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WO2002032996A1 - Composition de resine - Google Patents

Composition de resine Download PDF

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Publication number
WO2002032996A1
WO2002032996A1 PCT/JP2001/009151 JP0109151W WO0232996A1 WO 2002032996 A1 WO2002032996 A1 WO 2002032996A1 JP 0109151 W JP0109151 W JP 0109151W WO 0232996 A1 WO0232996 A1 WO 0232996A1
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Prior art keywords
weight
propylene
copolymer
compound
aromatic vinyl
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Japanese (ja)
Inventor
Hiroaki Takeda
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Idemitsu Petrochemical Co Ltd
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Idemitsu Petrochemical Co Ltd
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Publication of WO2002032996A1 publication Critical patent/WO2002032996A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • the present inventors have disclosed in Japanese Patent Application Laid-Open No. 11-24987.
  • SEBS and SEPS 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ Mw is 80,000 ⁇ 150,000 Propylene block copolymer 100 parts by weight
  • 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.
  • 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
  • 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
  • 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
  • low-temperature elution component 99 to 30% by weight.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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,
  • 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 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
  • MFR ° '33 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.
  • the propylene block copolymer used in the present invention contains a small amount of monomer units based on ⁇ -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.
  • it can be suitably obtained by the following method.
  • 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
  • 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.
  • the titanium trichloride compound include known ", ⁇ a 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.
  • the organic aluminum compound [b] a known compound used for polymerization of the olefin is employed without any limitation.
  • alkylaluminum halides such as chloride and ethylaluminum dichloride.
  • alkyl alkoxy aluminums such as monoethoxy getyl aluminum and ethoxy monoethyl aluminum can be used.
  • 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.
  • 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:
  • the combination of (1) is preferable.
  • R is an iodine atom or an alkyl group having 1 to 7 carbon atoms or a phenyl group.
  • iodine compound [e] examples 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.
  • 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.
  • 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 ⁇ -olefin other than propylene, as long as it does not adversely affect the physical properties of the propylene-based block copolymer.
  • a mixture of ethylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene-11 and propylene may be used.
  • the prepolymerization can be performed in multiple stages, and different ⁇ -olefins can be prepolymerized in each stage, and hydrogen can coexist in each prepolymerization stage.
  • 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.
  • 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.
  • the organoaluminum compound [b] used in the main polymerization 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.
  • 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.
  • propylene is firstly polymerized.
  • the polymerization of propylene may be carried out by polymerizing propylene alone or a mixture of propylene and ⁇ -olefin other than propylene within a range satisfying the requirements of the present invention.
  • 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.
  • 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.
  • 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.
  • random copolymerization of propylene and ethylene is performed.
  • 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.
  • a specific catalyst is selected to produce a propylene block copolymer having the desired molecular weight distribution and crystallinity distribution in one step.
  • 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.
  • 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.
  • 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.
  • additives such as an antioxidant, a heat stabilizer, and a chlorine scavenger
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • kneading of the propylene block copolymer and the organic peroxide is carried out.
  • 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.
  • 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.
  • the melt-kneading can be performed under a stream of an inert gas such as nitrogen gas.
  • preliminary kneading can also be performed using a known mixing device, for example, a tumbler, Henschel mixer or the like.
  • 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.
  • 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.
  • vinyl aromatic compound examples include styrene, o-methylstyrene, alkyl styrene such as ⁇ -methylstyrene and ⁇ _t-butylstyrene, p-methoxystyrene, and bulnaphthalene. Among them, styrene is particularly preferred. New
  • 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.
  • a conjugated gen at least partially hydrogenated hereinafter referred to as a hydrogenated conjugated gen
  • the compatibility with the propylene block copolymer used in the present invention is poor and transparency is impaired, which is not preferred.
  • conjugated diene compounds examples 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.
  • 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.
  • 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.
  • 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
  • A—B—A block copolymers hereinafter also referred to as triblock types
  • a mixture of these copolymers is preferable.
  • 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
  • D is a conjugated gen compound hydrogenated with an aromatic butyl compound.
  • 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
  • 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.
  • 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.
  • the propylene-based polymer include a propylene homopolymer, 90% mol or more of propylene and an ⁇ -olefin other than propylene, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 1 — Heptene.
  • 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 ⁇ ;
  • 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.
  • 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.
  • a known mixing device such as a tumbler or a Henschel mixer can be used without any limitation.
  • 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.
  • the measurement was performed under the following measurement conditions using an SSC-7300 model manufactured by Senshu Ichigaku Co., Ltd.
  • Detector Infrared detector, wavelength 3.14 m
  • the measurement was performed using 13 C-NMR spectrometer using JEOLGSX-270.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • Example 2 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.
  • Example 2 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 2 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.
  • 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 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.
  • 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.
  • Example 2 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.
  • 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.
  • 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.
  • 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 FB3 ⁇ 4 Reinforcement 1 N.B 2.6 o 8 2 8 8 Reinforcement 2 N.B 3 8 o 7 1 R 0 l3 ⁇ 4y class uii 3 N.B 4. .9 o U ⁇ ⁇ o Q
  • 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.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine comprenant (1) 100 parties en poids d'un copolymère séquencé de propylène renfermant entre 1 % et 70 % en poids d'un composé élué à une température supérieure ou égale à 100 °C et entre 30 % et 99 % en poids d'un composé élué à une température inférieure à 100 °C en fonction du procédé de fractionnement par élution à élévation de température, le composé élué à température élevée renfermant entre 90 % et 100 % en mol d'unités monomères de propylène et entre 0 % et 10 % en mol d'unités monomères d'éthylène et le composant élué à température inférieure renfermant entre 50 % et 90 % en mol d'unités monomères de propylène et entre 10 % et 50 % en mol d'unités monomères d'éthylène, satisfaisant la relation suivante : log((Mw/Mn) x MFR0,33)=0,57 à 1,5, dans laquelle MFR représente l'indice de fluidité à chaud du copolymère et Mw et Mn représentent les poids moléculaires moyens en poids et en nombre du copolymère, respectivement, tel qu'il apparaît dans une chromatographie de perméation sur gel, et présentant un poids moléculaire moyen en poids (Mw) compris entre 80'000 et 1'500'000, et (2) entre 1 et 100 parties en poids d'un copolymère renfermant entre 5 % et 25 % en poids d'unités vinyliques aromatiques et entre 75 % et 95 % en poids d'unités diéniques conjuguées au moins partiellement hydrogénées.
PCT/JP2001/009151 2000-10-19 2001-10-18 Composition de resine Ceased WO2002032996A1 (fr)

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JP2000318693 2000-10-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107531565A (zh) * 2015-04-22 2018-01-02 日本瑞翁株式会社 夹层玻璃

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134324A (ja) * 1994-11-15 1996-05-28 Tokuyama Corp 樹脂組成物
JPH1160888A (ja) * 1997-08-27 1999-03-05 Tokuyama Corp 難燃性軟質樹脂組成物
JPH11240987A (ja) * 1997-12-25 1999-09-07 Tokuyama Corp 樹脂組成物
EP0982328A1 (fr) * 1998-08-25 2000-03-01 Tokuyama Corporation Compositions de résine propylénique, procédé pour leur préparation et utilisation
JP2001049060A (ja) * 1999-08-09 2001-02-20 Tokuyama Corp プロピレン系樹脂組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134324A (ja) * 1994-11-15 1996-05-28 Tokuyama Corp 樹脂組成物
JPH1160888A (ja) * 1997-08-27 1999-03-05 Tokuyama Corp 難燃性軟質樹脂組成物
JPH11240987A (ja) * 1997-12-25 1999-09-07 Tokuyama Corp 樹脂組成物
EP0982328A1 (fr) * 1998-08-25 2000-03-01 Tokuyama Corporation Compositions de résine propylénique, procédé pour leur préparation et utilisation
JP2001049060A (ja) * 1999-08-09 2001-02-20 Tokuyama Corp プロピレン系樹脂組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107531565A (zh) * 2015-04-22 2018-01-02 日本瑞翁株式会社 夹层玻璃

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