Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
  • C08F4/652—Pretreating with metals or metal-containing compounds
  • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/16—Ethylene-propylene or ethylene-propylene-diene copolymers

Definitions

• the present invention relates to an effervescent polypropylene composition and an injection foam molded article formed from the composition.
• Polypropylene injection foam molded products have excellent physical properties and are widely used in applications such as automobile parts.
• the effervescent polypropylene composition is required to have high melt fluidity and a high effervescence ratio that can be filled in a thinner mold cavity.
• the effervescent polypropylene composition is also required to have excellent mechanical properties such as high rigidity and high impact resistance.
• Patent Document 1 discloses an effervescent polypropylene composition containing an inorganic filler having an excellent balance between fluidity and mechanical properties.
• Patent Document 2 discloses a method for producing a resin foam, which comprises a step of expanding the volume of the cavity to foam the foamable resin composition after the injection step.
• Patent Document 3 discloses a foamed molded product formed from a composition containing a propylene-based block copolymer using a specific catalyst.
• the foamed molded product disclosed in Patent Document 1 had room for improvement in terms of foaming ratio. Further, the resin foam disclosed in Patent Document 2 does not contain a filler component, and there is room for improvement in terms of rigidity. Further, the composition disclosed in Patent Document 3 has room for improvement in the balance between the fluidity, rigidity and impact resistance and the foaming ratio of the obtained foamed molded product.
• a polypropylene composition containing a filler component such as talc a molded product in a desired foamed state may not be stably obtained when continuously produced under the same injection foam molding conditions. There was room for improvement in. In view of such circumstances, it is an object of the present invention to provide a foamable polypropylene composition which has an excellent balance of fluidity, rigidity and impact resistance and can stably achieve a high foaming ratio.
• (Aspect 1) In the total weight of the components (A1) to (C), As the component (A1), 55 to 80% by weight of a polypropylene composition composed of (A1-1) and (A1-2), (A1-1) Polypropylene 70-85% by weight, (A1-2) 15-30% by weight of propylene-ethylene copolymer containing 25-40% by weight of ethylene-derived units; As the component (A2), 3 to 15% by weight of a polypropylene composition composed of (A2-1) and (A2-2), (A2-1) Polypropylene 50-80% by weight, (A2-2) 20-50% by weight of propylene-ethylene copolymer containing 25-50% by weight of ethylene-derived units; 10 to 20% by weight of elastomer as component (B); The component (C) contains 5 to 15% by weight of the talc-calcium carbonate composite filler, and the component (D) contains a lithium salt, which is 0 based on 100 parts by weight of the total weight of
• An effervescent composition comprising .05 to 0.5 parts by weight; and a foaming agent as component (F).
• It is a polypropylene composition obtained by polymerizing propylene and ethylene using a catalyst containing the mixture, and has an extreme viscosity (XSIV) of a xylene-soluble component of 1.0 to 3.0 dl / g.
• the ultimate viscosity (XSIV) of the xylene-soluble component of the component (A2) is 5.5 to 9.0 dl / g.
• the MFR (temperature 190 ° C., load 2.16 kg) of the component (B) is 20 to 50 g / 10 minutes.
• (Aspect 2) The effervescent polypropylene composition according to embodiment 1, wherein the MFR (temperature 230 ° C., load 2.16 kg) of the component (A1) is 50 to 150 g / 10 minutes.
• (Aspect 3) The effervescent polypropylene composition according to aspect 1 or 2, wherein the MFR (temperature 230 ° C., load 2.16 kg) of the component (A2) is 0.1 to 20 g / 10 minutes.
• (Aspect 4) The effervescent property according to any one of aspects 1 to 3, wherein the lubricant as the component (E) is contained in an amount of 0.05 to 0.5 parts by weight based on 100 parts by weight of the total weight of the components (A1) to (C). Polypropylene composition.
• X to Y includes X and Y which are fractional values thereof.
• the effervescent polypropylene composition of the present invention includes: Component (A1): Polypropylene composition Component (A2): Polypropylene composition having high XSIV Component (B): Elastomer Component (C): Talc-calcium carbonate composite filler Component (D): Lithium salt Component (F): Foaming Agent
• Component (A1) Polypropylene Composition
• the polypropylene composition as component (A1) is made from (A1-1) polypropylene and (A1-2) a propylene-ethylene copolymer containing 25-40% by weight of ethylene-derived units. Become.
• the weight ratio of the components (A1-1) and (A1-2) is 70:30 to 85:15. If the amount of the component (A1-2) exceeds this upper limit, the rigidity of the injection foam molded product decreases, and if it is less than the lower limit, it is necessary to increase the amount of the component (B) in order to maintain impact resistance. , Economic efficiency is reduced. From these viewpoints, the ratio is preferably 75:25 to 80:20.
• the polypropylene component (A1-1) is a homopolymer. However, 0.5% by weight or less of comonomer derived from the mixture of recycled monomers may be contained.
• the component (A1-2) is a propylene-ethylene copolymer and contains 25-40% by weight of ethylene-derived units. If the content of ethylene-derived units is less than the lower limit value or exceeds the upper limit value, the impact resistance of the injection foam molded product is lowered. From these viewpoints, the content of the ethylene-derived unit is preferably 30 to 38% by weight, more preferably 32 to 37% by weight.
• the MFR (temperature 230 ° C., load 2.16 kg) of the component (A1) is preferably 50 to 150 g / 10 minutes, and more preferably 80 to 120 g / 10 minutes. If the MFR exceeds the upper limit, it may be difficult to produce the effervescent polypropylene composition, and the impact resistance of the injection foam molded product may be lowered. Further, if the MFR is less than the lower limit, the fluidity of the effervescent polypropylene composition may decrease.
• the ultimate viscosity (XSIV) of the xylene-soluble component (XS) of the component (A1) is an index of the molecular weight of the non-crystalline component in the component (A1).
• XSIV is obtained by obtaining a component soluble in xylene at 25 ° C. and measuring the ultimate viscosity of the component by a conventional method.
• the XSIV of the component (A1) is 1.0 to 3.0 dl / g, preferably 1.5 to 2.5 dl / g. If the XSIV exceeds the upper limit, lumps or gels may be generated and the appearance of the injection foam molded product may be deteriorated. If the XSIV is less than the lower limit, the impact resistance of the injection foam molded product may decrease.
• the amount of the component (A1) is 55 to 80% by weight with respect to the total weight of the components (A1) to (C). If the amount is less than the lower limit, the fluidity of the effervescent polypropylene composition is lowered and the rigidity of the injection foam molded product is lowered. Further, when the amount exceeds the upper limit value, the impact resistance of the injection foam molded product is lowered. From these viewpoints, the amount of the component (A1) is preferably 60 to 75% by weight. In the present invention, the total weight of the components (A1) to (C) is the total weight of the components (A1), (A2), (B), and (C).
• the component (A1) is a solid containing the raw material monomers of the component (A1-1) and the component (A1-2) and an internal electron donor selected from (component a) magnesium, titanium, halogen, and a succinate compound. It is produced by a method including a step of polymerizing using a catalyst containing a catalyst, (component b) an organoaluminum compound, and (component c) an external electron donor compound. Succinate compounds give a wide molecular weight distribution. Generally, it is known that the molecular weight distribution can be increased by polymerizing in multiple steps, but a polypropylene composition polymerized using the catalyst is a pellet or powder blend of a polymer polymerized using another catalyst.
• the component (A1) produced by using the catalyst has a wide molecular weight distribution in which a high molecular weight component and a low molecular weight component are integrated in a state close to the molecular level. Therefore, the effervescent polypropylene composition containing the component (A1) can push the mold with a strong force during injection foam molding, and as a result, uniform effervescence becomes possible.
• the catalyst will be described.
• the component a can be prepared by a known method, for example, by bringing the magnesium compound, the titanium compound, and the succinate compound as the internal electron donor compound into mutual contact.
• the succinate compound is a succinic acid diester or a substituted succinic acid diester.
• the succinate-based compound preferably used in the present invention is represented by the following formula (I).
• the groups R 1 and R 2 are linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkyl of C 1 to C 20 , which are the same or different from each other and sometimes contain a heteroatom.
• Aryl groups; groups R 3 to R 6 are linear or branched alkyl, alkenyl, cycloalkyl, aryl, of C 1 to C 20 , which are identical or different from each other and contain hydrogen or, in some cases, heteroatoms.
• Groups R 3 to R 6 which are arylalkyl or alkylaryl groups and are bonded to the same or different carbon atoms, may be bonded together to form a ring.
• R 1 and R 2 are preferably C 1 to C 8 alkyl, cycloalkyl, aryl, arylalkyl, and alkylaryl groups.
• suitable R 1 and R 2 groups are alkyl groups C 1 to C 8 , such as methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Ethyl, isobutyl, and neopentyl are particularly preferred.
• One of the preferred groups of compounds represented by formula (I) is branched alkyl, cycloalkyl, aryl, arylalkyl, where R 3 to R 5 are hydrogen and R 6 has 3 to 10 carbon atoms. , And an alkylaryl group.
• Preferred specific examples of such a monosubstituted succinate compound are diethyl-sec-butyl succinate, diethyl texyl succinate, diethyl cyclopropyl succinate, diethyl norbonyl succinate, diethyl perihydro succinate, diethyl.
• Another preferred group of compounds within the range of formula (I) is a linear C 1 to C 20 in which at least two groups from R 3 to R 6 differ from hydrogen and in some cases contain heteroatoms. Alternatively, it is selected from branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups.
• a compound in which two groups different from hydrogen are bonded to the same carbon atom is particularly preferable. Specifically, it is a compound in which R 3 and R 4 are different groups from hydrogen, and R 5 and R 6 are hydrogen atoms.
• disubstituted succinates are diethyl-2,2-dimethylsuccinate, diethyl-2-ethyl-2-methylsuccinate, diethyl-2-benzyl-2-isopropylsuccinate, diethyl.
• compounds in which at least two groups different from hydrogen are bonded to different carbon atoms are also particularly preferable.
• R 3 and R 5 are different groups from hydrogen.
• R 4 and R 6 may be hydrogen atoms or groups different from hydrogen, but it is preferable that one of them is a hydrogen atom (trisubstituted succinate).
• Preferred specific examples of such compounds are diethyl-2,3-bis (trimethylsilyl) succinate, diethyl-2,2-sec-butyl-3-methylsuccinate, diethyl-2- (3,3,3-).
• the compounds are several forms a ring together of the radicals R 3 ⁇ R 6 can also be preferably used.
• the compounds listed in Special Table 2002-542347 for example, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2,6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1-( Ethoxyacetyl) -2,51 dimethylcyclopentane, 1- (ethoxycarbonyl) -1- (ethoxyacetylmethyl) 2-1methylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxy (cyclohexyl) acetyl) cyclohexane Can be mentioned.
• cyclic succinate compounds such as diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylic acid and diisobutyl cyclohexane-1,2-dicarboxylic acid as disclosed in International Publication No. 2009/069483 are also preferable. Can be used. As an example of other cyclic succinate compounds, the compounds disclosed in WO 2009/0577747 are also preferred.
• group R 3 ⁇ R 6 is a hetero atom
• it heteroatom is 16 atoms containing Group 15 atom or an oxygen and sulfur atom containing nitrogen and phosphorus atoms preferable.
• Examples of the compound in which the groups R 3 to R 6 contain a Group 15 atom include compounds disclosed in JP-A-2005-306910.
• group R 3 ⁇ R 6 is The compound containing a Group 16 atom include compounds disclosed in JP-2004-131537.
• Organoaluminium compound (component b)
• organoaluminum compound of component b examples include the following.
• Trialkylaluminum such as triethylaluminum and tributylaluminum
• Trialkenyl aluminum such as triisoprenyl aluminum:
• Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide
• Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxydo and butylaluminum sesquibutoxide;
• Partially halogenated alkylaluminum such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, diethylaluminum chloride, dipropylaluminum chloride, dibutylaluminum chloride; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; partially hydrogenated alkylaluminum such as alkylaluminum hydrides such as ethylaluminum dihydride and propylaluminum dihydride; Partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butokicyclolide, ethylaluminum ethoxybromid.
• External electron donor compound (component c)
• the electron donor compound of component c which is used separately from the internal electron donor contained in component a, is generally referred to as "external electron donor".
• an external electron donor compound an organosilicon compound is preferable.
• Preferred organosilicon compounds include: Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyl Dimethoxysilane, diphenyldiethoxysilane, biso-tolyldimethoxysilane, bism-tolyldimethoxysilane, bisp-tolyldimethoxysilane, bisp-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane Silane, Cyclohexylmethyldimethoxysi
• ethyltriethoxysilane n-propyltriethoxysilane, n-propyltrimethoxysilane, t-butyltriethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-butylethyldimethoxysilane, t-Butylpropyldimethoxysilane, t-butylt-butoxydimethoxysilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane, isobutylmethyldimethoxysilane, i-butylsec-butyldimethoxysilane, ethyl (perhydroisoquinolin 2- Il) dimethoxysilane, bis (decahydroisoquinolin-2-yl) dimethoxysilane, tri (isopropyldime
• the raw material monomer is brought into contact with the catalyst prepared as described above to polymerize. At this time, prepolymerization may be performed using the catalyst.
• the prepolymerization is a step of forming a polymer chain as a foothold for the subsequent main polymerization of the raw material monomer in the solid catalyst component.
• Prepolymerization can be carried out by a known method.
• the prepolymerization is usually carried out at 40 ° C. or lower, preferably 30 ° C. or lower, and more preferably 20 ° C. or lower.
• the prepolymerized catalyst (prepolymerization catalyst) is introduced into the polymerization reaction system to carry out the main polymerization of the raw material monomer.
• the polymerization may be carried out in a liquid phase, a gas phase or a liquid-gas phase.
• the polymerization temperature is preferably 0 to 90 ° C, more preferably 20 to 80 ° C.
• the polymerization pressure is preferably in the range of 0.8 to 6.0 MPa when carried out in the liquid phase, and preferably in the range of 0.5 to 3.0 MPa when carried out in the gas phase.
• a trace amount of a conventional molecular weight adjusting agent known in the art such as a chain transfer agent (for example, hydrogen or ZnEt 2 ) can be used.
• a known method can be used for the polymerization of the component (A1) or the component (A2). For example, polymerizing the raw material monomers of the component (A1-1) and the component (A1-2) or the raw material monomers of the component (A2-1) and the component (A2-2) using two or more reactors. Is preferable. Further, a polymerizer having a gradient of monomer concentration and polymerization conditions may be used. In such a polymerizer, for example, one in which at least two polymerization regions are connected can be used, and the monomer can be polymerized by vapor phase polymerization.
• a monomer is supplied and polymerized in a polymerization region consisting of an ascending tube, and a monomer is supplied and polymerized by a descending tube connected to the ascending tube.
• the polymer product is recovered while circulating.
• This method comprises means to prevent the gas mixture present in the ascending tube from entering the descending tube in whole or in part. Further, a gas or liquid mixture having a composition different from that of the gas mixture existing in the rising pipe is introduced into the falling pipe.
• the above polymerization method for example, the method described in JP-A-2002-520426 can be applied.
• Component (A2) Polypropylene composition
• the polypropylene composition as the component (A2) is polypropylene (A2-1) homopolymer (however, 0.5% by weight or less derived from the mixing of recycled monomers or the like). It may contain a comonomer) and (A2-2) consists of a propylene-ethylene copolymer containing 25-50% by weight of ethylene-derived units. The weight ratio of the two is 50:50 to 80:20, preferably 55:45 to 75:25, and more preferably 60:40 to 70:30.
• the ethylene-derived unit of (A2-2) is preferably 25 to 45% by weight, particularly preferably 30 to 40% by weight. It is considered that the component (A2) has an affinity for both the component (A1) and the component (B), and as a result, the balance between the rigidity and the impact resistance in the composition is maintained.
• the ultimate viscosity (XSIV) of the xylene-soluble component of the component (A2) is 5.5 to 9.0 dl / g, which is higher than that of the component (A1) XSIV.
• the xylene-soluble component is a component soluble in xylene at 25 ° C. and corresponds to an amorphous component. That is, since the component (A2) contains an amorphous high molecular weight component, it is considered that the appearance defect of the injection foam molded product is reduced by suppressing the foam breakage during molding. Specifically, the component (A2) can reduce the streaky or spiral-shaped swirl marks that occur on the surface of the injection-foamed molded product.
• XSIV exceeds the upper limit, the fluidity of the effervescent polypropylene composition decreases. From these viewpoints, XSIV is preferably 6.0 to 8.0 dl / g.
• the MFR (temperature 230 ° C., load 2.16 kg) of the component (A2) is preferably 0.1 to 20 g / 10 minutes, and more preferably 0.5 to 5 g / 10 minutes. If the MFR exceeds the upper limit, it may be difficult to produce the component (A2), and the foaming properties of the expandable polypropylene composition may be deteriorated. Further, if the MFR is less than the lower limit, the production of the component (A2) may be difficult, and the fluidity of the effervescent polypropylene composition may be lowered.
• the amount of the component (A2) is 3 to 15% by weight based on the total weight of the components (A1) to (C). If the amount is less than the lower limit, swirl marks are likely to occur on the surface of the injection foam molded product and the appearance is deteriorated. Further, when the amount exceeds the upper limit value, the fluidity of the effervescent polypropylene composition decreases. From these viewpoints, the amount of the component (A2) is preferably 5 to 10% by weight.
• Component (B) Elastomer
• the elastomer is a polymer having elasticity.
• the elastomer used in the present invention is different from the propylene-ethylene copolymer of the component (A1-2) and the component (A2-2).
• the amount of the component (B) is 10 to 20% by weight based on the total weight of the components (A1) to (C).
• the component (B) improves the impact resistance of the injection foam molded product, the appearance and scratch resistance of the injection foam molded product. On the other hand, if the amount of the component (B) is excessive, the rigidity of the injection foam molded product is lowered, and the economy is also lowered. From these viewpoints, the amount of the component (B) is preferably 12 to 18% by weight.
• MFR 190 ° C. The MFR at an elastomer temperature of 190 ° C. and a load of 2.16 kg (hereinafter, the MFR measured under these conditions is also referred to as “MFR 190 ° C. ”) is 20 to 50/10 minutes. If the MFR 190 ° C. exceeds the upper limit, the production of the component (B) becomes difficult, and the impact resistance of the injection foam molded product deteriorates. If the MFR of 190 ° C. is less than the lower limit, the fluidity of the effervescent polypropylene composition decreases. From these viewpoints, MFR 190 ° C. is preferably 25 to 40 g / 10 minutes.
• the elastomer examples include a copolymer of ethylene and ⁇ -olefin.
• the ⁇ -olefin include ⁇ -olefins having 3 to 12 carbon atoms, and specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and the like are preferable.
• the elastomer preferably has a lower density than the propylene-ethylene copolymer of component (A1-1) and component (A1-2).
• the density of the elastomer is not limited is 0.850 ⁇ 0.890g / cm 3, more preferably 0.860 ⁇ 0.880g / cm 3.
• Such an elastomer can be prepared, for example, by polymerizing a monomer using a homogeneous catalyst such as metallocene or half metallocene as described in Japanese Patent Application Laid-Open No. 2015-113363.
• the talc-calcium carbonate composite filler is a composite filler in which calcium carbonate fine particles are present on the surface of talc, and for example, those disclosed in JP-A-2002-80631 are used. it can.
• the weight ratio of talc to calcium carbonate is not limited, but is preferably 80:20 to 20:80, more preferably 70:30 to 30:70. If the amount of talc is small, the rigidity of the injection foam molded product may decrease. Further, if the amount of calcium carbonate is small, the uniformity of the foamed molded product may decrease. From these viewpoints, the weight ratio is more preferably 70:30 to 55:45.
• the filler reduces appearance defects called swirl marks that occur on the surface of the molded product by suppressing the foaming of the foamable polypropylene composition during molding.
• the reason for this is not limited, but it is considered that calcium carbonate having a particle size smaller than that of talc is finely dispersed in the effervescent polypropylene composition.
• the average particle size of the talc constituting the filler is preferably 1 to 10 ⁇ m, more preferably 2 to 8 ⁇ m.
• the average particle size of talc is measured by laser diffraction / scattering method according to JIS Z8825.
• the average particle size of calcium carbonate constituting the filler is preferably 30 to 500 nm, more preferably 50 to 200 nm.
• the average particle size of calcium carbonate is measured by electron microscopy.
• the amount of the component (C) is 5 to 15% by weight with respect to the total weight of the components (A1) to (C). If the amount is less than the lower limit, the foaming characteristics of the effervescent polypropylene composition are lowered, and the rigidity of the injection foam molded product is lowered. Further, when the amount exceeds the upper limit value, the density of the injection foam molded product increases, and it becomes difficult to reduce the weight. From these viewpoints, the amount of the component (C) is preferably 8 to 12% by weight.
• Lithium salt is used to achieve uniform foaming.
• the lithium salt include inorganic salts such as lithium carbonate, lithium chloride, lithium bromide, lithium fluoride and lithium nitrite, and organic salts such as lithium stearate. Of these, lithium carbonate is preferable from the viewpoint of foaming uniformity and availability.
• the average particle size of the inorganic salt such as lithium carbonate measured by the laser diffraction / scattering method is preferably 1 to 10 ⁇ m, more preferably 2 to 8 ⁇ m.
• the inorganic salt which has a different shape from talc, which is a plate-like filler contained in the component (C), and a particle size different from that of calcium carbonate, is uniformly dispersed in the composition, so that the bubble size becomes uniform during foaming. It is believed that it is easy and as a result more uniform foaming is achieved.
• the amount of the component (D) is 0.05 to 0.5 parts by weight with respect to 100 parts by weight of the total weight of the components (A1) to (C). If the amount is less than the lower limit, the effect cannot be achieved. Moreover, even if the amount exceeds the upper limit, the effect will reach a plateau and the economic efficiency will decrease. From these viewpoints, the amount of the component (D) is preferably 0.1 to 0.4 parts by weight.
• a decomposition type foaming agent or a solvent type foaming agent can be used.
• the decomposition type foaming agent is a compound that decomposes under the cylinder temperature condition of an injection molding machine to generate a gas such as carbon dioxide gas or nitrogen gas.
• a gas such as carbon dioxide gas or nitrogen gas.
• the decomposable foaming agent either an inorganic type or an organic type can be used.
• Examples of the inorganic decomposition foaming agent include sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, ammonium nitrite and the like.
• Examples of the organic decomposition foaming agent include N-nitroso compounds such as N, N'-dinitrosoterephthalamide and N, N'-dinitrosopentamethylenetetramine; azodicarboxylicamide, azobisisobutyronitrile, and azocyclohexyl.
• Azo compounds such as nitriles, azodiaminobenzenes, barium azodicarboxylates; Sulfonyl hydrazide compounds; examples thereof include azo compounds such as calcium azide, 4,4'-diphenyldisulfonyl azide, and p-toluene sulfonyl azide.
• hydrogen carbonate such as sodium hydrogen carbonate is preferable from the viewpoint of having less impact on the environment, being safe, and stabilizing the effervescent cell.
• citric acid and malic acid are used as auxiliary agents. It is preferable to use an organic carboxylic acid such as acid, tartrate, and lactic acid, or an organic carboxylic acid salt such as sodium citrate, calcium citrate, sodium malate, sodium tartrate, and sodium lactate in combination.
• the blending ratio of the hydrogen carbonate and the auxiliary agent is preferably 10 to 70% by weight of the hydrogen carbonate and 30 to 90% by weight of the auxiliary agent.
• the solvent-type foaming agent is a substance that functions as a foaming agent by injecting it into a composition containing no foaming agent from the cylinder portion of the injection molding machine and evaporating it in the injection molding mold.
• Low-boiling aliphatic hydrocarbons such as propane, butane, neopentane, heptane, isohexane, hexane, isoheptane, and heptane, and low-boiling fluorine-containing hydrocarbons typified by freon gas can be used.
• the foaming agent used in the foamable polypropylene composition of the present invention can be added in the form of a foaming agent masterbatch using polyolefin as a carrier.
• the polyolefin include polypropylene, polyethylene, polystyrene and the like.
• the carriers contained in the masterbatch correspond to other components described later.
• the content of the decomposing foaming agent contained in the foaming agent masterbatch is usually 5 to 80% by weight, preferably 10 to 70% by weight, and a commercially available product can be used as it is.
• the amount of the foaming agent added is defined as the amount of the components (A1) to (C) with respect to 100 parts by weight of the total weight.
• the lower limit is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more.
• the upper limit is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and further preferably 3 parts by weight or less. Further, within this range, the optimum amount is selected in consideration of the amount of generated gas, the foaming ratio, and the like.
• the foamable polypropylene composition of the present invention preferably contains a lubricant as the component (E).
• Lubricants are additives used to reduce friction. In the present invention, the lubricant improves the scratch resistance of the injection foam molded product.
• Known lubricants can be used, but fatty acid amides are preferable, and higher fatty acid amides are more preferable, from the viewpoint of availability.
• the fatty acid constituting the fatty acid amide may be a saturated fatty acid or an unsaturated fatty acid.
• the higher fatty acid group has 10 or more carbon atoms, preferably 12 or more carbon atoms.
• Specific higher fatty acid amides include saturated fatty acid amides such as lauric acid amide, palmitate amide, stearic acid amide, and behemic acid amide; Saturated fatty acid amides; examples thereof include bis fatty acid amides such as methylene bisstearic acid amide, methylene bisstearic acid amide, ethylene bisstearic acid amide, and ethylene bisoleic acid amide. Of these, erucic acid amide, oleic acid amide, and ethylene bisoleic acid amide are preferable.
• the amount of the lubricant (component (E)) is preferably 0.05 to 0.5 parts by weight, more preferably 0.1 to 0, based on 100 parts by weight of the total weight of the components (A1) to (C). .4 parts by weight. If the amount is less than the lower limit, the effect of improving the scratch resistance of the effervescent polypropylene composition may not be sufficient. Moreover, even if the amount exceeds the upper limit, the effect may reach a plateau and the economic efficiency may decrease.
• the effervescent polypropylene composition includes antioxidants, chlorine absorbers, heat stabilizers, light stabilizers, ultraviolet absorbers, antiblocking agents, antistatic agents, crystal nucleating agents, antifogging agents, etc.
• antioxidants chlorine absorbers, heat stabilizers, light stabilizers, ultraviolet absorbers, antiblocking agents, antistatic agents, crystal nucleating agents, antifogging agents, etc.
• additives commonly used in the art such as flame retardants, dispersants, copper damage inhibitors, neutralizers, plasticizers, crosslinkers, peroxides, oil spreads, and other organic and inorganic pigments. You may.
• the amount of each additive added may be a known amount.
• the effervescent polypropylene composition may contain a resin or elastomer other than the components (A1) to (B) as long as the effects of the present invention are not impaired.
• the effervescent polypropylene composition may contain only one type of resin or elastomer, or two or more types. The content may be a known amount.
• the MFR (temperature 230 ° C., load 2.16 kg) of the effervescent polypropylene composition of the present invention is 40 to 80 g / 10 minutes when a foaming agent is not contained (hereinafter, also referred to as “non-expandable polypropylene composition”). .. If the MFR exceeds the upper limit value, the impact resistance of the injection foam molded product is lowered, and if it is less than the lower limit value, the fluidity of the foamable polypropylene composition is lowered. From these viewpoints, the upper limit is preferably 70 g / 10 minutes or less, more preferably 66 g / 10 minutes or less. The lower limit is preferably 50 g / 10 minutes or more, and more preferably 54 g / 10 minutes or more.
• the density of the non-foaming polypropylene composition is preferably 1.00 g / cm 3 or less, and more preferably 0.98 g / cm 3 or less.
• the flexural modulus of the non-foaming polypropylene composition is preferably 1000 MPa or more, more preferably 1100 MPa or more, still more preferably 1200 MPa or more at 23 ° C.
• Charpy impact strength of impact resistance non-foamed polypropylene composition at 23 ° C. preferably 10 kJ / m 2 or more, more preferably 20 kJ / m 2 or more, more preferably 25 kJ / m 2 or more.
• the Charpy impact strength is preferably 2.0 kJ / m 2 or more, more preferably 2.5 kJ / m 2 or more, and further preferably 3.0 kJ / m 2 or more at ⁇ 30 ° C.
• the effervescent polypropylene composition of the present invention comprises components (A1) to (D) and, if necessary, other components such as component (E) and additives, or both. Is melt-kneaded to produce a non-foamable polypropylene composition, which is dry-blended with a foaming agent (component (F)).
• the dry blend may be melt-kneaded before molding in an extruder attached to an injection molding machine.
• Each component is prepared as described above.
• a foaming agent masterbatch using polyolefin as a carrier may be used as a carrier.
• the non-foamable polypropylene composition can be prepared and mixed with the solvent-type foaming agent in an injection molding machine as described above to produce a foamable polypropylene composition.
• An injection-foamed molded article can be produced by injection-foaming the effervescent polypropylene composition of the present invention.
• the injection foam molding process includes an injection process and a foaming process. Injection foam molding can be roughly divided into a method in which the volume of the cavity is not changed and a method in which the volume is changed.
• the former is a method in which a foamable polypropylene composition is filled in a cavity of a mold, and a foaming agent is vaporized and foamed inside the molded product by a pressure decrease accompanying shrinkage of a polymer component.
• the latter is a method of foaming by core backing the mold or moving a slide core or the like in the mold to expand the volume of the cavity during or after filling the cavity with the foamable polypropylene composition. is there. In the latter case, it is preferable to expand the volume of the cavity faster than the expansion rate of the effervescent polypropylene composition.
• the molding temperature is generally 150 to 350 ° C, preferably 170 to 250 ° C. If the molding temperature exceeds 350 ° C., it causes deterioration of the composition and molding defects, and if it is lower than 150 ° C., poor appearance such as insufficient filling, sink marks or warpage, and molding defects occur.
• the mold temperature is preferably 10 to 60 ° C. When the mold temperature exceeds 60 ° C., an injection foam molded product having excellent surface finish and excellent rigidity can be obtained, but the molding cycle becomes long and the productivity decreases. On the contrary, when the mold temperature is lower than 10 ° C., sink marks, warpage, shrinkage, etc. become remarkable, and it becomes difficult to obtain a satisfactory injection foam molded product. Furthermore, since dew condensation is likely to occur on the mold, it causes the mold to corrode, and the energy cost for cooling also increases.
• the foaming ratio of the injection foam molded product is preferably 1.8 or more, more preferably 2.0 or more, still more preferably 2.2 or more.
• the injection foam molded product of the present invention is useful as a molded product for automobile interior parts.
• the molded product for automobile interior parts include a door trim, a glove box, a column cover, an instrument panel, a package tray, a rear tray, a pillar garnish, a console box, and the like.
• the molded body has ribs formed on the non-designed surface. Since the effervescent polypropylene composition of the present invention has a large MFR and high fluidity, the groove for forming the rib of the mold can be sufficiently filled with the molten resin. Furthermore, the generation of swirl marks and the like is suppressed, and an injection foam molded product having an excellent appearance is provided. In particular, the effervescent polypropylene composition of the present invention exerts a remarkable effect in application to a door trim having a large design surface area.
• Prepolymerization was carried out by holding the obtained catalyst system in a suspended state in liquid propylene at 20 ° C. for 5 minutes.
• the obtained prepolymer is introduced into the first-stage liquid-phase polymerization reactor of a polymerization apparatus equipped with a two-stage polymerization reactor in series to produce a propylene homopolymer (component (A1-1)), and two A propylene-ethylene copolymer (component (A1-2)) was produced in the gas phase polymerization reactor of the stage.
• the temperature and pressure were adjusted, and hydrogen was used as a molecular weight modifier.
• the ratio of the polymerization temperature to the reactants was as follows: in the first stage reactor, the polymerization temperature and hydrogen concentration were 70 ° C. and 1.83 mol%, respectively, and in the second stage reactor, the polymerization temperature and hydrogen concentration, C2 / ( C2 + C3) had a ratio of 80 ° C., 2.45 mol% and 0.29 mol, respectively. Further, the residence time distributions of the first stage and the second stage were adjusted so that the amount of the copolymer component was 22% by weight. To 100 parts by weight of the obtained polymer, 0.1 part by weight of BASF B225 as an antioxidant and 0.05 part by weight of Tannan Chemical Co., Ltd.
• the obtained prepolymer was introduced into the first-stage liquid-phase polymerization reactor of a polymerization apparatus equipped with a two-stage polymerization reactor in series to produce a propylene homopolymer (component (A1-1)).
• a propylene-ethylene copolymer (component (A1-2)) was produced in the gas phase polymerization reactor of the stage.
• the temperature and pressure were adjusted, and hydrogen was used as a molecular weight modifier.
• the polymerization temperature and the hydrogen concentration were 70 ° C. and 4.08 mol%, respectively.
• the obtained prepolymer is introduced into the first-stage gas-phase polymerization reactor of a polymerization apparatus equipped with a three-stage gas-phase polymerization reactor in series to produce a propylene homopolymer, and the second-stage gas-phase polymerization is produced.
• a propylene-ethylene copolymer was produced in the reactor, and a propylene homopolymer was produced in the third-stage gas phase polymerization reactor.
• the unreacted monomer was removed before introducing the polymer obtained in the first stage into the second stage and before introducing the polymer obtained in the second stage into the third stage.
• the temperature and pressure were adjusted, and hydrogen was used as the molecular weight modifier.
• the polymerization temperature and H2 / C3 were 65 ° C. and 0.002 molar ratios, respectively.
• the polymerization temperature, H2 / C2, and C2 / (C2 + C3) were 75 ° C., 0.006 molar ratio, and 0.25 molar ratio, respectively.
• the polymerization temperature and H2 / C3 were 75 ° C. and 0.644 molar ratios, respectively.
• the amounts of the first-stage propylene homopolymer component, the second-stage copolymer component, and the third-stage propylene homopolymer component are 35% by weight, 35% by weight, and 30% by weight, respectively.
• the residence time distributions of the eyes and the third stage were adjusted.
• Non-foamable polypropylene composition The components (A1) to (C) are blended in the composition shown in Table 1, and the components (D) to (D) to 100 parts by weight of the total weight of the components (A1) to (C). (E) is added in the amounts shown in Table 1, 0.1 parts by weight of BASF B225 as an antioxidant, 0.3 parts by weight of Adecastab LA502XP manufactured by ADEKA Co., Ltd. as a weather resistant agent, and Kao shares as an antioxidant. 0.3 parts by weight of TS-5 manufactured by the company and 0.2 parts by weight of magnesium stearate GR manufactured by Nichiyu Co., Ltd.
• Foam molded product 3 parts by weight of a foaming agent masterbatch (including component (F)) is added to the above non-foamable polypropylene composition, melt-kneaded in the cylinder of an injection molding machine, and then injected under the following conditions. Foam molding was performed to produce an injection foam molded product.
• the foaming agent masterbatch contains a degradable foaming agent and polyethylene as a carrier.
• the evaluation results of the foam molded product are shown in Table 1. The amount of the foaming agent with respect to 100 parts by weight of the total weight of the components (A1) to (C) was about 2 parts by weight.
• injection foam molding conditions As an injection molding machine, an injection molding machine manufactured by JSW Co., Ltd. (equipped with a single flight screw having a screw diameter of 53 mm ⁇ and a screw stroke of 210 mm) was used. As a mold, a flat plate molding mold (cavity surface is a mirror surface) having a cavity of 200 mm ⁇ 400 mm manufactured assuming automobile interior parts and having strength reinforcing ribs (height 10 mm ⁇ thickness 1 mm) formed on one side. ) was used. The conditions were set as follows.
• the non-foamable polypropylene composition of the present invention has, in addition to excellent rigidity and impact resistance, a characteristic that the maximum foaming ratio is high when a foaming agent is added to obtain a foamable composition. From the above, it is clear that the effervescent polypropylene composition of the present invention provides a foam molded product useful as an automobile interior part or the like.
• the maximum value was defined as the maximum foaming ratio. That is, the composition in which a high foaming ratio is observed in the evaluation is a composition capable of stably achieving a high foaming ratio.
• a surface measuring machine HIDON-14D manufactured by Shinto Kagaku Co., Ltd.
• the brightness difference ⁇ L * between the scratched portion and the normal portion on the surface of the foamed molded product was measured by a spectrocolorimeter (SE2000 manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS Z8730.
• ⁇ L * is an index of scratch resistance, and the smaller this value is, the better the scratch resistance is.
• the ⁇ L * of the injection foam molded product is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.5 or less.
• Amount of component (A1) or copolymer of component (A2)> It was calculated by the following formula.
• Amount of copolymer (% by weight) total ethylene content of composition / (content of ethylene-derived units in copolymer / 100)

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• 2020
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