performed except that the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at a ratio shown in Table 3. Table 3 shows the results.

Comparative Example 10 The pellets of the low-crystalline polypropylene obtained in Production Example 1 and SEPTON 1650 (trade name: butadiene having a hydrogenation rate of 90% or more, styrene content, styrene-hydrogenated butadiene copolymer) were obtained. 29 wt%, triblock, diblock type melt flow rate (not flowable) was mixed with the copolymer at the ratio shown in Table 3, and the same operation as in Example 1 was performed. Table 3 shows the results.

Comparative Example 11 Ethylene-propylene rubber having a melt flow rate of 3.0 g / 10 min, 50 wt% of polypropylene, a melt flow rate of 1.8 g / 10 min produced using a vanadium catalyst, and an ethylene unit of 88 mol%. (EP
R) The same operation as in Example 1 was performed, except that the blending was performed at a ratio of 50% by weight. Table 3 shows the results.

Comparative Example 12 50 wt% of polypropylene having a melt flow rate of 3.0 g / 10 min, propylene-butene-1 copolymer (butene-1 content: 40 mol%, weight average molecular weight: 50,000) 5
The same operation as in Example 1 was performed except that the blending was performed at a ratio of 0% by weight. Table 3 shows the results.

[0132]

[Table 3]

[Brief description of the drawings]

FIG. 1 is an elution curve of a low-temperature polypropylene elution fractionation method of low-crystalline polypropylene of Example 1.

Claims (4)

[Claims] (1) A propylene homopolymer or a copolymer of propylene and an α-olefin having a content of α-olefin units other than propylene of 5 mol% or less,
(I) a melt flow rate of 0.1 to 20 g / 10 minutes,
(II) The amount of the eluting component (component A) at a temperature lower than 20 ° C. in the elution curve obtained by the elevated temperature elution fractionation method, in which the horizontal axis represents the elution temperature and the vertical axis represents the integrated weight ratio of the elution component. Is 5
35% by weight, eluted component at 20 ° C or higher and lower than 100 ° C (B
Component) in an amount of 10 to 40% by weight, an elution component (component C) at 100 ° C. or higher of 40 to 80% by weight, a total of the components A, B and C being 100% by weight, and a mixture of the components B and A 100 parts by weight of a low-crystalline polypropylene, characterized in that the weight ratio (B / A) is 0.6 or more, and the peak top temperature of the component C is 115 ° C. or more. Copolymer consisting of 5 to 25% by weight of a compound unit and 95 to 75% by weight of an aliphatic conjugated diene compound unit partially hydrogenated.
A resin composition comprising: parts by weight. 2. The structure of the copolymer (2) is (ab-b-
Blocks having any one of structures a) and (ab) (where a is a polymer block based on an aromatic vinyl compound, and b is a polymer block based on a hydrogenated aliphatic conjugated diene compound) The resin composition according to claim 1, which is a polymer or a mixture thereof. 3. The copolymer (2) has a structure of (ac-c-
a) any one of the structures of (ac) and (acd) (where a is a polymer block based on an aromatic vinyl compound, c is a hydrogenated aliphatic conjugated diene compound and aromatic compound) A random copolymer block with an aromatic vinyl compound, d is a block copolymer that is an aromatic vinyl compound and a hydrogenated aliphatic conjugated diene compound, a tapered block in which the aromatic vinyl compound is gradually increased), or a mixture thereof. The resin composition according to claim 1. 4. The resin composition according to claim 1, wherein the peak top temperature of the component C in the low-crystalline polypropylene is 120 ° C. or higher.