WO2002032996A1

WO2002032996A1 - Resin composition

Info

Publication number: WO2002032996A1
Application number: PCT/JP2001/009151
Authority: WO
Inventors: Hiroaki Takeda
Original assignee: Idemitsu Petrochemical Co., Ltd.
Priority date: 2000-10-19
Filing date: 2001-10-18
Publication date: 2002-04-25

Abstract

A resin composition comprising (1) 100 parts by weight of a propylene block copolymer which is composed of 1 to 70 wt% of a component eluted at 100 °C or above and 99 to 30 wt% of a component eluted at lower than 100 °C as determined by the temperature raising elution fractionation method with the higher -temperature eluted component being constituted of 100 to 90 mole % of propylene monomer units and 0 to 10 mole % of ethylene monomer units and the lower-temperature eluted component being constituted of 90 to 50 mole % of propylene monomer units and 10 to 50 mole % of ethylene monomer units, satisfies the relationship: log((Mw/Mn) x MFR0.33)= 0.57 to 1.5 [wherein MFR is melt mass flow rate of the copolymer; and Mw and Mn are weight- and number-average molecular weights of the copolymer respectively as determined by gel permeation chromatography, and has a weight-average molecular weight (Mw) of 80,000 to 1,500,000, and (2) 1 to 100 parts by weight of a copolymer comprising 5 to 25 wt% of aromatic vinyl units and 95 to 75 wt% of conjugated diene units which are at least partially hydrogenated.

Description

Description Resin composition Technical field

The present invention relates to a resin composition which is excellent in flexibility, low-temperature impact resistance, good in moldability, and suppresses the pread of a low molecular weight product after molding, and has excellent transparency. Background art

Conventionally, as a method for improving the flexibility of crystalline polypropylene, crystalline polypropylene has been added to ethylene-propylene copolymer rubber, ethylene-butene copolymer rubber, propylene-butene copolymer, low-density, and linear low-density. A method of blending a modifier such as polyethylene is generally known. However, such a method of blending a modifier could not satisfy both flexibility and transparency at the same time.

On the other hand, a method for imparting flexibility in the polymerization stage such as a two-stage polymerization method in which propylene is polymerized in the first stage and propylene and ethylene are copolymerized in the second stage is obtained by the above-mentioned blend method. Although the transparency is better than that of the polymer particles, it is necessary to lower the melt mass flow rate and narrow the molecular weight distribution in order to reduce the tackiness of the obtained polymer particles. There was a problem with moldability, and improvement was desired.

Regarding these problems, the present inventors have already disclosed in Japanese Patent Application Laid-Open No. Hei 8-134324 a specific propylene block copolymer as a styrene-ethylene-butadiene-styrene copolymer (SEBS). , By blending styrene-ethylene-propylene-styrene copolymer (SEPS), we have proposed a resin composition with improved flexibility, transparency, and impact resistance. However, the specific propylene block copolymer used in the above-mentioned Japanese Patent Application Laid-Open No. 8-134324 has a narrow molecular weight distribution with respect to the melt mass flow rate, and thus is not sufficiently moldable. Was not satisfactory.

Further, the present inventors have disclosed in Japanese Patent Application Laid-Open No. 11-24987. By blending SEBS and SEPS with low-crystalline polypropylene, flexibility and heat resistance are excellent, and We have proposed a resin composition that suppresses bleed after molding and has excellent transparency. However, the resin composition proposed in the above-mentioned Japanese Patent Application Laid-Open No. 11-24097 has some room for improvement in flexibility, and was not sufficiently satisfactory in low-temperature impact resistance.

Disclosure of the invention

Therefore, an object of the present invention is to provide a resin composition which is excellent in flexibility, transparency, and low-temperature impact property, has good moldability, and suppresses bleeding of low molecular weight substances.

The inventors of the present invention have conducted studies to solve the above-mentioned problems, and as a result, have found that a resin composition of a propylene-based block copolymer composed of a specific component and a specific aromatic vinyl-conjugated gen-based copolymer is used. However, they have found that flexibility, transparency, and low molecular weight compounds can be suppressed, and that both low-temperature impact resistance and moldability can be achieved, and the present invention has been completed.

That is, the present invention provides: (1) 1 to 70% by weight of eluted components at 100 ° C. or higher, which are measured by a temperature-rise elution fractionation method; The content is 99 to 30% by weight, and the monomer unit based on propylene of the elution component at 100 ° C. or higher is 100 to 90% by mole, and the monomer unit based on ethylene. 0 to 10 mol%, 90 to 50 mol% of a propylene-based monomer unit of the elution component below 100 ° C, and 10 to 50 mol of an ethylene-based monomer unit. % Of the copolymer, the weight-average molecular weight (Mw) and the number-average molecular weight (Mw) of the copolymer measured by melt-mass mouth rate (MFR), gel permeation chromatography. n) (MwZMn) and 1 og ((Mw / Mn) XMFR ° ³³ ) is 0.57 ~; L.5 ヽ Mw is 80,000 ~ 150,000 Propylene block copolymer 100 parts by weight

(2) Fragrance in which the monomer unit based on an aromatic vinyl compound is 5 to 25% by weight, and the monomer unit based on at least a partially conjugated diene compound is 95 to 75% by weight. Aromatic vinyl-conjugated diene copolymer 1-; L 00 parts by weight

And a resin composition characterized by comprising: BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the elevated temperature elution fractionation method is referred to as JournalofAppliedPolymeerScienec;

The method is described in detail in A pplied Polymer Symposium 45, 1-24 (1990). More specifically, first, a high-temperature polymer solution is introduced into a column filled with a diatomaceous earth filler, and the column temperature is gradually reduced, so that components having a high melting point appear on the surface of the filler. Crystallize in order and then gradually raise the ram temperature to elute the components in order from the one with the lowest melting point This is a method of separating one component of lima.

In the present invention, as shown in the examples, the values obtained by the temperature rising elution fractionation method are as follows: SSC_730 type manufactured by Sensh-Ichi Kagaku Co., Ltd., solvent: o-dichlorobenzene, flow rate: 2.5 m 1 / min-Heating rate: 4 ° CZH r, Column: 0 3 O mm X 3 OO mm The elution curve showing the relationship between the elution temperature and the cumulative weight ratio of the elution components. Is a value derived from

The propylene-based block copolymer used in the present invention has an elution component of 10 ° C. or more (hereinafter abbreviated as “high-temperature elution component”) in an amount of 1 to 70% by weight when separated by heating and elution under the above measurement conditions. Elution components below 100 ° C

(Hereinafter abbreviated as low-temperature elution component) is 99 to 30% by weight.

When the amount of the high-temperature eluting component is less than 1% by weight and the amount of the low-temperature eluting component exceeds 99% by weight, the propylene-based block copolymer particles are likely to stick, and the production becomes difficult. On the other hand, when the proportion of the high-temperature eluting component exceeds 70% by weight and the low-temperature eluting component is less than 30% by weight, the flexibility, transparency and low-temperature impact resistance of the obtained resin composition are reduced. The desired composition cannot be obtained. The proportion of high-temperature eluting components and low-temperature eluting components is 3 to 3 for high-temperature eluting components, considering flexibility, transparency, low-temperature impact resistance, etc.

60% by weight, low-temperature-eluting components 97 to 40% by weight are preferable, and high-temperature-eluting components 5 to 50% by weight, and low-temperature-eluting components 95 to 50% by weight are more preferable.

In the present invention, the monomer unit based on propylene of the high-temperature eluting component is 100 to 90 mol%, preferably 100 to 95 mol%, and the monomer unit based on ethylene is It is 0 to 10 mol%, preferably 0 to 5 mol%. If the above-mentioned high-temperature eluting component satisfies the above ratio, propylene homopolymer, propylene-ethylene copolymer, Alternatively, a mixture of a propylene homopolymer and a propylene-ethylene copolymer may be used.

On the other hand, the monomer unit based on propylene of the low-temperature eluting component is 90 to 50 mol%, preferably 85 to 50 mol%, and the monomer unit based on ethylene is 10 to 50 mol%. Mole%, preferably 15 to 50 mol% is necessary to achieve the object of the present invention.

That is, when the monomer unit based on propylene exceeds 90 mol% and the monomer unit based on ethylene is less than 10 mol%, the flexibility and low-temperature impact resistance of the obtained resin composition are sufficient. On the other hand, when the monomer unit based on propylene is less than 50 mol% and the monomer unit based on ethylene exceeds 50 mol%, the transparency of the obtained resin composition is sufficient. I don't like it. The low-temperature eluting component may be a propylene-ethylene copolymer or a mixture of a propylene homopolymer and a propylene-ethylene copolymer as long as the above ratio is satisfied. Furthermore, the MFR of the propylene-based block copolymer used in the present invention and the molecular weight distribution represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) determined by gel permeation / chromatography. Log ((Mw / M n) x calculated from (Mw / Mn)

MF R ° ^'33 ) must be in the range of 0.5 7 to 1.5 1 og ((Mw / M n) x MFR. ³³ ) If it is less than 0.57 In addition, the molecular weight distribution is too narrow, or the MFR is too small, so that the appearance of defects such as melt fracture and sharkskin tends to occur. Also, if the film forming method is used as the molding method, neck-in is likely to occur. It is not preferable because the sex becomes worse. Also,

If log ((Mw / Mn) x MFR ° ³³ ) exceeds 1.5, the molecular weight distribution is too wide or the MFR is too large, and In the resin composition to be produced, the amount of low molecular weight substances increases, and it becomes difficult to suppress bleeding.

The log... ((Mw / M n) x MFR ° - 33) , when considering the pre-one de state of the resulting resin sets Narubutsu, is favored properly 0 6 0-1 4, more preferably 0 6 5 to: L.3.

Further, the weight average molecular weight (Mw) of the propylene block copolymer used in the present invention needs to be 80,000 to 150,000. When the weight average molecular weight is less than 80,000, the above 1 og is used. ((Mw / M n) X

Even when MFR ° ^'33 ) is in the range of 0.57 to: 1.5, it is not preferable because the melt tension is reduced and the formability is reduced. On the other hand, if the weight average molecular weight exceeds 150,000, the molecular weight is too large.

The propylene-based block copolymer used in the present invention includes a so-called block copolymer molecular chain in which a polypropylene component and a propylene-ethylene random copolymer component are arranged in one molecular chain, Z or polypropylene component, and propylene-ethylene copolymer. It is preferable that the random copolymer component is mixed with a molecular chain composed of each single component in a micro form in order to obtain good transparency.

As long as the effects of the present invention are not impaired, the propylene block copolymer used in the present invention contains a small amount of monomer units based on α-olefins other than ethylene and propylene, for example, in a range of 5 mol% or less. May be included.

The method for producing the propylene-based block polymer used in the present invention is not particularly limited as long as it satisfies the requirements of the present invention. For example, it can be suitably obtained by the following method.

That is, the following catalyst components [a], [b], [c] [A] Titanium compound

[B] Organic aluminum compound

[C] Organic gay compound

Is a method in which propylene is polymerized in the presence of water and then random copolymerization of propylene and ethylene is performed under the following conditions.

As the titanium compound [a], a known titanium compound used for polymerization of an olefin can be used without any limitation. Among them, a titanium compound that can obtain a highly stereoregular polymer in 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 Unexamined Patent Publication Nos. Sho 56-155206, JP-A 56-136806, JP

5 7-3 4 1 0 3 Publication, 5-8 7 06 Publication, 5-8 3 0 6 Publication, 5 1 8 13 8 7 08 Publication, 5 8 — 1 8 3 7 0 9 and 5 9 — 2 0 6 4 8 and 5 9 — 2 9 3 11 1 and 6 0 — 8 1 2 8 and 6 No. 0 _ 8 1 2 0 9

No. 6 0-1 8 6 5 08, No. 60 — 1 927 08, No. 6 1-2 1 1 3 09, No. 6 _ 2 7 1 3 0 4 No. 62-152 009, No. 62-117 106, No. 62-7272, No. 62-104080, etc. The method shown in is adopted. Specifically, for example, a method in which titanium tetrachloride is co-ground with a magnesium compound such as magnesium chloride, and a method in which titanium halide is mixed with titanium halide in the presence of an electron donor such as alcohol, ether, ester, ketone or aldehyde. Examples include a method of co-milling a magnesium compound and a method of bringing a titanium halide, a magnesium compound and an electron donor into contact with each other in a solvent. Examples of the titanium trichloride compound include known ", βa and (5-titanium trichloride. The method for preparing these titanium trichloride compounds is described in, for example, Japanese Patent Application Laid-Open No. 47-34447. No. 8, No. 50 _ 1 265 0 90, No. 50 — 1 1 4 3 9 4 No., No. 50-9 3 888 No., No. 50 — 1 230 No. 91, No. 50 — No. 7 4 5 9 4 No., No. 50 _ 1041 191 No., No. 50 _ 9 8 489 No. 5, No. 5-1 3 6 6 The methods disclosed in JP-A Nos. 25-52, 52-308888, 52-325283, etc. are adopted.

Next, as the organic aluminum compound [b], a known compound used for polymerization of the olefin is employed without any limitation. For example, trimethylaluminum, triethylaluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, tri-i-butyl aluminum, tri-n-hexyl aluminum, Tri-n-octyl aluminum, tri-n-trialkylaluminums such as decylaluminum; getylaluminum monohalides such as getylaluminum monochloride, getylaluminum promide, etc. And alkylaluminum halides such as chloride and ethylaluminum dichloride. In addition, alkyl alkoxy aluminums such as monoethoxy getyl aluminum and ethoxy monoethyl aluminum can be used.

Further, as the organic gay compound (c), a known compound used for improving the stereoregularity of the olefin is used without any limitation, but a chain-like structure in which the atom directly connected to the gay atom is tertiary carbon. An organosilicon compound having a bulky substituent such as a cyclic hydrocarbon which is a hydrocarbon or a secondary carbon can increase the stereoregularity of the resulting polypropylene component. Combination is preferred because it exhibits good heat resistance. Specifically, di-t-butyldimethoxysilane, t-butylethyldimethoxysilane, di-t-amyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane , Cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, organic hexylisobutyldimethoxysilane, etc. Can be listed. Among them, t-butylethyldimethoxysilane and dicyclopentyldimethoxysilane are particularly preferred. It is also possible to use a plurality of these organic gay compounds at the same time.

The combination of the titanium compound (a), the organic aluminum compound (b) and the organic gay compound (c) used in the present invention is as follows:

(1) Titanium trichloride compound-trialkylaluminum

(2) Supported titanium compounds-trialkylaluminum-organic silicon compounds

as well as, .

(3) Titanium compound supported-Titanium trichloride compound-Trialkylaluminum-Organic silicon compound

It is preferable that In particular, in order to satisfy the constitution of the propylene block copolymer of the present invention in combination with other production conditions, the combination of (1) is preferable.

In the present invention, prior to the main polymerization in the presence of each of the above components, the titanium compound [a], the organic aluminum compound [b], and Pre-polymerization of one-year-old olefins in the presence of an organic silicon compound [C], if necessary, reduces the amount of low-molecular-weight components in the resulting propylene-based block copolymer and reduces This is preferable because stickiness in the case of a product can be suppressed.

Further, in addition to the above components, an iodine compound represented by the following formula [e] R-I

(However, R is an iodine atom or an alkyl group having 1 to 7 carbon atoms or a phenyl group.)

When prepolymerization of a-olefin is performed in the presence of styrene, the amount of low-molecular-weight components produced in the resulting propylene-based block copolymer is further reduced, and the stickiness of a molded article is further reduced. This is a more preferable mode.

Specific examples of the above-mentioned iodine compound [e] include iodine, methyl iodide, thiol iodide, iopropyl, butyl iodide, benzene, p-toluene iodide and the like. Among them, methyl iodide and thiol iodide are particularly preferred.

The amount of each of the catalyst components (a) and (b) used in the prepolymerization of the present invention and (c) and / or (e) used as necessary depends on the type of the catalyst component. Since it varies depending on the conditions of polymerization, the optimal amount may be appropriately used according to each of these conditions. An example of a generally preferred range is as follows.

The ratio of the organoaluminum compound [b] used in the prepolymerization is 0.1 to 100, preferably 0.1 to 100, in terms of A1 / Ti (molar ratio) with respect to the titanium compound [a]. A range of 20 is preferred.

Further, the organic gay compound [c] used as needed is 0.01 to 1 in terms of [c] / Ti (molar ratio) with respect to the titanium compound [a]. 100, preferably 0.01 to 10 is preferable, and the proportion of the iodine compound [e] used as necessary is I / T with respect to the titanium compound [a]. The i (molar ratio) is preferably in the range of 0.1 to 100, preferably 0.5 to 50.

In the presence of the catalyst component, the amount of prepolymerization for polymerizing the olefin is dependent on the prepolymerization conditions, but is generally from 0.1 to 500 g / g · Ti compound, preferably from 1 to: It is sufficient to be in the range of L 0 0 g Z g · Ti compound. The olefin used in the prepolymerization may be propylene alone, and may be, for example, 5 mol% or less of an α-olefin other than propylene, as long as it does not adversely affect the physical properties of the propylene-based block copolymer. For example, a mixture of ethylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene-11 and propylene may be used. In addition, the prepolymerization can be performed in multiple stages, and different α-olefins can be prepolymerized in each stage, and hydrogen can coexist in each prepolymerization stage.

For the prepolymerization, slurry polymerization is usually preferably applied, and a saturated aliphatic hydrocarbon and an aromatic hydrocarbon such as hexane, heptane, cyclohexane, benzene and toluene are used alone as a solvent. Alternatively, they can be used as a mixture. 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. The pressure in the prepolymerization is not limited, but in the case of slurry polymerization, it is generally from atmospheric pressure to about 0.5 MPa. The prepolymerization may be carried out in any of batch, semi-batch and continuous methods.

In the present invention, the present polymerization is carried out by first polymerizing propylene in the presence of the above-mentioned catalyst component or the catalyst-containing prepolymer obtained by the above prepolymer. An embodiment in which the copolymerization is carried out and then random copolymerization of propylene-ethylene is performed is preferable. 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 amount of each of the catalyst components (a), (b), and (c) used in the main polymerization of the present invention and the polymerization conditions vary depending on the type of the catalyst component. The optimum use amount and polymerization conditions may be determined in advance. Examples of the amounts of the catalyst components and the polymerization conditions suitably used are as follows.

As the organoaluminum compound [b] used in the main polymerization, the above compounds can be used without any limitation. The amount of the organic aluminum compound used in the main polymerization is A 1 Z Ti (molar ratio) with respect to the titanium atom in the catalyst; ~ 100, preferably 2 ~ 500.

As the organic gay compound [c] used in the main polymerization, the above compounds can be used without any limitation. The amount of the organic gay compound used in the main polymerization is S i / T i (molar ratio) with respect to the titanium atom in the catalyst.

0.001 to 100, preferably 0.1 to 500.

In the above main polymerization, propylene is firstly polymerized. The polymerization of propylene may be carried out by polymerizing propylene alone or a mixture of propylene and α-olefin other than propylene within a range satisfying the requirements of the present invention. When typical conditions of propylene polymerization are exemplified, the polymerization temperature is preferably employed at 80 ° C. or lower, and more preferably in the range of 20 to 70 ° C. If necessary, hydrogen can 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, solution polymerization, etc., simplicity of the process and reaction rate, and particle properties of the produced copolymer. In consideration of this, 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 carried out in two or more stages under different conditions such as hydrogen concentration and polymerization temperature.

Next, random copolymerization of propylene and ethylene is performed. In the random copolymerization of propylene and ethylene, in the case of slurry polymerization using propylene itself as a solvent, an ethylene gas is supplied following the propylene polymerization, and in the case of gas phase polymerization, propylene and ethylene are mixed. This is performed by supplying a mixed gas.

The polymerization temperature of the random copolymerization of propylene and ethylene is not more than 80 ° C, and preferably is in the range of 20 to 70 ° 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 that time in multiple stages.

In the random copolymerization of ethylene and propylene following propylene polymerization, a specific catalyst is selected to produce a propylene block copolymer having the desired molecular weight distribution and crystallinity distribution in one step. Alternatively, it can be produced by a method in which random copolymerization of ethylene and propylene is performed in multiple stages, and polymerization conditions such as hydrogen concentration and ethylene concentration are changed in each stage. In such multi-stage copolymerization, copolymerization is carried out by appropriately adjusting the ratio of the high-temperature eluting component and the low-temperature eluting component according to the polymerization conditions.

The random copolymerization of propylene and ethylene 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.

In particular, to obtain the propylene block copolymer of the present invention, It is preferred to carry out random copolymerization of propylene and ethylene by slurry polymerization following polymerization of propylene.

The monomer can be evaporated from the polymerization system after completion of the main polymerization to obtain the propylene-based block copolymer of the present invention. The propylene-based block copolymer can be subjected to known washing, for example, countercurrent washing, with a hydrocarbon having 7 or less carbon atoms.

The propylene block copolymer used in the present invention may be used after adding and mixing commercially available additives such as an antioxidant, a heat stabilizer, and a chlorine scavenger, and then pelletizing with an extruder. . In addition, 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.

In the present invention, as a method for controlling the melt mass rate and the molecular weight of the propylene-based block copolymer, a small amount of hydrogen is allowed to coexist at the time of polymerization to reduce the molecular weight and the molecular weight of the propylene-based copolymer. It is preferable to adjust the melt mass flow rate and the molecular weight within a predetermined range by adjusting the melt mass flow rate and the molecular weight to some extent with an organic peroxide.

In particular, the polymer obtained by allowing a small amount of hydrogen to coexist during the polymerization has a melt mass flow rate of 0.001 to: L 0 g / 10 min or less, more preferably 0.01 to 5 g. / l 0 min, more preferably

A method of once adjusting the viscosity to 0.01 to 3 g Z 10 min or less, melting and kneading the mixture with an organic peroxide, and adjusting the melt mass mouth opening rate and the molecular weight to a predetermined range is preferable.

As the organic peroxide to be used when decomposing the propylene block copolymer used in the present invention, known compounds can be used without any limitation. Representative examples include, for example, methyl ether. Luque Tonpeoxyde, Methyl Isobutyl Ketone Tonpeoxide. Ketone peroxides such as cyclohexanone peroxide; isobutylyl peroxide, lauroyl peroxide, benzoyl peroxide, etc .; diacyl peroxides such as diisopropylbenzenhydroxide, etc. Dicumyl peroxide, 2,5-dimethyl-2-, 5-di- (t-butylperoxy) hexane, 1,3-bis- (t-butylvinyloxy-isopropyl) -benzene, di-t-butyl Diperoxides, such as ruperoxide, 2,5-dimethyl-1,2,5-di- (t-butyl-hydroxy) 1-hexane-3; 1,1, -di-t-butyl-oxy 1,3,3 , 5 — trimethylcyclohexane, 2, 2 — dioxy (t-butylperoxy) monobutane It can be mentioned Pakabone bets such as t one Puchirupa one O carboxymethyl isopropyl Kabone preparative like; le t _ Buchiruba one Okishipibare, alkyl peresters such as t Buchiruba one Okishibenzoe bets. The above-mentioned kneading of the propylene block copolymer and the organic peroxide is carried out. Generally, a known kneading apparatus is used at a temperature not lower than the melting point of the propylene block copolymer and the decomposition temperature of the organic peroxide. Done using. For example, a method of kneading at 160 to 330 ° C, preferably 170 to 300 ° C using a screw extruder, a Banbury mixer, a mixing roll, or the like is employed. can do. Further, the melt-kneading can be performed under a stream of an inert gas such as nitrogen gas. Prior to melt-kneading, preliminary kneading can also be performed using a known mixing device, for example, a tumbler, Henschel mixer or the like.

On the other hand, the following aromatic vinyl-hydrogenated conjugated diene copolymer used in the present invention is particularly excellent in flexibility and low-temperature impact resistance while maintaining the transparency of the propylene-based block copolymer. After molding This is important for obtaining a resin composition having an excellent effect of suppressing low molecular weight bleed products.

That is, the monomer unit of the aromatic vinyl compound of the aromatic vinyl-hydrogenated conjugated gen-based copolymer is 5 to 25% by weight, preferably 8 to 20% by weight. If the monomer unit based on the aromatic vinyl compound is less than 5% by weight, blocking occurs during molding, which is not preferable. On the other hand, if the monomer unit based on the aromatic vinyl compound exceeds 25% by weight, It is not preferred because not only the transparency is lowered but also the effect of improving flexibility is lowered.

Examples of the vinyl aromatic compound include styrene, o-methylstyrene, alkyl styrene such as ρ-methylstyrene and ρ_t-butylstyrene, p-methoxystyrene, and bulnaphthalene. Among them, styrene is particularly preferred. New

In the present invention, at least a part of the double bond of the conjugated gen moiety in the copolymer is a monomer unit based on a conjugated gen at least partially hydrogenated (hereinafter referred to as a hydrogenated conjugated gen) compound. Is not particularly limited as long as it is hydrogenated, but considering transparency, it is preferable that 80% or more of the double bonds in the conjugated gen part be hydrogenated and saturated. Conversely, if the double bond of the conjugated gen moiety is not hydrogenated, the compatibility with the propylene block copolymer used in the present invention is poor and transparency is impaired, which is not preferred.

Examples of the conjugated diene compounds include butadiene, isoprene, pyrylene, methylpentenediene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-dimethyl-1,3-octadiene, and the like. Among them, at least one kind is mentioned, but butadiene and isoprene are particularly preferred. The aromatic vinyl-hydrogenated conjugated diene copolymer used in the present invention is not particularly limited as long as it satisfies the above-mentioned rules, and the above-mentioned known ones can also be used.

Specific examples of commercially available aromatic vinyl-hydrogenated conjugated gen-based copolymers include, for example, Clayton G1657 manufactured by Shile, Septon 2043 manufactured by Kuraray, and Nubra® (1) HVS-3, and DynaPin 1320 P manufactured by Nippon Synthetic Rubber Co., Ltd.

The copolymerization form of the aromatic vinyl compound and the hydrogenated conjugated gen compound in the aromatic vinyl-hydrogenated conjugated gen-based copolymer used in the present invention suppresses the bleeding of low molecular weight products after molding. In view of maintaining transparency, the following copolymers are preferred.

That is, when A is a polymer block based on an aromatic butyl compound and B is a polymer block based on a hydrogenated conjugated gen compound, an AB block copolymer (hereinafter also referred to as a diblock type) And A—B—A block copolymers (hereinafter also referred to as triblock types), or a mixture of these copolymers is preferable.

On the other hand, in consideration of obtaining particularly excellent transparency in the resin composition of the present invention, the copolymer of the aromatic vinyl compound and the hydrogenated conjugated gen in the aromatic vinyl-conjugated gen-based copolymer is considered. The form is preferably a copolymer shown below.

A is a polymer block based on an aromatic vinyl compound; C is a random polymer block of a hydrogenated conjugated gen compound and an aromatic vinyl compound; and D is a conjugated gen compound hydrogenated with an aromatic butyl compound. In the case of a polymer block, the monomer unit based on the aromatic vinyl compound is gradually increased. A-C block copolymer, A-C-A block copolymer, A-C-D block copolymer (hereinafter also referred to as random block type), or a mixture of these copolymers I like it.

The aromatic vinyl-hydrogenated conjugated diene copolymer component has a melt mass flow rate force of 0.1 to 20 measured at a load of 230 ° C-2.16 kg (2.1.18 N). The one with g / 10 minutes is preferably used.

The method for producing the aromatic vinyl-hydrogenated conjugated copolymer is not particularly limited, and may be produced by a conventionally known method. Usually, a method of copolymerizing an aromatic vinyl compound and a conjugated diene compound and then hydrogenating the double bond of the conjugated diene part in the copolymer is adopted. The resin composition of the present invention comprises (1) propylene Block copolymer 1

100 parts by weight, (2) aromatic vinyl-hydrogenated conjugated diene copolymer 1 to 100 parts by weight, preferably 3 to 80 parts by weight. If the amount of the aromatic vinyl-hydrogenated conjugated gen-based copolymer is less than 1 part by weight, the effect of improving the transparency and flexibility is not sufficient, and if it exceeds 100 parts by weight, the adhesiveness increases, so molding is performed. It is not preferable when the body is piled up, especially when a film sheet is obtained by a scroll, because violent blocking occurs.

Further, the resin composition of the present invention may contain propylene other than the propylene-based block copolymer defined in the present invention, based on 10 Q parts by weight of the resin composition of the present invention, as long as the effects of the present invention are not impaired. It is possible to add 0 to 40 parts by weight, preferably 0 to 30 parts by weight, of the polymer. Examples of the propylene-based polymer include a propylene homopolymer, 90% mol or more of propylene and an α-olefin other than propylene, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 1 — Heptene.

1-Methyl-1 Run with at least 10 mol% of one or more such as one pentene Dam copolymers can be suitably used.

Further, the resin composition of the present invention preferably contains 1 to 30 parts by weight of a resin other than those described above with respect to 100 parts by weight of the resin composition as long as the effects of the present invention are not impaired. Alternatively, it is also possible to carry out the reforming by adding 2 to 20 parts by weight. The resin used is high density polyethylene (HDPE), low density polyethylene (LDPE), ethylene and carbon number 4 ~

Polyethylene resins such as linear polyethylene (LLDPE), ethylene vinyl acetate copolymer (EVA), and ethylene methacrylate (EMMA), which are copolymerized with 10 α; Orylene-based soft resins such as pyrene copolymer (EPR, EPDM), ethylene * butene_1 copolymer (EBM), propylene / butene-1 copolymer (PBM), styrene / butadiene block copolymer

Known materials such as (SBR), petroleum resin, rosin resin, and hydrogenated terpene resin can be used without limitation.

The resin composition of the present invention may contain known additives such as antioxidants, light stabilizers, antistatic agents, lubricants, copper damage inhibitors, flame retardants, molding agents, and pigments. Can be.

The resin composition of the present invention is produced by a known method without any particular limitation. Generally, the resin composition is obtained by blending the above-mentioned components, followed by mixing and melt-kneading. The method of melt-kneading is not particularly limited, but, for example, using a screw extruder, a non-amber mixer, a mixing roll, or the like, preferably at 160 to 300 ° C. It is preferable to perform the reaction at a temperature of 180 to 270 ° C. Further, the melting and kneading can be performed under a flow of an inert gas such as a nitrogen gas. Before the 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 components of the resin composition as necessary after mixing, and directly putting the mixture into a molding machine without melt-kneading and molding. It is possible.

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

Hereinafter, the measurement method used in the examples will be described.

1) Measurement of polypropylene component

The measurement was performed under the following measurement conditions using an SSC-7300 model manufactured by Senshu Ichigaku Co., Ltd.

Solvent: o-dichlorobenzene

Flow velocity; 2.5 m1 / min

Heating rate: 4.0 ° C / Hr

Sample concentration; 0.7 w t%

Sample injection volume; 100 m 1

Detector: Infrared detector, wavelength 3.14 m

Column: 0 3 O mm x 3 O O mm

Packing agent; Chromosorb P30 to 60m column Cooling rate of column; 2.0 ° C / Hr

2) Measurement of monomer units based on propylene and ethylene

The measurement was performed using ¹³ C-NMR spectrometer using JEOLGSX-270.

3) Measurement of Menole Tomasof Mouth Rate (MFR)

Measured at 230 ° C and 2.16 kg load (2.1.18 N) in accordance with ASTM D-123.

4) Weight average molecular weight and molecular weight distribution

Measured by GPC (gel permeation chromatography) Specified. The measurement was performed at 135 ° C with o-dichlorobenzene as a solvent using SSC-7100 manufactured by Sensi Kagaku. The column used was Shodex UT 807806 M. The calibration curve is used as a standard sample. The weight-average molecular weight is 95,900,000, 50,000, 49,000,

It was made using 2.7 million and 4.90 million polystyrene.

5) Flexural modulus

Compliant with JISK 7203.

6) Izod impact value (notched, _30 ° C)

Compliant with JIS K 7110.

7) Transparency (haze value)

Compliant with JIS K6714.

8) Melt tension (methylen tension)

Using Toyo Seiki Co., Ltd. Capillograph 1B, melt tension at orifice (L = 20 mm D = 2 mm), 190 ° C, extrusion speed 5 mm / min, winding speed 10 m / min (Melt tension) o

Production example 1 1 1

(Preliminary polymerization)

After a 1-liter glass autoclave reactor equipped with a stirrer was sufficiently replaced with nitrogen gas, 400 milliliters of heptane was charged. The temperature in the reactor was kept at 20 ° C, and dicyclopentyldimethoxysilane, 4.2 mmol, thiol iodide, 21.5 mmol, triethylaluminum, 21.5 mmol, and Titanium trichloride (manufactured by Marubeni Solvay Chemical Co., Ltd.) After adding 21.5 millimoles, propylene was continuously introduced into the reactor for 30 minutes at 3 g per 1 g of titanium trichloride. did. The temperature during this period was kept at 20 ° C. Propylene supply After the supply was stopped, the inside of the reactor was sufficiently replaced with nitrogen gas, and the obtained polypropylene containing titanium was washed four times with purified heptane. As a result of the analysis, 2.9 g of propylene was polymerized per gram of titanium trichloride.

(Main polymerization)

In a 300 liter N 2 -substituted polymerization apparatus, 100 kg of liquid propylene, 85.0 millimoles of triethylaluminum, 42.5 millimoles of dicyclopentyl dimethoxysilane, Hydrogen was added so that the concentration in the gas phase became 2.5 mol%, and the internal temperature of the autoclave was raised to 55 ° C. Next, ethylene was supplied so that the concentration in the gas phase became 1.0 mol%, and 8.5 mmol of titanium-containing propylene obtained as a result of prepolymerization was added as titanium trichloride. Polymerization of propylene was carried out for 20 minutes (step 1). Next, ethylene was supplied at a concentration of 10 mol% while confirming the ethylene gas concentration in the gas phase by gas chromatography, and polymerization was carried out for 120 minutes (step 2). The unreacted monomer was purged to obtain a polymer. The obtained polymer was dried at 70 ° C. for 1 hour. The melt flow rate of the obtained powder was 0.32 g / 10 min. Next, an antioxidant [Ilganox 101 (Ciba Specialty Chemicals)] 0.2 parts by weight, heat stabilizer [P-EPQ (Ciba Specialty Chemicals)] 0.1 Parts by weight, chlorine scavenger [DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.)], 0.2 parts by weight, and then extruded at 250 ° C using a 50 mm extruder to pelletize. I got it. The results are shown in Table 1.

Production example 1 1 2

10 kg of the polymer obtained in Production Example 1 was added to an antioxidant [IRGA Knox 10 10 (Chino Specialty Chemicals) 0.2 parts by weight, heat stabilizer [P-EPQ (Ciba Specialty Chemicals)] 0.1 part by weight, chlorine scavenger [DHT-4A (Kyowa Chemical Industry Co., Ltd.)] 0.2 parts by weight, and 0.3 parts by weight of 1,3-bis- (t-butylvinyloxyisopropyl) benzene as an organic peroxide are added. After mixing, the mixture was extruded at 250 ° C. using a 5 O mm 0 extruder to obtain a pellet. The results are shown in Table 1.

Production Example 1 1 3

To 10 kg of the polymer obtained in Production Example 1 was added 0.2 parts by weight of an antioxidant [ILGANOX 10100 (Ciba Specialty 'Chemicals Co., Ltd.)], 2 parts by weight, a heat stabilizer [P—EPQ (Ciba Specialty Chemicals) 0.1 parts by weight, chlorine scavenger [DHT-4A (Kyowa Chemical Industry)] 0.2 parts by weight, 1,3-bis as organic peroxide -0.1 parts by weight of (t-butylvinyloxypropyl) benzene was added, mixed, and then extruded at 250 ° C using a 50 mm extruder to obtain a pellet. The results are shown in Table 1.

Production Example 2

In Step 1 of the main polymerization in Production Example 1, the hydrogen concentration in the gas phase was 1.5 mol%, the polymerization time of propylene was 30 minutes, and the ethylene gas concentration in the gas phase was 15.0 mol in Step 2. %, And the same operation as in Production Example 1 was performed except that ethylene was supplied and random copolymerization was performed for 120 minutes. The melt flow rate of the obtained powder was 0.05 g / 1 O min. Add 10 kg to the obtained polymer. Antioxidant [Ilganox 10100 (Ciba 'Specialty Chemicals)] 0.2 parts by weight, heat stabilizer [P_EPQ (Cibas (Charty Chemicals) 0.1 parts by weight, chlorine scavenger [D HT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.)] 0.2 parts by weight, and 0.03 parts by weight of 1,3-bis_ (t-butylvinyloxyisopropyl) benzene as an organic peroxide are added. After mixing, the mixture was extruded at 250 ° C. using a 5 O mm 0 extruder to obtain a pellet. The results are shown in Table 1.

Production Example 3 — 1

In step 1 of Production Example 1, the hydrogen concentration in the gas phase was set to 2.0 mol%, the ethylene gas concentration was supplied so as to be maintained at 0.5 mol%, and the propylene polymerization time was set to 10 minutes. In step 2, the same operation as in Production Example 1 was performed except that ethylene was supplied and polymerization was performed for 120 minutes so that the concentration of ethylene gas in the gas phase was maintained at 14.0 mol%. The melt flow rate of the obtained powder was 0.15 g / 10 min. The obtained polymer was added to 10 kg in an amount of 0.2% by weight of an antioxidant [Ilganox 11010 (Ciba Specialty Chemicals)], 0.2 parts by weight, and a heat stabilizer [P-EPQ (Ciba). Specialty 'Chemicals')' 0.1 parts by weight, chlorine scavenger [DHT-4A (Kyowa Chemical Industry)] 0.2 parts by weight, 1,3-bis as organic peroxide -(T-Butyloxypropyl) benzene was added in an amount of 0.03 part by weight, mixed, and extruded at 250 ° C using a 50 mm ø extruder to obtain a pellet. The results are shown in Table 1.

Production Example 3 — 2

To 10 kg of the polymer obtained in Production Example 3 was added 0.2 parts by weight of an antioxidant [ILGANOX 10100 (Ciba Specialty 'Chemicals Co., Ltd.)] and 2 parts by weight of a heat stabilizer [P- EPQ (Ciba Specialty Chemicals) 0.1 parts by weight, chlorine scavenger [DHT-4A (Kyowa Chemical Industry Co., Ltd.)] Q. 2 parts by weight, organic peroxide 1, 0.07 weight of 3_bis- (t-butyl-hydroxy-isopropyl) benzene After adding and mixing, a pellet was obtained by extruding at 250 ° C. using a 5 Omm 0 extruder. The results are shown in Table 1.

Production Example 4

The same operation as in Production Example 1 was performed except that the polymerization time of propylene was changed to 90 minutes in Step 1 of the main polymerization in Production Example 2. The resulting maleole flow rate was 0.09 g / 10 min. To 10 kg of the obtained polymer, 0.2 parts by weight of an antioxidant [Ilganox 110 (Ciba Specialty Chemicals)], 0.2 parts by weight, a thermal stabilizer [P_EPQ (Ciba Specialty, Chemi-Chem) 0.1% by weight, chlorine scavenger [DHT-4A (Kyowa Chemical Industry Co., Ltd.)] 0.2 parts by weight, 1,3-bis (t-butylamine) as an organic peroxide —Oxyisopropyl) Benzene was added in an amount of 0.02 parts by weight, mixed, and then extruded at 250 ° C. using a 50 mm 押出 extruder to obtain a beret. The results are shown in Table 1.

Production Example 5

The same operation as in Production Example 1 was performed except that hydrogen was added in Step 1 of the main polymerization in Production Example 1 so that the concentration in the gas phase became 1.0 mol. The resulting powder had a mouth-to-mouth mouth rate of 0.07 g / 10 min. To 10 kg of the obtained polymer, 0.2 parts by weight of an antioxidant [Irganox 11010 (Ciba 'Specialty' Chemicals)], 0.2 parts by weight, a heat stabilizer [P-EPQ (Ciba 0.1% by weight, chlorine scavenger [DHT-4A (Kyowa Chemical Industry Co., Ltd.)] 0.2 parts by weight, 1, 3-bis as organic peroxide After adding and mixing 0.06 parts by weight of (t-butylpropylisopropyl) benzene, the mixture was extruded at 250 ° C. using a 5 mm0 extruder to obtain a pellet. The results are shown in Table 1. Comparative Production Example 1

In the process of Production Example 1, a propylene-based block copolymer was polymerized without adding hydrogen. Melt toe rate of powder obtained is

0.01 g / 1 0 min or less. An antioxidant [Ilganox 101 (Ciba Specialty 'Chemicals Co., Ltd.)] 0.2 parts by weight, a heat stabilizer [P-EPQ (Ciba Specialty) Chemicals)] 0.1 parts by weight, chlorine scavenger [DHT-4A (Kyowa Chemical Industry)] Q. 2 parts by weight, 1,3-bis (t) as organic peroxide The same operation as in Production Example 1 was performed except that granulation was carried out by adding 0.2 parts by weight of -benzene-hydroxypropyl) -benzene. The results are shown in Table 1.

Comparative Production Example 2

The same operation as in Production Example 2 was performed, except that the polymerization was carried out for 120 minutes in Step 1 of the main polymerization in Production Example 2 and for 20 minutes in Step 2. The melt powder mouth rate of the obtained powder was 0.15 g / 10 min. Antioxidant [Ilganox 101 (Ciba Specialty Chemicals)] 0.2 parts by weight, heat stabilizer [P-EPQ (Ciba Specialty Chemicals)] ] 0.1 part by weight, chlorine scavenger [DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.)] 0.2 part by weight, 1,3-bis (t-butyl peroxy) as an organic peroxide Isopropyl) —The same operation as in Production Example 2 was performed except that granulation was performed by adding 0.01 part by weight of benzene. The results are not shown in Table 1.

Examples 1-3

Production Example 11 The pellets of the propylene-based block copolymer obtained in 1-1, 1--2, and 113 and the styrene-hydrogenated isoprene copolymer A Kuraray-made Septon 204 (brand name: isoprene hydrogenation rate of 90% or more, styrene content of 13 wt%, triblock, diblock type melt flow rate 4 g ZIO content) After mixing at the ratios shown in the table, the mixture was melted and kneaded with a 50 mm 0 extruder, and a 50-ton injection molding machine was used at a cylinder temperature of 230 ° C and a mold temperature of 40 ° C. Bending test piece, Izod impact test piece, and a thickness of 300 μm with a cylinder temperature of 250 ° C and a roll temperature of 40 ° C using a 40 mm 0 T die extruder. A sheet for measuring haze was created. The sheets evaluated as good were evaluated for appearance, and those evaluated as poor when melt fracture occurred and evaluated as X. The sheet width at which neck ine was evaluated as an index of formability was measured and determined by the following method.

Net In (cm) = Die Width (40cm) —Film Width The evaluation of the bleed was the external haze of the obtained sheet immediately after molding and 40. C, evaluated by the difference in external haze after aging for 2 weeks. The results are shown in Table 2.

Example 4

Same as Example 1 except that the propylene block copolymer obtained in Production Example 2 was used, and the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at the ratio shown in Table 2. Was performed. Table 2 shows the results.

Examples 5, 6

Except that the propylene-based block copolymer resin obtained in Production Example 3-1, 3-2 was used, and the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed in the proportions shown in Table 2, The same operation as in Example 1 was performed. The results are shown in Table 2.

Example 7 Same as Example 1 except that the propylene block copolymer obtained in Production Example 4 was used and the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at the ratio shown in Table 2. The operation was performed. Table 2 shows the results.

Example 8

Same as Example 1 except that the propylene block copolymer obtained in Production Example 5 was used, and the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at the ratio shown in Table 2. Was performed. Table 2 shows the results.

Example 9

A pellet of the propylene-based block copolymer obtained in Production Examples 1-2 and a styrene-hydrogenated butadiene copolymer, Cleton G 1657 (trade name: Table 2 shows the hydrogenation rate of 90% or more (rubber structure: ethylene-butylene), styrene content of 13 wt%, triblock, diblock type, menoleto flow rate of 8 g / 10 minutes) The same operation as in Example 1 was performed except that the components were mixed. The results are shown in Table 2.

Example 10

Production Example 12 Nippon Synthetic Rubber Dynallon 132 0 P, a pellet of the propylene-based block copolymer obtained in 1-2 and a styrene-hydrogenated benzene copolymer, trade name: The hydrogenation rate of benzene was 90% or more, the styrene content was 10% by weight, the random block structure, Meltoff mouth rate 3.5 g Z 10 minutes) were mixed at the ratios shown in Table 2. The same operation as in 1 was performed. The results are shown in Table 2.

Example 1 1

Production Example 1 Pellet of the propylene-based block copolymer obtained in 1-2 Kuraray HVS-3 (trade name: vinyl 'isoprene, hydrogenation rate of at least 80%, styrene content of 20% by weight, triblock structure) The same operation as in Example 1 was carried out, except that the melt (6 g of Zol) was mixed at the ratio shown in Table 2. The results are shown in Table 2.

Comparative Example 1

Using the propylene-based block copolymer obtained in Comparative Production Example 1. Same as Example 1 except that the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at the ratio shown in Table 2. Was performed. The results are shown in Table 2.

Comparative Example 2

Same as Example 1 except that the propylene-based block copolymer obtained in Comparative Production Example 2 was used and the styrene-hydrogenated isoprene copolymer used in Example 11 was mixed at the ratio shown in Table 2. Table 2 shows the results.

Comparative Example 3

Using the propylene block copolymer obtained in Production Example 1-2. Same as Example 1 except that the styrene-hydrogenated isoprene copolymer used in Example 1 was mixed at the ratio shown in Table 2. Was performed. The results are shown in Table 2.

Comparative Example 4

Production Example 1 The propylene block copolymer obtained in 1-2 was used. Except that the styrene monohydrogenated isoprene copolymer used in Example 1 was mixed at the ratio shown in Table 2, the same as in Example 1 was used. The same operation was performed. The results are shown in Table 2.

Comparative Example 5 Production Example 12 A pellet of the propylene block copolymer obtained in Example 1-2 and a Cleton G 1652 (a trade name of butadiene hydrogen, a styrene-hydrogenated butadiene copolymer) Addition rate 90% or more Styrene content 29 wt%, triblock, diblock structure, menoleto flow rate 1.3 g / 10 min.) The same operation as in Example 1 was performed. The results are shown in Table 2.

Comparative Example 6

Banajiumu catalyst MFR of 1. 8 g Z 1 0 mi _n at ethylene unit 8 8 mole percent ethylene one propylene rubber (EPR styrene content 0%) was prepared using 1 0 part by weight, MFR Chikaraku 3.0 The same operation as in Example 1 was performed, except that 100 parts by weight of random polypropylene (ethylene content: 3 mol%) of g / 10 min was blended. The results are shown in Table 2.

Table 1

High temperature elution component Low temperature elution component

Propylene ethylene Propylene ethylene

1 (g-pp / g-cat) (%) 3 ri 3 ri (%) None as

(mol%) (mol%) (mol%) (mol%) Observation 1-1 4500 8.0 97.5 2.5 92.0 76.0 24.0

4500 8.0 97.5 2.5 92.0 76.0 240

4500 8.0 97.5 2.5 92.0 76.0 24.0 Energy 112 4900 16.0 97.0 2.0 840 66.3 33.7 Keying 3-1 4600 9.0 98.6 1.4 91.0 66.9 33.1 Keying 3 2 4600 9.0 98.6 1.4 91.0 66.9 33.1

5000 40.8 97.3 2.7 59.2 73.2 26.7

4900 8.2 98.1 1.9 91.8 75.6 24.4 ^ ι 4200 10.6 96.5 3.5 89.4 76.4 23.6

2 3500 82.0 99.2 0.8 18 70.3 29.7

Table 1 I 2

Formula (X): l og (( Mw / Mn) XMFR 0 - 33)

Table 2 1

* 1 Septon 2043: (A_B), (A-B-A) type, Styrene ^ * 13%, Melt mouth-rate 4g / 10min

* 2 Krait Ϊ1657 (AB) (ABA) type, Styrene ^ ¾3%, Melt mouth-rate 8g / 10min 氺 3 Dynalone 1320P (A "C), (A ~ C-A), (A" C- D) type, styrene ^ * 10%

Meltov mouth-rate 3.5g / 10min

* 4 HYBRA HVS-3 (A-B), (A-B-A) type, styrene ¾ * 20%, melt-off mouth-rate 1.5 g / 10 min. * 5 Krait Ϊ1652 (A-B), (A_B-A) type, styrene 9%, melt-off mouth-rate 1.3g / 10min

* 6 Ethylene-propylene rubber: Styrene content 0%, melt tip-rate 3g / min Izot Neck-in External haze (%) -30 ° C (KJ / m ² ) (cm) Appearance 40 ° C li circumference FB¾ Reinforcement 1 N.B 2.6 o 8 2 8 8 Reinforcement 2 N.B 3 8 o 7 1 R 0 l¾y class uii 3 N.B 4. .9 o U δ ■ o Q

Hi rope 4 N.B 3.8 o O. 9 1 n o Fiber 5 N.B 36 o O. ΰ Q 1 nU, 9 Okina 6 N.B 4 4 o 7 Q 1 o

列 liϋiί | row 7 B 3 9 o 0. Q y Q

o y, y

NT R U. O, 0 0 Q furnace 1 4 1 7. o o

Okinabe 10 N R 4 5 o 6.2.9.8 Okinabe 11 N R 4 3 o 6.0 1 0.3

NR 7 1 X 1 1. 4 1 5.3 Note example 2 2. 3 2.9 o 6.3 7.3 Example 3 N. B 4.1 〇 7.2 1 8.9 Job example 4 N. B '4.2 X water 7

J: 瞧 5 N.B 3.6 〇1 9.3 22.1 Female example 6 N.B 4.2 〇2 1.3.2.4.227 J: t ¾ row 4 due to severe blocking , External haze force, flaw.

Industrial applicability

In the present invention, although the mechanism of the effect of suppressing the pread of low-molecular-weight materials after molding by transparency is not clear, the mechanism of blending the aromatic vinyl compound-hydrogenated conjugated diene compound copolymer is not clear. This is probably because the compatibility between the copolymer block copolymer and the aromatic vinyl compound monohydrogenated conjugated gen compound copolymer is good. Particularly, in the case of an aromatic vinyl compound monohydrogenated conjugated gen compound copolymer having a jib mouth type block type structure, it has good compatibility with the low molecular weight propylene-ethylene copolymer component to be bridged. Therefore, it is considered that these bleeds are suppressed.

On the other hand, in the case of an aromatic-based compound and a hydrogenated conjugated-gen compound copolymer having a random block type structure, it is considered that they are finely dispersed in a propylene-based block copolymer, and therefore, excellent transparency is obtained. It is thought that it can have flexibility.

The resin composition of the present invention is excellent in flexibility, low-temperature impact resistance, and moldability, has excellent transparency after molding, and effectively suppresses low molecular weight components after molding. It can be suitably used in various fields in which conventional thermoplastic elastomers are used. For example, film applications include wrap film, shrink film, storage film, film for sealant, sizing film, adhesive tape, masking film, agricultural film, and medical use. Sheets such as stationery sheets, occlusal sheets, desk mats, agricultural sheets, waterproof sheets, interior skin materials for automobile parts, colum, etc. Gates, wind moldings, air duct hoses, jewelry strips, wire coverings, etc., wallpaper, flooring, molded articles as decorative boxes, decorative bags, and packaging It can be suitably used for boxes, packaging bags, food containers, miscellaneous goods parts, toys and the like. Also, in the injection field, bumpers, matsudogs, horn pads, and lamp packings for automobile parts. 0 Can be suitably used for various molded parts of A equipment.

Claims

The scope of the claims

1. (1) 1 to 70% by weight of eluted components at 100 ° C or more and 99 to 30% by weight of eluted components below 100 ° C as measured by the temperature-elution fractionation method And 100 to 90 mol% of a monomer unit based on propylene of the eluted component at 100 ° C. or higher, 0 to 10 mol% of a monomer unit based on ethylene, A copolymer having 90 to 50 mol% of a monomer unit based on propylene and 10 to 50 mol% of a monomer unit based on ethylene as an elution component at a temperature lower than 0 ° C, Weight average molecular weight (Mw) and number average molecular weight of polymer measured by gel melt chromatography (MFR), gel permeation chromatography

The ratio of (M n) (M w / M n) and 1 is calculated from og ((M wZ M n) x MFR .. 33) force 0. 5 7~: 1. 5, Mw is 80000-1 100,000 parts by weight of propylene-based block copolymer

(2) Fragrance in which the monomer unit based on an aromatic vinyl compound is 5 to 25% by weight, and the monomer unit based on at least a partially conjugated diene compound is 95 to 75% by weight. Aromatic vinyl-hydrogenated conjugated diene copolymer 1 to 10 Q parts by weight

A resin composition comprising:

2. The structure of the aromatic butyl-hydrogenated conjugated copolymer is A_B block copolymer or A_B—A block copolymer (where A is a polymer block based on an aromatic vinyl compound). 2. The resin composition according to claim 1, wherein B is a polymer block based on a conjugated gen compound to which at least a part of hydrogen has been added, or a mixture of these copolymers.

3. The structure of the aromatic vinyl-hydrogenated conjugated gen-based copolymer is as follows: A—C block copolymer, A—C—A block copolymer, A—C—D block copolymer (A Is a polymer block based on an aromatic vinyl compound, C is a random polymer block of a conjugated gen compound at least partially hydrogenated and an aromatic vinyl compound, and D is at least one block of an aromatic vinyl compound. Block copolymer, which is a taper block in which the monomer unit based on an aromatic vinyl compound gradually increases in a polymer block with a hydrogenated conjugated diene compound) or a mixture of these copolymers 2. The resin composition according to claim 1.