WO2014046086A1 - ポリプロピレン系樹脂組成物およびその用途 - Google Patents
ポリプロピレン系樹脂組成物およびその用途 Download PDFInfo
- Publication number
- WO2014046086A1 WO2014046086A1 PCT/JP2013/075030 JP2013075030W WO2014046086A1 WO 2014046086 A1 WO2014046086 A1 WO 2014046086A1 JP 2013075030 W JP2013075030 W JP 2013075030W WO 2014046086 A1 WO2014046086 A1 WO 2014046086A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- propylene
- parts
- ethylene
- mol
- Prior art date
Links
Images
Classifications
-
- 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
- C08L23/12—Polypropene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D25/00—Superstructure or monocoque structure sub-units; Parts or details thereof not otherwise provided for
- B62D25/04—Door pillars ; windshield pillars
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D29/00—Superstructures, understructures, or sub-units thereof, characterised by the material thereof
- B62D29/04—Superstructures, understructures, or sub-units thereof, characterised by the material thereof predominantly of synthetic material
- B62D29/043—Superstructures
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/16—Anti-static materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0085—Copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
- B29L2031/3005—Body finishings
- B29L2031/3041—Trim panels
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention relates to a polypropylene resin composition and its use. Specifically, the present invention relates to a polypropylene resin composition suitable for manufacturing automobile interior and exterior parts such as pillar trim materials, door trims, door panels, and the like, and a molded body comprising the same.
- Patent Document 1 a method for improving hardness by using a resin component having excellent crystallinity
- Patent Document 2 a polypropylene composition having high Izod impact strength and scratch whitening load, including talc and a scratch modifier A thing (refer patent document 3) etc. were proposed. According to these methods, the resistance to scratches caused by scratching can be improved to some extent.
- An object of the present invention is to provide a polypropylene resin composition and a molded product comprising the same.
- the polypropylene resin composition of the present invention is (A) (a-1) A structure in which a melt flow rate (MFR, 230 ° C., 21.16 N load) measured by a method according to JIS K 7210 is 10 g / 10 min or more and 300 g / 10 min or less and is derived from propylene
- MFR melt flow rate
- JIS K 7210 a melt flow rate measured by a method according to JIS K 7210
- the content of the unit is 98 mol% or more and 100 mol% or less
- the content of the structural unit derived from at least one ⁇ -olefin selected from ethylene and an ⁇ -olefin having 4 to 8 carbon atoms is 0 mol% or more and 2 mol% or less.
- a propylene / ethylene copolymer having an intrinsic viscosity [ ⁇ ] measured in decalin of 135 ° C. of 1.5 dl / g or more and 8 dl / g or less and a content of structural units derived from ethylene of 30 mol% or more and 60 mol% or less.
- a polypropylene resin comprising 0 to 30 parts by weight of a polymer, and the total of (a-1) and (a-2) being 30 to 80 parts by weight; (B) an ethylene / ⁇ -olefin copolymer 20 comprising ethylene and at least one ⁇ -olefin selected from ⁇ -olefins having 3 to 8 carbon atoms and having an ethylene content of 65 mol% or more and 90 mol% or less.
- the fatty acid amide is at least one selected from fatty acid amides having 8 to 25 carbon atoms and dimers thereof, and
- the (D) surfactant is preferably a compound having one or two ester groups having 8 to 25 carbon atoms.
- the molded product of the present invention is composed of the above-described polypropylene resin composition of the present invention.
- Such a molded article of the present invention is preferably an injection molded article.
- the molded body of the present invention is preferably an automobile interior / exterior member, and more preferably, the automobile interior / exterior member is an automobile door member or a pillar member.
- the present invention it is excellent in moldability such as injection moldability, rigidity, impact resistance and the like, and it is effective for deterioration of surface properties due to friction with soft materials such as rubber-like materials (foot kick resistance). It is possible to provide a polypropylene-based resin composition that can produce a molded product that is suppressed.
- the molded article of the present invention is excellent in rigidity, impact resistance and the like, and has excellent surface lubricity, and the surface properties are not easily deteriorated when subjected to friction by a soft material, particularly for automotive interior and exterior parts. It can be used suitably.
- FIG. 1 shows an outline of a scuff foot kick test apparatus used in the examples.
- FIG. 2 shows an overview of the test piece after the scuff foot kick test in Example 3 and Comparative Example 1.
- the polypropylene resin composition of the present invention comprises a polypropylene resin (A), an ethylene / ⁇ -olefin copolymer (B), and, if necessary, (E) a base material component comprising an inorganic filler, a fatty acid amide ( C) and surfactant (D).
- the base material component constituting the polypropylene resin composition of the present invention comprises a polypropylene resin (A), an ethylene / ⁇ -olefin copolymer (B), and, if necessary, (E) an inorganic filler. Consists of.
- the polypropylene resin (A) contains (a-1) a propylene polymer as an essential component, and (a-2) a propylene / ethylene copolymer as necessary.
- the propylene polymer of the component (a-1) according to the present invention is a homopolymer of propylene or a copolymer of propylene and a small amount of ⁇ -olefin.
- the ⁇ -olefin is at least one ⁇ -olefin selected from ethylene and an ⁇ -olefin having 4 to 8 carbon atoms, preferably ethylene.
- the propylene polymer (a-1) is a copolymer of propylene and a small amount of ⁇ -olefin
- the content of the structural unit derived from propylene is 98 mol% or more
- the structural unit derived from the ⁇ -olefin Is 2 mol% or less.
- the melt flow rate (MFR, 230 ° C., 21.16 N load) of the propylene polymer (a-1) measured by a method according to JIS K 7210 is usually 10 g / 10 min or more and 300 g / 10 min or less.
- a preferable lower limit of the melt flow rate is 30 g / 10 min, a more preferable lower limit is 50 g / 10 min, a preferable upper limit is 270 g / 10 min, and a more preferable upper limit is 250 g / 10 min.
- Such a propylene polymer (a-1) is not particularly limited, and polymerizes propylene alone or together with a small amount of ⁇ -olefin as necessary in the presence of a known olefin polymerization catalyst. Alternatively, it can be obtained by copolymerization.
- the olefin polymerization catalyst include titanium-based catalysts and metallocene-based catalysts. Of these, titanium-based catalysts are more preferably used.
- any polymer having an amount of structural units derived from propylene of 98 mol% or more and a melt flow rate of 10 g / 10 min to 300 g / 10 min is used as the propylene polymer (a-1), any polymer having an amount of structural units derived from propylene of 98 mol% or more and a melt flow rate of 10 g / 10 min to 300 g / 10 min is used. A commercially available product corresponding to this may be used as appropriate.
- (A-2) Propylene / ethylene copolymer
- a propylene / ethylene copolymer for the polypropylene resin (A), in addition to the above-mentioned propylene polymer (a-1), if necessary, (a-2) a propylene / ethylene copolymer May be included.
- the content of structural units derived from ethylene is usually from 30 mol% to 60 mol%, preferably from 30 mol% to 55 mol%, more preferably from 30 mol% to 50 mol%. It is a copolymer of propylene and ethylene.
- the propylene / ethylene copolymer (a-2) that can be used in the present invention has an intrinsic viscosity [ ⁇ ] measured in decalin at 135 ° C. of 1.5 dl / g or more and 8 dl / g or less.
- the lower limit of the intrinsic viscosity of the propylene / ethylene copolymer (a-2) is preferably 1.6 dl / g, more preferably 1.8 dl / g, and the upper limit is preferably 7.5 dl / g. More preferably, it is 7.0 dl / g.
- Such a propylene / ethylene copolymer (a-2) is not particularly limited, and can be obtained by copolymerizing propylene and ethylene in the presence of a known olefin polymerization catalyst.
- the olefin polymerization catalyst include titanium-based catalysts and metallocene-based catalysts. Of these, titanium-based catalysts are more preferably used.
- the propylene / ethylene copolymer (a-2) may be a propylene / ethylene copolymer component contained in the block copolymer or a random copolymer as long as the above properties are satisfied.
- it is a propylene / ethylene copolymer component contained in a block copolymer produced by two or more polymerization steps.
- the polypropylene resin (A) according to the present invention comprises (a-1) a propylene polymer as an essential component, and (a-2) a propylene / ethylene copolymer as necessary.
- the (A) polypropylene resin according to the present invention is preferably composed only of (a-1) a propylene polymer, and (a-1) a propylene polymer and (a-2) It may be composed of a propylene / ethylene copolymer.
- the blending amounts of (a-1) and (a-2) are as follows: (a-1): 30 to 80 parts by weight, (a-2): 0 to 30 parts by weight in the polypropylene resin composition of the present invention.
- (A) which is the sum of (a-1) and (a-2) may be an amount satisfying 30 to 80 parts by weight.
- the blending amount of (a-1) and (a-2) is preferably (a-1): 30 to 75 parts by weight, (a-2): 5 to 25 parts by weight, (A), which is the sum of 1) and (a-2), may be an amount satisfying 35 to 80 parts by weight, more preferably (a-1): 30 to 73 parts by weight, (a-2) : 7 to 25 parts by weight, and (A), which is the sum of (a-1) and (a-2), is an amount satisfying 37 to 80 parts by weight.
- the polypropylene resin comprises (a-1) a propylene polymer and (a-2) a propylene / ethylene copolymer
- the polypropylene resin is (a-1) It may be a mixture of a propylene polymer and (a-2) a propylene / ethylene copolymer, or (a-1) a segment of a propylene polymer and (a-2) It may be a block copolymer having a propylene / ethylene copolymer segment.
- the (A) polypropylene resin is a block copolymer having (a-1) a propylene polymer segment and (a-2) a propylene / ethylene copolymer segment. preferable.
- the room temperature n-decane insoluble part (D insol ) constituting the propylene / ethylene block copolymer is mainly composed of a propylene polymer component. That is, it corresponds to the above-mentioned (a-1) propylene polymer.
- the portion soluble in room temperature n-decane (D sol ) is mainly composed of a propylene-ethylene copolymer rubber component. That is, it corresponds to the above-mentioned (a-2) propylene / ethylene copolymer.
- the polypropylene resin is a block copolymer having (a-1) a propylene polymer segment and (a-2) a propylene / ethylene copolymer segment.
- a portion insoluble in room temperature n-decane (D insol ) in (A) polypropylene resin is (a-1) a portion in which propylene polymer is soluble in room temperature n-decane (D sol ).
- the propylene polymer (a-1) and, if necessary, the propylene / ethylene copolymer (a-2) constituting the polypropylene resin (A) are known as described above. It can be prepared by polymerization or copolymerization in the presence of a catalyst for olefin polymerization.
- a catalyst for olefin polymerization catalyst specifically, for example, a catalyst containing a solid titanium catalyst component (I) and an organometallic compound catalyst component (II) can be used.
- Solid titanium catalyst component (I) contains titanium, magnesium, halogen and, if necessary, an electron donor.
- a known solid titanium catalyst component can be used without limitation.
- magnesium compounds include magnesium halides such as magnesium chloride and magnesium bromide; alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride and phenoxymagnesium chloride; ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, 2 -Known magnesium compounds such as alkoxymagnesium such as ethylhexoxymagnesium; aryloxymagnesium such as phenoxymagnesium; and carboxylates of magnesium such as magnesium stearate.
- magnesium halides such as magnesium chloride and magnesium bromide
- alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride and phenoxymagnesium chloride
- ethoxymagnesium isopropoxymagnesium, butoxymagnesium
- 2 -Known magnesium compounds such as alkoxymagnesium such as ethylhexoxymagnesium; aryloxymagnesium such
- magnesium compounds may be used alone or in combination of two or more.
- These magnesium compounds may be complex compounds with other metals, double compounds, or mixtures with other metal compounds.
- a magnesium compound containing a halogen is preferable, and a magnesium halide, particularly magnesium chloride is preferably used.
- alkoxymagnesium such as ethoxymagnesium is also preferably used.
- the magnesium compound may be derived from another substance, for example, obtained by contacting an organic magnesium compound such as a Grignard reagent with a halogenated titanium, a halogenated silicon, a halogenated alcohol or the like. Good.
- titanium compound examples include a tetravalent titanium compound represented by the following formula.
- Ti (OR) g X 4-g (In the formula, R is a hydrocarbon group, X is a halogen atom, and g is 0 ⁇ g ⁇ 4.) More specifically, titanium tetrahalides such as TiCl 4 and TiBr 4 ; Ti (OCH 3 ) Cl 3 , Ti (OC 2 H 5 ) Cl 3 , Ti (On—C 4 H 9 ) Cl 3 , Trihalogenated alkoxytitanium such as Ti (OC 2 H 5 ) Br 3 , Ti (O-isoC 4 H 9 ) Br 3 ; Ti (OCH 3 ) 2 Cl 2 , Ti (OC 2 H 5 ) 2 Cl 2, etc.
- Dihalogenated alkoxytitanium such as Ti (OCH 3 ) 3 Cl, Ti (On-C 4 H 9 ) 3 Cl, Ti (OC 2 H 5 ) 3 Br; Ti (OCH 3 ) 4 And tetraalkoxytitanium such as Ti (OC 2 H 5 ) 4 , Ti (OC 4 H 9 ) 4 , and Ti (O-2-ethylhexyl) 4 .
- titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable.
- These titanium compounds may be used alone or in combination of two or more.
- magnesium compound and the titanium compound examples include compounds described in detail in JP-A-57-63310, JP-A-5-170843, and the like.
- Preferred examples of the preparation of the solid titanium catalyst component (I) used in the production of the polypropylene resin (A) in the present invention include the following methods (P-1) to (P-4). .
- a solid adduct comprising a magnesium compound and an electron donor component (a), an electron donor component (b), and a liquid titanium compound are suspended in the presence of an inert hydrocarbon solvent. The method of making it contact in a state and making it contact in multiple times.
- a preferable reaction temperature is in the range of ⁇ 30 ° C. to 150 ° C., more preferably ⁇ 25 ° C. to 130 ° C., and still more preferably ⁇ 25 to 120 ° C.
- the production of the above solid titanium catalyst component can be carried out in the presence of a known medium, if necessary.
- the medium include slightly polar aromatic hydrocarbons such as toluene, and known aliphatic hydrocarbons such as heptane, octane, decane, and cyclohexane, and alicyclic hydrocarbon compounds. Among these, aliphatic carbons are used. Hydrogen is a preferred example.
- the electron donor component (a) used for forming the solid adduct or the magnesium compound in a liquid state a known compound that can solubilize the magnesium compound in a temperature range of about room temperature to about 300 ° C. is preferable.
- a known compound that can solubilize the magnesium compound in a temperature range of about room temperature to about 300 ° C. is preferable.
- alcohol, aldehyde, amine, carboxylic acid and a mixture thereof are preferable.
- Examples of these compounds include compounds described in detail in JP-A-57-63310 and JP-A-5-170843.
- alcohols having solubilizing ability for the magnesium compound include methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, and n-octanol.
- Aliphatic alcohols such as 2-ethylhexanol, decanol and dodecanol; alicyclic alcohols such as cyclohexanol and methylcyclohexanol; aromatic alcohols such as benzyl alcohol and methylbenzyl alcohol; and alkoxy groups such as n-butyl cellosolve. Examples thereof include aliphatic alcohols.
- carboxylic acid examples include organic carboxylic acids having 7 or more carbon atoms such as caprylic acid and 2-ethylhexanoic acid.
- aldehydes examples include aldehydes having 7 or more carbon atoms such as capric aldehyde and 2-ethylhexyl aldehyde.
- amines having 6 or more carbon atoms such as heptylamine, octylamine, nonylamine, laurylamine, 2-ethylhexylamine.
- the electron donor component (a) the above alcohols are preferable, and ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, decanol and the like are particularly preferable.
- the composition ratio of magnesium and the electron donor component (a) in the obtained solid adduct or liquid magnesium compound varies depending on the type of compound used, and thus cannot be defined unconditionally.
- the electron donor component (a) is preferably in a range of 2 mol or more, more preferably 2.3 mol or more, still more preferably 2.7 mol or more and 5 mol or less.
- the electron donor used as necessary for the solid titanium catalyst component (I) used in the present invention include an aromatic carboxylic acid ester and / or two or more ethers via a plurality of carbon atoms.
- a compound having a bond hereinafter also referred to as “electron donor component (b)” may be contained.
- Examples of the electron donor component (b) include known aromatic carboxylic acid esters and polyether compounds that are preferably used in conventional olefin polymerization catalysts, such as JP-A Nos. 5-170843 and 2001-354714. Etc. can be used without limitation.
- aromatic carboxylic acid ester examples include aromatic polycarboxylic acid esters such as phthalic acid esters, in addition to aromatic carboxylic acid monoesters such as benzoic acid esters and toluic acid esters.
- aromatic polycarboxylic esters are preferred, and phthalates are more preferred.
- phthalic acid alkyl esters such as ethyl phthalate, n-butyl phthalate, isobutyl phthalate, hexyl phthalate, and heptyl phthalate are preferable, and diisobutyl phthalate is particularly preferable.
- polyether compound more specifically, a compound represented by the following formula (1) can be mentioned.
- m is an integer of 1 ⁇ m ⁇ 10, more preferably an integer of 3 ⁇ m ⁇ 10, and R 11 to R 36 are each independently a hydrogen atom, or carbon, hydrogen, oxygen , Fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron, and silicon, and a substituent having at least one element selected from silicon.
- R 11 and R 12 may be the same or different. Any R 11 to R 36 , preferably R 11 and R 12 may jointly form a ring other than a benzene ring.
- Such compounds include 2-isopropyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane and the like. Substituted dialkoxypropanes; 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2 -Methyl-2-cyclohexyl-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) ) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxyprop
- 1,3-diethers are preferable, and in particular, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl.
- 1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, and 2,2-bis (cyclohexylmethyl) 1,3-dimethoxypropane are preferred.
- the halogen / titanium (atomic ratio) (that is, the number of moles of halogen atom / number of moles of titanium atom) is 2 to 100, preferably 4 to 90. It is desirable that the electron donor component (a) and the electron donor component (b) have an electron donor component (a) / titanium atom (molar ratio) of 0 to 100, preferably 0 to 10.
- the electron donor component (b) / titanium atom (molar ratio) is 0-100, preferably 0-10.
- the magnesium / titanium (atomic ratio) (that is, the number of moles of magnesium atoms / the number of moles of titanium atoms) is desirably 2 to 100, preferably 4 to 50.
- EP585869A1 European Patent Application Publication No. 0585869
- JP-A-5-170843 The conditions described in the gazette and the like can be preferably used.
- organometallic compound catalyst component (II) containing a metal element selected from Group 1, Group 2 and Group 13 of the periodic table will be described.
- organometallic compound catalyst component (II) As the organometallic compound catalyst component (II), a compound containing a Group 13 metal, for example, an organoaluminum compound, a complex alkylated product of a Group 1 metal and aluminum, an organometallic compound of a Group 2 metal, or the like is used. it can.
- a compound containing a Group 13 metal for example, an organoaluminum compound, a complex alkylated product of a Group 1 metal and aluminum, an organometallic compound of a Group 2 metal, or the like is used. it can.
- organoaluminum compounds are preferred.
- organometallic compound catalyst component (II) examples include organometallic compound catalyst components described in known documents such as EP585869A1.
- a known electron donor component (c) may be used in combination with the electron donor component (a) or the electron donor component (b).
- Such an electron donor component (c) is preferably an organosilicon compound.
- organosilicon compound for example, a compound represented by the following formula can be exemplified.
- R n Si (OR ′) 4-n (In the formula, R and R ′ are hydrocarbon groups, and n is an integer of 0 ⁇ n ⁇ 4.) Specific examples of the organosilicon compound represented by the above formula include diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, and cyclohexylmethyldimethoxy.
- vinyltriethoxysilane diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, and dicyclopentyldimethoxysilane are preferably used.
- a silane compound represented by the following formula described in International Publication No. 2004/016662 is also a preferred example of the organosilicon compound.
- R a is a hydrocarbon group having 1 to 6 carbon atoms
- examples of Ra include an unsaturated or saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, particularly preferably 2 carbon atoms.
- ⁇ 6 hydrocarbon groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n- A hexyl group, a cyclohexyl group, etc. are mentioned, Among these, an ethyl group is particularly preferable.
- R b is a hydrocarbon group having 1 to 12 carbon atoms or hydrogen, and examples of R b include an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or hydrogen. Specific examples include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, an n-pentyl group, an iso-pentyl group, and a cyclopentyl group. N-hexyl group, cyclohexyl group, octyl group and the like, among which ethyl group is particularly preferable.
- R c is a hydrocarbon group having 1 to 12 carbon atoms, and examples of R c include an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or hydrogen. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n- A hexyl group, a cyclohexyl group, an octyl group, etc. are mentioned, Among these, an ethyl group is particularly preferable.
- the compound represented by the above formula examples include dimethylaminotriethoxysilane, diethylaminotriethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, diethylaminotri-n-propoxysilane, di-n-propylaminotriethoxysilane, Examples include methyl n-propylaminotriethoxysilane, t-butylaminotriethoxysilane, ethyl n-propylaminotriethoxysilane, ethyl iso-propylaminotriethoxysilane, and methylethylaminotriethoxysilane.
- organosilicon compound examples include compounds represented by the following formula.
- RN is a cyclic amino group
- examples of the cyclic amino group include a perhydroquinolino group, a perhydroisoquinolino group, a 1,2,3,4-tetrahydroquinolino group, 1,2,3 , 4-tetrahydroisoquinolino group, octamethyleneimino group and the like.
- silane compound represented by the above formula examples include (perhydroquinolino) triethoxysilane, (perhydroisoquinolino) triethoxysilane, and (1,2,3,4-tetrahydroquinolino) triethoxysilane. , (1,2,3,4-tetrahydroisoquinolino) triethoxysilane, octamethyleneiminotriethoxysilane and the like.
- organosilicon compounds can be used in combination of two or more.
- the polypropylene resin (A) used in the present invention can be produced by polymerizing or copolymerizing an olefin-based raw material in the presence of the above-mentioned olefin polymerization catalyst.
- propylene is polymerized alone in the presence of the above-mentioned olefin polymerization catalyst, or propylene, ethylene, and ⁇ having 4 to 8 carbon atoms.
- olefin polymerization catalyst or propylene, ethylene, and ⁇ having 4 to 8 carbon atoms.
- -At least one ⁇ -olefin selected from olefins can be copolymerized in a quantitative ratio such that the content of structural units derived from propylene is 98 mol% or more.
- propylene and ethylene can be copolymerized in one stage or in multiple stages in the presence of the above-mentioned catalyst for olefin polymerization. Specifically, propylene is polymerized, and then propylene is polymerized in the presence of a prepolymerization catalyst (prepolymerization catalyst) obtained by copolymerizing propylene and ethylene or by prepolymerization (prepolymerization), Subsequently, it can manufacture by methods, such as performing copolymerization of propylene and ethylene.
- a prepolymerization catalyst prepolymerization catalyst
- the prepolymerization is performed by prepolymerizing the olefin in an amount of usually 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g per 1 g of the olefin polymerization catalyst.
- a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used.
- the concentration of the solid titanium catalyst component (I) in the prepolymerization is usually about 0.001 to 200 mmol, preferably about 0.01 to 50 mmol, particularly preferably about 0.1 to 50 mmol in terms of titanium atom per liter of the liquid medium. A range of 1 to 20 mmol is desirable.
- the amount of the organometallic compound catalyst component (II) in the prepolymerization may be such that a polymer of 0.1 to 1000 g, preferably 0.3 to 500 g, is usually produced per 1 g of the solid titanium catalyst component (I).
- the amount is usually about 0.1 to 300 moles, preferably about 0.5 to 100 moles, particularly preferably 1 to 50 moles per mole of titanium atoms in the solid titanium catalyst component (I). Is desirable.
- the electron donor component and the like can be used as necessary.
- these components are usually 0.1 to 50 per mole of titanium atom in the solid titanium catalyst component (I). It is used in an amount of mol, preferably 0.5 to 30 mol, more preferably 1 to 10 mol.
- the prepolymerization can be performed under mild conditions by adding an olefin and the above catalyst components to an inert hydrocarbon medium.
- inert hydrocarbon medium used examples include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, methylcyclopentane, cyclohexane, cyclohexane And alicyclic hydrocarbons such as heptane, methylcycloheptane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; or a mixture thereof.
- aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene
- cyclopentane methylcyclopentane, cyclohexan
- inert hydrocarbon media it is particularly preferable to use aliphatic hydrocarbons.
- prepolymerization can be carried out using olefin itself as a solvent, or it can be prepolymerized in a substantially solvent-free state. In this case, it is preferable to perform preliminary polymerization continuously.
- the olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described later, but is preferably propylene.
- the temperature during the prepolymerization is usually ⁇ 20 to + 100 ° C., preferably ⁇ 20 to + 80 ° C., more preferably 0 to + 40 ° C.
- the main polymerization is divided into a process for producing a propylene polymer component and a process for producing a propylene-ethylene copolymer rubber component.
- the prepolymerization and the main polymerization can be performed by any of a liquid phase polymerization method such as a bulk polymerization method, a solution polymerization, and a suspension polymerization, or a gas phase polymerization method.
- a preferred process for producing the propylene polymer component is liquid phase polymerization such as bulk polymerization or suspension polymerization or gas phase polymerization.
- liquid phase polymerization or gas phase polymerization method such as bulk polymerization or suspension polymerization is preferable as a process for producing the propylene-ethylene copolymer rubber component, and a gas phase polymerization method is more preferable.
- the reaction solvent may be an inert hydrocarbon used during the above-described prepolymerization, or an olefin that is liquid at the reaction temperature and pressure.
- the solid titanium catalyst component (I) is usually about 0.0001 to 0.5 mmol, preferably about 0.005 to 0.1 mmol in terms of titanium atom per liter of polymerization volume. Used in quantity.
- the organometallic compound catalyst component (II) is used in an amount of usually about 1 to 2000 mol, preferably about 5 to 500 mol, relative to 1 mol of titanium atom in the prepolymerization catalyst component in the polymerization system. It is done.
- the electron donor component When used, it is 0.001 to 50 mol, preferably 0.01 to 30 mol, and particularly preferably 0.001 mol with respect to 1 mol of the organometallic compound catalyst component (II). Used in an amount of 05 to 20 mol.
- the molecular weight of the resulting polymer can be adjusted (lowered), and a polymer having a high melt flow rate can be obtained.
- the amount of hydrogen necessary to adjust the molecular weight varies depending on the type of production process used, the polymerization temperature, and the pressure, and may be adjusted as appropriate.
- the MFR can be adjusted by adjusting the polymerization temperature and the amount of hydrogen.
- the intrinsic viscosity can be adjusted by adjusting the polymerization temperature, pressure, and amount of hydrogen.
- the polymerization temperature of the olefin is usually about 0 to 200 ° C., preferably about 30 to 100 ° C., more preferably 50 to 90 ° C.
- the pressure is usually set to normal pressure to 100 kgf / cm 2 (9.8 MPa), preferably about 2 to 50 kgf / cm 2 (0.20 to 4.9 MPa).
- the polymerization can be carried out by any of batch, semi-continuous and continuous methods.
- the reactor can be tubular or tank type.
- the polymerization can also be carried out in two or more stages by changing the reaction conditions. In this case, tubular and tank reactors can be combined.
- the ethylene / (ethylene + propylene) gas ratio is controlled to obtain a propylene / ethylene copolymer.
- the ethylene / (ethylene + propylene) gas ratio is controlled to 5 to 80 mol%, preferably 10 to 70 mol%, more preferably 15 to 60 mol%.
- the portion insoluble in room temperature n-decane (D insol ) constituting the propylene / ethylene block copolymer is mainly composed of a propylene polymer component. That is, it corresponds to the above-mentioned (a-1) propylene polymer.
- the portion soluble in room temperature n-decane (D sol ) is mainly composed of a propylene-ethylene copolymer rubber component. That is, it corresponds to the above-mentioned (a-2) propylene / ethylene copolymer.
- Polymerization step 1 A step of producing propylene polymer component by polymerizing propylene in the presence of a solid titanium catalyst component (propylene polymer production step).
- Polymerization step 2 A step of copolymerizing propylene and ethylene in the presence of a solid titanium catalyst component to produce a propylene-ethylene copolymer rubber component (copolymer rubber production step).
- the propylene / ethylene block copolymer used in the present invention is preferably produced by the production method described above, and it is more preferred that the polymerization step 1 is performed in the previous stage and the polymerization step 2 is performed in the subsequent stage.
- Each polymerization step (polymerization step 1, polymerization step 2) can also be performed using two or more polymerization vessels.
- the content of the decane-soluble part in the block copolymer can be adjusted by controlling the polymerization time (residence time) in Step 1 and Step 2.
- the polymerization step 1 may be performed in two or more series polymerization apparatuses. In that case, the ratio of propylene and hydrogen in each stage may be different for each polymerization reactor. Further, a propylene homopolymer obtained by separately performing only the polymerization step 1 may be mixed with the propylene / ethylene block copolymer produced above.
- the ethylene / ⁇ -olefin copolymer (B) constituting the polypropylene resin composition of the present invention comprises a copolymer of ethylene and an ⁇ -olefin having 3 to 8 carbon atoms. It is a polymer.
- ⁇ -olefin propylene, 1-butene, 1-hexene, 1-octene and the like are preferable.
- One ⁇ -olefin may be used, or two or more ⁇ -olefins may be mixed and used.
- the ethylene / ⁇ -olefin copolymer (B) is preferably an ethylene-octene copolymer or an ethylene-butene copolymer.
- the ethylene / ⁇ -olefin copolymer (B) according to the present invention has an ethylene content of 65 mol% or more and 90 mol% or less.
- the upper limit with preferable ethylene content rate is 85 mol%, More preferably, it is 80 mol%.
- the base material component constituting the polypropylene resin composition of the present invention may contain an inorganic filler (E).
- inorganic filler (E) known inorganic fillers can be used without particular limitation.
- talc, mica, calcium carbonate, barium sulfate, glass fiber, gypsum, magnesium carbonate, magnesium oxide examples thereof include titanium oxide, iron oxide, metal powder such as zinc, copper, iron, and aluminum, or metal fibers. These can be used alone or in combination.
- talc talc, mica, calcium carbonate, glass fiber and the like are preferable, and talc is particularly preferable.
- talc those having an average particle diameter of 1 to 15 ⁇ m, preferably 1 to 6 ⁇ m can be suitably used.
- the base material component constituting the polypropylene resin composition of the present invention is a polypropylene system comprising the above-mentioned propylene polymer (a-1) and, if necessary, a propylene / ethylene copolymer (a-2). Resin (A), ethylene / ⁇ -olefin copolymer (B), and (E) inorganic filler as required.
- Such a base material component comprises 30 to 80 parts by weight of (a-1) in a total of 100 parts by weight of (a-1), (a-2), (B) and (E), (a- 2) 0 to 30 parts by weight, (B) 20 to 50 parts by weight, and (E) 0 to 40 parts by weight, preferably (a-1) 30 to 75 parts by weight, ( a-2) 0 to 25 parts by weight, (B) 20 to 40 parts by weight, and (E) 0 to 40 parts by weight.
- the base material component of the present invention comprises (a-1), (a-2), (B), and (E) in a total of 100 parts by weight of (a-1) and (a-2).
- the total that is, the amount of component (A)) is 30 to 80 parts by weight, preferably 30 to 75 parts by weight. More preferably, 0.5 to 25 parts by weight of (a-2) and 0.5 to 40 parts by weight of (E) are contained.
- the polypropylene resin composition of the present invention contains 20 parts by weight or more of the ethylene / ⁇ -olefin copolymer (B) in 100 parts by weight of the base component, so that the resulting molded product has good impact resistance.
- the polypropylene resin (A) is contained in an amount of 30 parts by weight or more, the obtained molded body has good rigidity.
- the base material component of the present invention has a total of (a-2) and (B) of 20 in a total of 100 parts by weight of (a-1), (a-2), (B), and (E). -50 parts by weight, preferably 20-40 parts by weight.
- the propylene / ethylene copolymer (a-2) and the ethylene / ⁇ -olefin copolymer (B) are components that can be soluble in normal temperature xylene.
- the total amount of (a-2) and (B) is 20 parts by weight or more in 100 parts by weight of the base material component, sufficient Izod impact strength can be easily obtained, and when it is 50 parts by weight or less, Sufficient rigidity is easily obtained, and it is suitable for applications such as automobile interior and exterior parts.
- the ratio of the parts by weight of the ethylene / ⁇ -olefin copolymer (B) to the sum of the parts by weight of the propylene / ethylene copolymer (a-2) and the ethylene / ⁇ -olefin copolymer (B); ) / ((A-2) + (B)) is preferably 0.5 to 1, more preferably 0.7 to 1.
- (B) / ((a-2) + (B)) of 0.5 or more means that among the components that can be soluble in normal temperature xylene contained in the base material component, It shows that the polymer (B) is relatively large.
- the ethylene / ⁇ -olefin copolymer (B) accounts for more than half of the room temperature xylene-soluble component contained in the base material component, the fatty acid amide (C) and surfactant described later are used. It is assumed that the transition to the surface of the molded article (D) can be made easier.
- the content of the inorganic filler (E) contained in the base material component of the present invention as needed can be appropriately adjusted depending on the desired properties of the molded body molded from the resin composition, and is particularly limited. Although not intended, the amount is preferably 40 parts by weight or less with respect to 100 parts by weight in total of (a-1), (a-2), (B), and (E).
- the fatty acid amide (C) constituting the polypropylene resin composition of the present invention is preferably a fatty acid amide that acts as a lubricant or an antistatic agent.
- the fatty acid amide used in the present invention may be a saturated fatty acid amide or an unsaturated fatty acid amide, preferably a fatty acid amide having 8 to 25 carbon atoms and a dimer thereof, more preferably A fatty acid amide having 8 to 25 carbon atoms, more preferably a fatty acid amide having 15 to 25 carbon atoms.
- fatty acid amide (C) examples include oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, palmitic acid amide, myristic acid amide, lauric acid amide, caprylic acid amide, and caproic acid.
- the body is preferred.
- Such a fatty acid amide (C) is 0.2 to 1 part by weight, preferably 0.2 to 0.8 part by weight with respect to 100 parts by weight of the base component in the polypropylene resin composition of the present invention. Part, more preferably 0.2 to 0.6 part by weight.
- the surfactant (D) constituting the polypropylene resin composition of the present invention preferably has an action as an antistatic agent in the polypropylene resin composition.
- any surfactant that can be used by adding to a polypropylene resin can be used as the surfactant, but an ester-type surfactant is preferably used and has 8 to 8 carbon atoms. More preferably, compounds having one or two ester groups having 25, preferably 15 to 25 carbon atoms are used.
- surfactant (D) examples include glycerin fatty acid ester, diglycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, alkyl glucoside, and polyvalent carboxylic acid ester. Of these, glycerin fatty acid esters and diglycerin fatty acid esters are preferably used.
- glycerin fatty acid ester that is, fatty acid monoglyceride
- stearic acid monoglyceride examples include stearic acid monoglyceride, oleic acid monoglyceride, linolenic acid monoglyceride, lauric acid monoglyceride, palmitic acid monoglyceride, myristic acid monoglyceride, behenic acid monoglyceride and margaric acid monoglyceride.
- stearic acid monoglyceride and oleic acid monoglyceride are preferably used.
- Examples of the diglycerin fatty acid ester include stearic acid diglyceride, oleic acid diglyceride, linolenic acid diglyceride, lauric acid diglyceride, palmitic acid diglyceride, myristic acid diglyceride, behenic acid diglyceride, and margaric acid diglyceride. . Of these, stearic acid diglyceride and oleic acid diglyceride are preferably used.
- ester compounds a surfactant having a fatty acid ester group having 8 to 25 carbon atoms is preferably used.
- Such a surfactant (D) in the polypropylene resin composition of the present invention is 0.2 to 1 part by weight, preferably 0.2 to 0.8 part by weight with respect to 100 parts by weight of the base component. Parts by weight, more preferably 0.2 to 0.6 parts by weight.
- the fatty acid amide (C) and the surfactant (D) are each contained in an amount of 0.2 to 1 part by weight with respect to 100 parts by weight of the base component, these (C) It can be obtained from the resin composition by the interaction of the component (C) and the component (D) without causing problems such as mold contamination during molding, which is a concern when the component and the component (D) are excessive.
- the molded product exhibits excellent resistance to friction caused by a soft material such as a rubber-like material.
- the polypropylene resin composition of the present invention includes, as necessary, a heat stabilizer, a weather stabilizer, a light stabilizer, an antioxidant, an antioxidant, a fatty acid metal salt, a softener, Other additives (F) such as a dispersant, a filler, a colorant, and a pigment may be blended within a range that does not impair the object of the present invention.
- the mixing order of additives to be blended is arbitrary, and may be mixed at the same time, or a multistage mixing method in which some components are mixed and then other components are mixed.
- the polypropylene resin composition of the present invention comprises (a-1) a polypropylene resin (A) comprising a propylene polymer and, if necessary, (a-2) a propylene / ethylene copolymer; , An ethylene / ⁇ -olefin copolymer (B), and, if necessary, a base material component comprising an inorganic filler (E), a fatty acid amide (C) and a surfactant (D).
- the base component contains 30 to 80 parts by weight of a propylene polymer (a-1), 0 to 30 parts by weight of a propylene / ethylene copolymer (a-2), an ethylene / ⁇ -olefin copolymer ( B) 20 to 50 parts by weight and inorganic filler (E) 0 to 40 parts by weight are included.
- the base component contains (a-1) 30 to 75 parts by weight, (a-2) 0 to 25 parts by weight, and ethylene / ⁇ -olefin copolymer (B) 20 to 40 parts by weight. Is included.
- the base component contains (a-1) 30 to 75 parts by weight, (a-2) 0 to 25 parts by weight, and ethylene / ⁇ -olefin copolymer (B) 25 to 40 parts by weight. Part is included. However, the total of (a-1), (a-2), (B) and (E) is 100 parts by weight, and the polypropylene resin (A ) Is 30 to 80 parts by weight, preferably 30 to 75 parts by weight.
- the fatty acid amide (C) is 0.2 to 1 part by weight, preferably 0.2 to 0.8 part by weight, based on 100 parts by weight of the base component.
- the surfactant (D) is 0.2 to 1 part by weight, preferably 0.2 to 0.8 parts by weight, more preferably 0.2 to 0.6 parts by weight. Including parts by weight.
- Such a polypropylene resin composition of the present invention may contain other components as long as the object of the present invention is not impaired.
- other components include the other additives (F) described above.
- the blending amount of the other components is an appropriate amount in accordance with the manifestation of the effect of the component to be added, and an amount that does not impair the object of the present invention is appropriately selected.
- the polypropylene resin composition of the present invention containing each component in such a quantitative ratio has sufficient impact resistance and rigidity when the molded resin is produced by molding the resin composition, It has excellent lubrication properties, and can effectively suppress scratches and whitening caused by friction with soft materials such as rubber.
- the polypropylene resin composition of the present invention comprises a base material component comprising a polypropylene resin (A), an ethylene / ⁇ -olefin copolymer (B) and, if necessary, an inorganic filler (E), a fatty acid amide (C ), A surfactant (D), and other components such as other additives (F).
- the polypropylene resin composition of the present invention comprises the components (A), (B) and (E) blended as necessary, (C) and (D) and (F) blended as necessary. It can be obtained by mixing or melt-kneading with a mixing device such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, or a high-speed twin-screw extruder.
- a mixing device such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, or a high-speed twin-screw extruder.
- the polypropylene resin composition of the present invention can be appropriately molded by a known molding method, and is particularly suitable for injection molding.
- the molded product of the present invention is composed of the above-described polypropylene resin composition of the present invention.
- the molded body of the present invention has excellent moldability and has sufficient rigidity because the polypropylene resin composition of the present invention, which is a raw material, contains the polypropylene resin (A) in the above-mentioned quantitative ratio. It has sufficient impact resistance because it contains ethylene / ⁇ -olefin (B) in a quantity ratio of. Furthermore, since the fatty acid amide (C) and the surfactant (D) are included in the above-mentioned quantitative ratio, the molded product exhibits excellent friction resistance without causing problems such as mold contamination during molding. Excellent resistance to friction caused by soft materials such as rubber.
- the polypropylene resin composition containing the ethylene / ⁇ -olefin copolymer is essential is that the polypropylene resin composition contains only propylene / ethylene copolymer rubber as a soft component. Since the compatibility between the polypropylene amorphous part and the propylene / ethylene copolymer rubber is good, the rubber dissolves into the polypropylene amorphous part and the matrix (sea phase) becomes soft.
- lubricants and surfactants are considered as follows. It is considered that at least a part of the lubricant or surfactant exudes to the surface of the molded body after molding and contributes to the improvement of surface lubricity. It is considered that there were cases where sufficient lubricity could not be given to the entire surface. In contrast, in a molded product obtained using the polypropylene resin composition of the present invention in which fatty acid amide and surfactant coexist in a specific amount, fatty acid amide and surfactant are dispersed with each other by interaction. It is considered that high lubricity could be imparted to the entire surface even when the amount of addition was small without making localization on the surface of the molded body.
- the polypropylene-based resin composition according to the present invention is excellent in moldability and can be applied to molded articles by various molding methods.
- Molded articles made of a polypropylene resin composition include injection molded articles, foam molded articles, injection foam molded articles, extrusion molded articles, blow molded articles, vacuum / pressure molded articles, calendar molded articles, stretched films, inflation films, and the like. In particular, it can be suitably used for injection molded articles.
- the molding conditions are not particularly limited, and conventionally known conditions can be employed.
- the use of the molded body of the present invention is not particularly limited, but interior and exterior parts of automobiles such as door panels, pillar trims, door trims, door lower garnishes, and instrument panels, engine room peripheral parts, other automobile parts, and home appliance parts. It can be suitably used for food containers, beverage containers, medical containers, containers and the like. Among these, it is suitable for automobile interior and exterior member applications, and particularly suitable for applications such as automobile door members and pillar members.
- melt flow rate was measured on condition of 230 degreeC and a 21.16N load.
- Rubber component amount room temperature n-decane soluble component amount [wt%]: First, 5 g of a sample was precisely weighed and placed in a 1,000 ml eggplant-shaped flask. Further, 1 g of BHT (dibutylhydroxytoluene, phenolic antioxidant) was added, and then a rotor and 700 ml of n-decane were added. .
- BHT dibutylhydroxytoluene, phenolic antioxidant
- a cooler was attached to the eggplant-shaped flask, and the flask was heated in an oil bath at 135 ° C. for 120 minutes while operating the rotor, so that the sample was dissolved in n-decane.
- the solution in the beaker was allowed to cool to room temperature (25 ° C.) while stirring with a stirrer (8 hours or longer), and then a precipitate was formed. Was filtered with a wire mesh.
- the obtained filtrate was further filtered with a filter paper, and then poured into 2,000 ml of methanol contained in a 3,000 ml beaker, and this liquid was stirred with a stirrer at room temperature (25 ° C.). Left for more than 2 hours.
- the obtained precipitate was filtered with a wire mesh, air-dried for 5 hours or more, and then dried in a vacuum dryer at 100 ° C. for 240 to 270 minutes, and the n-decane soluble part at 25 ° C. was recovered.
- Intrinsic viscosity of rubber component [ ⁇ ] It measured at 135 degreeC using the decalin solvent. About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity ⁇ sp was measured in an oil bath at 135 ° C. After diluting the decalin solution with 5 ml of decalin solvent, the specific viscosity ⁇ sp was measured in the same manner. This dilution operation was further repeated twice, and the value of ⁇ sp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity ([ ⁇ ]: [dl / g]).
- [ ⁇ ] lim ( ⁇ sp / C) (C ⁇ 0) ⁇ Scratch test due to rubber friction (Scuff foot kick test)
- a resin composition is manufactured by injection molding into a mold, and a molded article having a grain on the surface is allowed to stand for 2 hours or more in a constant temperature state at 23.degree. This was used as a test piece.
- the shape of the test piece was 120 cm long, 80 cm wide, and 0.3 cm high.
- a scuff foot kick test device that operates the pendulum from the height of the test piece and has the effect that the rubber test piece rubs through the test surface of the test piece and reproduces the model state of the foot kick at the shoe sole.
- a rubber test piece which is a friction material a rubber piece having a Shore A surface hardness of 75 (manufactured by Nissan Motor Co., Ltd., product number 18215-SA0-000) was used.
- the test was performed by two test workers according to the following operation procedure. 1.
- the test piece (1) is fixed on the pedestal (3) of the apparatus. 2.
- the tip of the pendulum mounted with the friction material (rubber test piece) (2) is pulled up to a predetermined height ((5), 20 cm from the scratched test surface). 5. Release the pendulum and rub the rubber against the test surface of the test piece (1). 6).
- the scratching property of the test surface (6) is judged visually.
- the results of the scuff foot kick test were evaluated based on the following evaluation criteria based on the visual observation of the surface state. As for the evaluation results, grade 5 represents the best and grade 1 represents the worst.
- the surface of the friction part is slightly whitened.
- the solid part was again collected by hot filtration, and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.
- the solid titanium catalyst component prepared as described above was stored as a hexane slurry, and a part of the catalyst was dried to examine the catalyst composition.
- the solid titanium catalyst component contained 2% by weight of titanium, 57% by weight of chlorine, 21% by weight of magnesium and 20% by weight of DIBP.
- prepolymerization catalyst 87.5 g of solid titanium catalyst component, 99.8 mL of triethylaluminum, 28.4 ml of diethylaminotriethoxysilane, and 12.5 L of heptane were inserted into an autoclave with a stirrer having an internal volume of 20 L, and an internal temperature of 15 The temperature was kept at ⁇ 20 ° C., 875 g of propylene was inserted, and the reaction was carried out with stirring for 100 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 0.7 g / L.
- the obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized.
- Propylene was supplied to the polymerization vessel at 30 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 3.9 mol%.
- Polymerization was carried out at a polymerization temperature of 74.5 ° C. and a pressure of 3.4 MPa / G.
- the obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized.
- propylene was supplied at 20 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 3.4 mol%.
- Polymerization was performed at a polymerization temperature of 73 ° C. and a pressure of 3.4 MPa / G.
- the resulting slurry was gas-solid separated after being deactivated and vaporized.
- the resulting propylene homopolymer was vacuum dried at 80 ° C.
- the properties of the resulting propylene homopolymer (propylene polymer A-1) are shown in Table 1.
- the obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized.
- propylene was supplied at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 8.8 mol%.
- Polymerization was performed at a polymerization temperature of 69.5 ° C. and a pressure of 3.2 MPa / G.
- the obtained slurry was transferred to a transfer pipe having an internal volume of 2.4 L, gasified and gas-solid separated, and then the polypropylene homopolymer powder was sent to a gas phase polymerizer having an internal volume of 480 L.
- propylene block copolymer was vacuum dried at 80 ° C.
- the properties of the resulting propylene block copolymer are shown in Table 1.
- the obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized.
- propylene was supplied at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 5.8 mol%.
- Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.3 MPa / G.
- the obtained slurry was transferred to a transfer pipe having an internal volume of 2.4 L, gasified and gas-solid separated, and then the polypropylene homopolymer powder was sent to a gas phase polymerizer having an internal volume of 480 L.
- propylene block copolymer was vacuum dried at 80 ° C.
- the properties of the resulting propylene block copolymer (propylene polymer A-3) are shown in Table 1.
- Table 1 also shows the properties of commercially available homopolypropylene (product name: J-3000GV, manufactured by Prime Polymer Co., Ltd.) used in Examples and Comparative Examples as the propylene polymer A-4.
- rubber refers to an impurity component (for example, an olefin such as ethylene) contained in the raw material propylene used and propylene. This refers to a polymerization component.
- rubber refers to a copolymer component of propylene and ethylene.
- Ethylene / ⁇ -olefin copolymer B-1 ethylene / octene random copolymer having an ⁇ -olefin (octene) amount of 38.6% by weight and MFR of 2 g / 10 min, product name: EG8100, Dow Chemical Co., Ltd.
- Ethylene / ⁇ -olefin copolymer B-2 An ethylene / butene random copolymer with an ⁇ -olefin (butene) content of 27.3% by weight and an MFR of 2 g / 10 min.
- Example 1 The amounts of propylene-based polymer A-1, ethylene / ⁇ -olefin copolymer B-1, fatty acid amide C-1, and surfactant D-1 obtained in Production Example 1 are shown in Table 2 in amounts (weights).
- the obtained mixture was kneaded with a twin-screw extruder (trade name: TEX, manufactured by Nippon Steel) to produce polypropylene resin composition pellets.
- the kneading conditions were a kneading temperature of 180 ° C., a screw rotation speed of 750 rpm, and a discharge rate of 60 kg / h.
- the obtained pellets were manufactured by injection molding, and the above-mentioned test pieces were manufactured and evaluated by performing a scratch test (Scuff foot kick test) due to rubber friction. The results are shown in Table 2.
- Examples 2 to 11, Comparative Examples 1 to 9 Each component of A to E and its blending amount (that is, each component and blending amount other than other additives and parts by weight) are the same as in Example 1 except that it is as shown in Table 2 or Table 3. Then, a polypropylene resin composition pellet was produced, a test piece was produced by injection molding, and a scratch test (Scuff foot kick test) due to rubber friction was performed. The results are also shown in Table 2 or 3.
- FIG. 2 shows, as a representative example, a photograph of the surface condition of the test piece at the time of the scratch test evaluation of Example 3 and Comparative Example 1 (after the scuff foot kick test).
- the left side of the figure is the one at the time of the scratch test evaluation of Example 3 (the evaluation result is grade 4), and the right side of the figure is the one at the time of the scratch test evaluation of Comparative Example 1 (the evaluation result is grade 2).
- a fatty acid amide (C) and a surfactant (with respect to a base material component comprising a polypropylene resin (A) and an ethylene / ⁇ -olefin copolymer (B)) D) is obtained from a polypropylene-based resin composition containing a specific amount of each component, and even if the amount of fatty acid amide and surfactant is small, the scuff foot kick test results are all as high as 3 or more. It can be seen that surface degradation due to friction caused by rubber-like materials is sufficiently suppressed.
- the polypropylene-based resin composition of the present invention can be used without limitation in the production of various molded products such as injection molded products, and in particular, automotive interior and exterior components such as pillar trims, door panels, door trims, door lower garnishes, and instrument panels. Can be suitably used.
- Test piece Friction material (rubber test piece) (3) Pedestal (4) Pantograph (5) Pendulum height (20cm) (6) Test surface
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Transportation (AREA)
- Combustion & Propulsion (AREA)
- Crystallography & Structural Chemistry (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacturing & Machinery (AREA)
Abstract
Description
(A)(a-1)JIS K 7210に準拠した方法で測定したメルトフローレート(MFR、230℃、21.16N荷重)が10g/10min以上300g/10min以下であって、プロピレンから導かれる構成単位の含量が98mol%以上100mol%以下であり、エチレンと炭素原子数4~8のα-オレフィンから選ばれる少なくとも1種のα-オレフィンから導かれる構成単位の含量が0mol%以上2mol%以下であるプロピレン系重合体30~80重量部と、
(a-2)135℃デカリン中で測定した極限粘度[η]が1.5dl/g以上8dl/g以下、エチレンから導かれる構成単位の含量が30mol%以上60mol%以下であるプロピレン・エチレン共重合体0~30重量部と
からなり、(a-1)と(a-2)の合計が30~80重量部であるポリプロピレン系樹脂と、
(B)エチレン含有率が65mol%以上90mol%以下である、エチレンと、炭素原子数3~8のα-オレフィンから選ばれる少なくとも1種のα-オレフィンからなるエチレン・α-オレフィン共重合体20~50重量部と、
(E)無機充填材0~40重量部と、
からなり、(a-2)と(B)との合計が20~50重量部である基材成分(ただし、(A)、(B)、(E)との合計が100重量部である)100重量部に対して、
(C)脂肪酸アミド0.2~1重量部、および
(D)界面活性剤0.2~1重量部
を含む。
前記(C)脂肪酸アミドが、炭素原子数8~25の脂肪酸アミドおよびその2量体より選ばれる1種以上であり、かつ、
前記(D)界面活性剤が、炭素原子数が8~25であるエステル基を、1つまたは2つ有する化合物であることが好ましい。
<ポリプロピレン系樹脂組成物>
本発明のポリプロピレン系樹脂組成物は、ポリプロピレン系樹脂(A)とエチレン・α-オレフィン共重合体(B)と、必要に応じて(E)無機充填材からなる基材成分と、脂肪酸アミド(C)および界面活性剤(D)を含む。
本発明のポリプロピレン系樹脂組成物を構成する基材成分は、ポリプロピレン系樹脂(A)と、エチレン・α-オレフィン共重合体(B)と、必要に応じて(E)無機充填材からなる。
ポリプロピレン系樹脂(A)は、(a-1)プロピレン系重合体を必須成分とし、必要に応じて(a-2)プロピレン・エチレン共重合体を含む。
本発明に係る(a-1)成分のプロピレン系重合体は、プロピレンの単独重合体またはプロピレンと少量のα-オレフィンとの共重合体である。ここでα-オレフィンとは、エチレンと炭素原子数4~8のα-オレフィンから選ばれる少なくとも1種のα-オレフィンであり、好ましくはエチレンである。
ポリプロピレン系樹脂(A)には、上述したプロピレン系重合体(a-1)に加え、必要に応じて、(a-2)プロピレン・エチレン共重合体が含まれてもよい。
本発明に係るポリプロピレン系樹脂(A)は、(a-1)プロピレン系重合体を必須成分とし、必要に応じて(a-2)プロピレン・エチレン共重合体を含む。
ポリプロピレン系樹脂(A)を構成する、プロピレン系重合体(a-1)および必要に応じてプロピレン・エチレン共重合体(a-2)は、上述の通り、公知のオレフィン重合用触媒の存在下に、重合あるいは共重合を行って調製することができる。オレフィン重合用触媒としては、具体的には、たとえば、固体状チタン触媒成分(I)と、有機金属化合物触媒成分(II)とを含む触媒を用いることができる。
[固体状チタン触媒成分(I)]
固体状チタン触媒成分(I)は、チタン、マグネシウム、ハロゲン及び必要に応じて電子供与体を含む。この固体状チタン触媒成分(I)としては、公知の固体状チタン触媒成分を制限無く用いることができる。
(式中、Rは炭化水素基であり、Xはハロゲン原子であり、gは0≦g≦4である。)
より具体的には、TiCl4、TiBr4等のテトラハロゲン化チタン;Ti(OCH3)Cl3、Ti(OC2H5)Cl3、Ti(O-n-C4H9)Cl3、Ti(OC2H5)Br3、Ti(O-isoC4H9)Br3等のトリハロゲン化アルコキシチタン;Ti(OCH3)2Cl2、Ti(OC2H5)2Cl2等のジハロゲン化アルコキシチタン;Ti(OCH3)3Cl、Ti(O-n-C4H9)3Cl、Ti(OC2H5)3Br等のモノハロゲン化アルコキシチタン;Ti(OCH3)4、Ti(OC2H5)4、Ti(OC4H9)4、Ti(O-2-エチルヘキシル)4等のテトラアルコキシチタン等を挙げることができる。
任意のR11~R36、好ましくはR11及びR12は共同してベンゼン環以外の環を形成していてもよい。
有機金属化合物触媒成分(II)としては、第13族金属を含む化合物、たとえば、有機アルミニウム化合物、第1族金属とアルミニウムとの錯アルキル化物、第2族金属の有機金属化合物等を用いることができる。
(式中、R及びR’は炭化水素基であり、nは0<n<4の整数である。)
上記式で示される有機ケイ素化合物としては、具体的には、ジイソプロピルジメトキシシラン、t-ブチルメチルジメトキシシラン、t-ブチルメチルジエトキシシラン、t-アミルメチルジエトキシシラン、ジシクロヘキシルジメトキシシラン、シクロヘキシルメチルジメトキシシラン、シクロヘキシルメチルジエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、t-ブチルトリエトキシシラン、フェニルトリエトキシシラン、シクロヘキシルトリメトキシシラン、シクロペンチルトリメトキシシラン、2-メチルシクロペンチルトリメトキシシラン、シクロペンチルトリエトキシシラン、ジシクロペンチルジメトキシシラン、ジシクロペンチルジエトキシシラン、トリシクロペンチルメトキシシラン、ジシクロペンチルメチルメトキシシラン、ジシクロペンチルエチルメトキシシラン、シクロペンチルジメチルエトキシシラン等が用いられる。
式中、Raは、炭素数1~6の炭化水素基であり、Raとしては、炭素数1~6の不飽和あるいは飽和脂肪族炭化水素基等が挙げられ、特に好ましくは炭素数2~6の炭化水素基が挙げられる。具体例としてはメチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、sec-ブチル基、n-ペンチル基、iso-ペンチル基、シクロペンチル基、n-ヘキシル基、シクロヘキシル基等が挙げられ、これらの中でもエチル基が特に好ましい。
式中、RNは、環状アミノ基であり、この環状アミノ基として、例えば、パーヒドロキノリノ基、パーヒドロイソキノリノ基、1,2,3,4-テトラヒドロキノリノ基、1,2,3,4-テトラヒドロイソキノリノ基、オクタメチレンイミノ基等が挙げられる。
このように、不活性炭化水素媒体を用いる場合、予備重合はバッチ式で行うことが好ましい。
この場合には、予備重合を連続的に行うのが好ましい。
プロピレン重合体成分を製造する工程として好ましいのは、バルク重合や懸濁重合等の液相重合あるいは気相重合法である。
分子量を調整するために必要な水素量は、使用する製造プロセスの種類、重合温度、圧力によって異なるため、適宜調整すればよい。
本発明のポリプロピレン系樹脂組成物を構成する、エチレン・α-オレフィン共重合体(B)は、エチレンと炭素数3~8のα-オレフィンとの共重合体である。
本発明のポリプロピレン系樹脂組成物を構成する基材成分には、無機充填材(E)が含まれていてもよい。
本発明のポリプロピレン系樹脂組成物を構成する基材成分は、上述したプロピレン系重合体(a-1)および必要に応じてプロピレン・エチレン共重合体(a-2)からなるポリプロピレン系樹脂(A)と、エチレン・α-オレフィン共重合体(B)と、必要に応じて(E)無機充填材からなる。このような基材成分は、(a-1)、(a-2)、(B)、(E)の合計100重量部中に、(a-1)を30~80重量部、(a-2)を0~30重量部、(B)を20~50重量部、(E)を0~40重量部含有するものであり、好ましくは、(a-1)を30~75重量部、(a-2)を0~25重量部、(B)を20~40重量部、(E)を0~40重量部含有する。
本発明のポリプロピレン系樹脂組成物を構成する脂肪酸アミド(C)は、滑剤あるいは帯電防止剤として作用する脂肪酸アミドであることが好ましい。本発明で用いられる脂肪酸アミドは、飽和脂肪酸アミドであっても、不飽和脂肪酸アミドであってもよく、好ましくは、炭素原子数8~25の脂肪酸アミドおよびその2量体であり、より好ましくは炭素原子数8~25の脂肪酸アミド、さらに好ましくは炭素原子数15~25の脂肪酸アミドである。
本発明のポリプロピレン系樹脂組成物を構成する界面活性剤(D)は、ポリプロピレン系樹脂組成物中において、帯電防止剤としての作用を有するものであることが好ましい。
本発明のポリプロピレン系樹脂組成物には、必要に応じて、耐熱安定剤、耐候安定剤、耐光安定剤、老化防止剤、酸化防止剤、脂肪酸金属塩、軟化剤、分散剤、充填剤、着色剤、顔料などのその他の添加剤(F)が、本発明の目的を損なわない範囲で配合されていてもよい。
本発明のポリプロピレン系樹脂組成物は、(a-1)プロピレン系重合体と必要に応じて(a-2)プロピレン・エチレン共重合体とからなるポリプロピレン系樹脂(A)と、エチレン・α-オレフィン共重合体(B)と、必要に応じて無機充填材(E)からなる基材成分と、脂肪酸アミド(C)および界面活性剤(D)を含む。これらの含有量は、それぞれ以下のとおりである。
本発明の成形体は、上記本発明のポリプロピレン系樹脂組成物からなる。
JIS K 7210に準拠し、230℃、21.16N荷重の条件でメルトフローレート(MFR)を測定した。
まず、試料を5g精秤し、1,000ミリリットルのナス型フラスコに入れ、さらにBHT(ジブチルヒドロキシトルエン、フェノール系酸化防止剤)1gを添加した後、回転子及びn-デカン700ミリリットルを投入した。
フーリエ変換赤外線分光法(FT-IR)により測定した。
デカリン溶媒を用いて、135℃で測定した。サンプル約20mgをデカリン15mlに溶解し、135℃のオイルバス中で比粘度ηspを測定した。このデカリン溶液にデカリン溶媒を5ml追加して希釈後、同様にして比粘度ηspを測定した。この希釈操作をさらに2回繰り返し、濃度(C)を0に外挿した時のηsp/Cの値を極限粘度([η]:〔dl/g〕)として求めた。
・ゴム摩擦による傷付き試験(Scuff足蹴り試験)
樹脂組成物を金型に射出成形して製造し、表面にシボを有する成形体を、成形後1週間以上経過した状態で、試験前に23℃恒温状態で2時間以上静置して状態調節したものを、テストピースとして用いた。テストピースの形状は、縦120cm、横80cm、高さ0.3cmであった。
1.テストピース(1)を装置の台座(3)上に固定する。
2.デジタルデップスゲ-ジを振り子上部にセットし、ゲージの先端を振り子上部へ当て、ゲージの目盛りが0mmになることを確認する。
3.パンタグラフ(4)のレバーを回転させ、台座を上昇させゲージの目盛りが0.3mmになるよう合せる。
4.摩擦物(ゴム試験片)(2)を装着した振り子先端を所定の高さ((5)、傷付き試験面より20cm)の高さまで引き上げる。
5.振り子を放し、テストピース(1)の試験面へゴムを擦る。
6.試験面(6)の傷つき性を目視で判断する。
(1)固体状チタン触媒成分の調製
無水塩化マグネシウム952g、デカン4420mlおよび2-エチルヘキシルアルコール3906gを、130℃で2時間加熱して均一溶液とした。この溶液中に無水フタル酸213gを添加し、130℃にてさらに1時間攪拌混合を行って無水フタル酸を溶解させた。
固体状チタン触媒成分87.5g、トリエチルアルミニウム99.8mL、ジエチルアミノトリエトキシシラン28.4ml、ヘプタン12.5Lを内容量20Lの攪拌機付きオートクレーブに挿入し、内温15~20℃に保ちプロピレンを875g挿入し、100分間攪拌しながら反応させた。重合終了後、固体成分を沈降させ、上澄み液の除去およびヘプタンによる洗浄を2回行った。得られた前重合触媒を精製ヘプタンに再懸濁して、固体触媒成分濃度で0.7g/Lとなるよう、ヘプタンにより調整を行った。
内容量1000Lの攪拌機付きベッセル重合器に、プロピレンを131kg/時間、触媒スラリーを遷移金属触媒成分として0.70g/時間、トリエチルアルミニウム19.6mL/時間、ジエチルアミノトリエトキシシラン4.2mL/時間を連続的に供給し、水素を気相部の水素濃度が5.3mol%になるように供給した。重合温度75℃、圧力3.5MPa/Gで重合を行った。
製造例1の固体状チタン触媒成分の調製(1)で得た固体状チタン触媒成分を用い、前重合触媒の製造(2)および本重合(3)を以下のようにして行った。
固体触媒成分86.0g、トリエチルアルミニウム39.2mL、2-イソブチル-2-イソプロピル-1,3-ジメトキシプロパン11.0ml、ヘプタン4.6Lを内容量20Lの攪拌機付きオートクレーブに挿入し、内温10~15℃に保ちプロピレンを860g挿入し、180分間攪拌しながら反応させた。重合終了後、固体成分を沈降させ、上澄み液の除去およびヘプタンによる洗浄を2回行った。得られた前重合触媒を精製ヘプタンに再懸濁して、固体触媒成分濃度で1.0g/Lとなるよう、ヘプタンにより調整を行った。
内容量58Lのジャケット付循環式管状重合器にプロピレンを40kg/時間、水素を204NL/時間、(2)で製造した触媒スラリーを固体触媒成分として0.66g/時間、トリエチルアルミニウム2.5ml/時間、ジシクロペンチルジメトキシシラン1.4ml/時間を連続的に供給し、気相の存在しない満液の状態にて重合した。管状重合器の温度は69.5℃であり、圧力は3.5MPa/Gであった。
製造例1の固体状チタン触媒成分の調製(1)および前重合触媒の製造(2)により得た、前重合触媒(触媒スラリー)を用いて、本重合(3)を以下のようにして行った。
内容量58Lのジャケット付循環式管状重合器にプロピレンを45kg/時間、水素を182NL/時間、(2)で製造した触媒スラリーを固体触媒成分として0.41g/時間、トリエチルアルミニウム2.7ml/時間、ジエチルアミノトリエトキシシラン1.1ml/時間を連続的に供給し、気相の存在しない満液の状態にて重合した。管状重合器の温度は70℃であり、圧力は3.4MPa/Gであった。
・エチレン・α-オレフィン共重合体B-1:α-オレフィン(オクテン)量が38.6重量%であり、MFRが2g/10分であるエチレン・オクテンランダム共重合体、製品名:EG8100、ダウケミカル社製
・エチレン・α-オレフィン共重合体B-2:α-オレフィン(ブテン)量が27.3重量%であり、MFRが2g/10分であるエチレン・ブテンランダム共重合体、製品名:A1070S、三井化学(株)社製
・脂肪酸アミドC-1:エルカ酸アミド、製品名:ニュートロン‐S、日本製化(株)社製
・脂肪酸アミドC-2:オレイン酸アミド、製品名:ニュートロン‐P、日本製化(株)社製
・界面活性剤D-1:グリセロールモノステアレート、製品名:エレクトロストリッパーTS-5、花王(株)社製
・無機充填材E-1:タルク、平均粒径(レーザー回折)5μm、製品名:ハイフィラー5000PJ、浅田製粉(株)社製
[実施例1]
製造例1で得たプロピレン系重合体A-1、エチレン・α-オレフィン共重合体B-1、脂肪酸アミドC-1、界面活性剤D-1の各成分を、表2に示す量(重量部)で用いるとともに、その他の添加剤として、酸化防止剤としてIrganox1010(BASF(株))0.1重量部およびIrgafos168(BASF(株))0.1重量部、耐光剤としてLA-52((株)ADEKA製)0.1重量部、滑剤としてステアリン酸カルシウム((株)日本油脂)0.1重量部、核剤としてアデカスタブNA-11((株)ADEKA製)0.1重量部、および黒色顔料としてMB PPCM 888Y-232((株)東京インキ製)3重量部を用い、これらを順次配合してタンブラーでドライブレンドした。
A~E成分の各成分および配合量(すなわち、その他の添加剤以外の各成分および配合量。重量部)を、表2または表3に示す通りとしたことのほかは、実施例1と同様にしてポリプロピレン系樹脂組成物ペレットを製造し、射出成形にてテストピースを製造し、ゴム摩擦による傷付き試験(Scuff足蹴り試験)を行った。結果を表2または3に併せて示す。
(2)摩擦物(ゴム試験片)
(3)台座
(4)パンタグラフ
(5)振り子の高さ(20cm)
(6)試験面
Claims (6)
- (A)(a-1)JIS K 7210に準拠した方法で測定したメルトフローレート(MFR、230℃、21.16N荷重)が10g/10min以上300g/10min以下であって、プロピレンから導かれる構成単位の含量が98mol%以上100mol%以下であり、エチレンと炭素原子数4~8のα-オレフィンから選ばれる少なくとも1種のα-オレフィンから導かれる構成単位の含量が0mol%以上2mol%以下であるプロピレン系重合体30~80重量部と、
(a-2)135℃デカリン中で測定した極限粘度[η]が1.5dl/g以上8dl/g以下、エチレンから導かれる構成単位の含量が30mol%以上60mol%以下であるプロピレン・エチレン共重合体0~30重量部と
からなり、(a-1)と(a-2)の合計が30~80重量部であるポリプロピレン系樹脂と、
(B)エチレン含有率が65mol%以上90mol%以下である、エチレンと、炭素原子数3~8のα-オレフィンから選ばれる少なくとも1種のα-オレフィンからなるエチレン・α-オレフィン共重合体20~50重量部と、
(E)無機充填材0~40重量部と
からなり、(a-2)と(B)との合計が20~50重量部である基材成分(ただし、(A)、(B)、(E)の合計が100重量部である)100重量部に対して、
(C)脂肪酸アミド0.2~1重量部、および
(D)界面活性剤0.2~1重量部
を含むポリプロピレン系樹脂組成物。 - 前記(C)脂肪酸アミドが、炭素原子数8~25の脂肪酸アミドおよびその2量体より選ばれる1種以上であり、かつ、
前記(D)界面活性剤が、炭素原子数が8~25であるエステル基を、1つまたは2つ有する化合物である、請求項1に記載のポリプロピレン系樹脂組成物。 - 請求項1または2に記載のポリプロピレン系樹脂組成物からなる成形体。
- 前記成形体が射出成形体である請求項3に記載の成形体。
- 前記成形体が自動車内外装部材である請求項3に記載の成形体。
- 前記自動車内外装部材が、自動車ドア部材またはピラー部材である、請求項5に記載の成形体。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014536857A JP6038163B2 (ja) | 2012-09-18 | 2013-09-17 | ポリプロピレン系樹脂組成物およびその用途 |
CN201380048044.5A CN104640923B (zh) | 2012-09-18 | 2013-09-17 | 聚丙烯系树脂组合物及其用途 |
BR112015005907-4A BR112015005907B1 (pt) | 2012-09-18 | 2013-09-17 | Composição de resina de polipropileno e artigo conformado compreendendo a referida composição |
MX2015003366A MX2015003366A (es) | 2012-09-18 | 2013-09-17 | Composicion de resina de polipropileno y sus usos. |
US14/428,572 US10619039B2 (en) | 2012-09-18 | 2013-09-17 | Polypropylene resin composition and use thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012204602 | 2012-09-18 | ||
JP2012-204602 | 2012-09-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014046086A1 true WO2014046086A1 (ja) | 2014-03-27 |
Family
ID=50341396
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/075030 WO2014046086A1 (ja) | 2012-09-18 | 2013-09-17 | ポリプロピレン系樹脂組成物およびその用途 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10619039B2 (ja) |
JP (1) | JP6038163B2 (ja) |
CN (1) | CN104640923B (ja) |
BR (1) | BR112015005907B1 (ja) |
MX (1) | MX2015003366A (ja) |
WO (1) | WO2014046086A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017195787A1 (ja) * | 2016-05-10 | 2017-11-16 | 株式会社プライムポリマー | 繊維強化ポリプロピレン系樹脂組成物およびその成形体 |
WO2019117185A1 (ja) * | 2017-12-13 | 2019-06-20 | 株式会社プライムポリマー | ポリプロピレン系樹脂組成物及びその成形体 |
US10392492B2 (en) | 2013-12-04 | 2019-08-27 | Borealis Ag | Polypropylene composition suitable for primerless painting |
JP2020084052A (ja) * | 2018-11-27 | 2020-06-04 | 株式会社豊田中央研究所 | 樹脂組成物および樹脂成形体 |
WO2021192710A1 (ja) * | 2020-03-23 | 2021-09-30 | 株式会社プライムポリマー | ポリプロピレン系樹脂組成物及びその成形体 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6566842B2 (ja) * | 2015-11-11 | 2019-08-28 | 株式会社プライムポリマー | ポリプロピレン系樹脂組成物 |
US11220594B2 (en) | 2017-07-26 | 2022-01-11 | Ineos Styrolution Group Gmbh | Scratch-resistant styrene copolymer composition containing amide wax |
WO2019119392A1 (en) * | 2017-12-22 | 2019-06-27 | Borouge Compounding Shanghai Co., Ltd. | Soft polyolefin composition |
CN113614160B (zh) * | 2019-03-25 | 2023-03-31 | 三井化学株式会社 | 烯烃系聚合物组合物 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001261902A (ja) * | 2000-03-17 | 2001-09-26 | Tokuyama Corp | ポリプロピレン系樹脂組成物 |
JP2002060560A (ja) * | 2000-08-18 | 2002-02-26 | Idemitsu Petrochem Co Ltd | 自動車内装部品用ポリプロピレン系組成物 |
JP2002212353A (ja) * | 2001-01-19 | 2002-07-31 | Grand Polymer Co Ltd | ポリプロピレン樹脂組成物 |
JP2003171472A (ja) * | 2001-12-05 | 2003-06-20 | Japan Polychem Corp | マスターバッチ及びそれを用いた成形品の製造方法 |
JP2004051769A (ja) * | 2002-07-19 | 2004-02-19 | Nissan Motor Co Ltd | 自動車内装成形品 |
JP2007526345A (ja) * | 2003-05-05 | 2007-09-13 | 本田技研工業株式会社 | 耐スクラッチ性ポリプロピレン組成物 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1209255B (it) | 1980-08-13 | 1989-07-16 | Montedison Spa | Catalizzatori per la polimerizzazione di olefine. |
US6777508B1 (en) | 1980-08-13 | 2004-08-17 | Basell Poliolefine Italia S.P.A. | Catalysts for the polymerization of olefins |
US4734448A (en) * | 1985-07-10 | 1988-03-29 | Idemitsu Petrochemical Co., Ltd. | Propylene polymer composition |
JP3476793B2 (ja) | 1990-04-13 | 2003-12-10 | 三井化学株式会社 | オレフィン重合用固体状チタン触媒成分、オレフィン重合用触媒およびオレフィンの重合方法 |
JP3088164B2 (ja) | 1991-12-20 | 2000-09-18 | 三井化学株式会社 | プロピレン系ブロック共重合体の製造方法 |
JP3280477B2 (ja) | 1992-08-31 | 2002-05-13 | 三井化学株式会社 | オレフィン重合用固体状チタン触媒成分の調製方法 |
JP4963756B2 (ja) * | 2001-02-09 | 2012-06-27 | 株式会社ユポ・コーポレーション | ボイド含有熱可塑性樹脂延伸フィルムおよびその製造方法 |
EP1236769A1 (en) * | 2001-02-21 | 2002-09-04 | Borealis Technology Oy | Heterophasic propylene polymer |
AU2003257555A1 (en) | 2002-08-19 | 2004-03-03 | Ube Industries, Ltd. | CATALYSTS FOR POLYMERIZATION OR COPOLYMERIZATION OF Alpha-OLEFINS, CATALYST COMPONENTS THEREOF, AND PROCESSES FOR POLYMERIZATION OF Alpha-OLEFINS WITH THE CATALYSTS |
CN1580115A (zh) * | 2003-08-01 | 2005-02-16 | 上海普利特复合材料有限公司 | 一种耐划痕滑石粉填充聚丙烯组成及制备方法 |
EP1600480A1 (en) * | 2004-05-27 | 2005-11-30 | Borealis Technology OY | Novel propylene polymer compositions |
KR101044214B1 (ko) | 2005-05-18 | 2011-06-29 | 미쓰이 가가쿠 가부시키가이샤 | 올레핀 중합용 촉매, 올레핀 중합체의 제조방법, 프로필렌계 공중합체의 제조방법, 프로필렌 중합체, 프로필렌계 중합체 조성물 및 이들의 용도 |
JP5374606B2 (ja) | 2006-01-20 | 2013-12-25 | 三井化学株式会社 | プロピレン系重合体組成物およびその用途 |
KR100785084B1 (ko) * | 2006-03-30 | 2007-12-12 | 삼성전자주식회사 | 압전형 mems 스위치 및 그 제조방법 |
JP2009079117A (ja) | 2007-09-26 | 2009-04-16 | Prime Polymer:Kk | ポリプロピレン系樹脂組成物 |
JP5747561B2 (ja) * | 2011-03-02 | 2015-07-15 | 住友化学株式会社 | プロピレン樹脂組成物 |
-
2013
- 2013-09-17 BR BR112015005907-4A patent/BR112015005907B1/pt active IP Right Grant
- 2013-09-17 CN CN201380048044.5A patent/CN104640923B/zh active Active
- 2013-09-17 MX MX2015003366A patent/MX2015003366A/es unknown
- 2013-09-17 WO PCT/JP2013/075030 patent/WO2014046086A1/ja active Application Filing
- 2013-09-17 JP JP2014536857A patent/JP6038163B2/ja active Active
- 2013-09-17 US US14/428,572 patent/US10619039B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001261902A (ja) * | 2000-03-17 | 2001-09-26 | Tokuyama Corp | ポリプロピレン系樹脂組成物 |
JP2002060560A (ja) * | 2000-08-18 | 2002-02-26 | Idemitsu Petrochem Co Ltd | 自動車内装部品用ポリプロピレン系組成物 |
JP2002212353A (ja) * | 2001-01-19 | 2002-07-31 | Grand Polymer Co Ltd | ポリプロピレン樹脂組成物 |
JP2003171472A (ja) * | 2001-12-05 | 2003-06-20 | Japan Polychem Corp | マスターバッチ及びそれを用いた成形品の製造方法 |
JP2004051769A (ja) * | 2002-07-19 | 2004-02-19 | Nissan Motor Co Ltd | 自動車内装成形品 |
JP2007526345A (ja) * | 2003-05-05 | 2007-09-13 | 本田技研工業株式会社 | 耐スクラッチ性ポリプロピレン組成物 |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10392492B2 (en) | 2013-12-04 | 2019-08-27 | Borealis Ag | Polypropylene composition suitable for primerless painting |
EP3077458B1 (en) * | 2013-12-04 | 2020-03-18 | Borealis AG | Polypropylene composition suitable for primerless painting |
JP2020158787A (ja) * | 2016-05-10 | 2020-10-01 | 株式会社プライムポリマー | 繊維強化ポリプロピレン系樹脂組成物およびその成形体 |
JPWO2017195787A1 (ja) * | 2016-05-10 | 2019-03-28 | 株式会社プライムポリマー | 繊維強化ポリプロピレン系樹脂組成物およびその成形体 |
WO2017195787A1 (ja) * | 2016-05-10 | 2017-11-16 | 株式会社プライムポリマー | 繊維強化ポリプロピレン系樹脂組成物およびその成形体 |
US10858507B2 (en) | 2016-05-10 | 2020-12-08 | Prime Polymer Co., Ltd. | Fiber-reinforced polypropylene-based resin composition and molded product thereof |
JP7126532B2 (ja) | 2016-05-10 | 2022-08-26 | 株式会社プライムポリマー | 繊維強化ポリプロピレン系樹脂組成物およびその成形体 |
WO2019117185A1 (ja) * | 2017-12-13 | 2019-06-20 | 株式会社プライムポリマー | ポリプロピレン系樹脂組成物及びその成形体 |
JPWO2019117185A1 (ja) * | 2017-12-13 | 2020-11-19 | 株式会社プライムポリマー | ポリプロピレン系樹脂組成物及びその成形体 |
JP2020084052A (ja) * | 2018-11-27 | 2020-06-04 | 株式会社豊田中央研究所 | 樹脂組成物および樹脂成形体 |
JP7145055B2 (ja) | 2018-11-27 | 2022-09-30 | 株式会社豊田中央研究所 | 樹脂組成物および樹脂成形体 |
WO2021192710A1 (ja) * | 2020-03-23 | 2021-09-30 | 株式会社プライムポリマー | ポリプロピレン系樹脂組成物及びその成形体 |
JP7375164B2 (ja) | 2020-03-23 | 2023-11-07 | 株式会社プライムポリマー | ポリプロピレン系樹脂組成物及びその成形体 |
Also Published As
Publication number | Publication date |
---|---|
US20150274948A1 (en) | 2015-10-01 |
JPWO2014046086A1 (ja) | 2016-08-18 |
CN104640923B (zh) | 2017-08-22 |
CN104640923A (zh) | 2015-05-20 |
MX2015003366A (es) | 2015-06-05 |
JP6038163B2 (ja) | 2016-12-07 |
BR112015005907A2 (pt) | 2017-07-04 |
US10619039B2 (en) | 2020-04-14 |
BR112015005907B1 (pt) | 2021-03-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6038163B2 (ja) | ポリプロピレン系樹脂組成物およびその用途 | |
JP5828845B2 (ja) | ポリプロピレン系樹脂組成物 | |
EP2914649B1 (en) | Articles comprising broad molecular weight distribution polypropylene resins | |
JP5441909B2 (ja) | プロピレン系ブロック共重合体、該共重合体を含む組成物およびこれらから得られる成形体 | |
JP6566842B2 (ja) | ポリプロピレン系樹脂組成物 | |
WO2006114318A1 (en) | Alpha-olefin homo- or copolymer compositions | |
JP2016084386A (ja) | タルク含有ポリプロピレン系樹脂組成物 | |
JP7406922B2 (ja) | ポリプロピレン系樹脂組成物 | |
JP5613032B2 (ja) | ポリプロピレン系樹脂組成物 | |
JP6259751B2 (ja) | ポリプロピレン系樹脂組成物およびその用途 | |
WO2018092805A1 (ja) | マスターバッチ組成物およびこれを含むポリプロピレン樹脂組成物 | |
JP2015178568A (ja) | プロピレン系ブロック共重合体 | |
JP2014214202A (ja) | ポリプロピレン系樹脂組成物 | |
JP6068231B2 (ja) | 樹脂組成物およびその用途 | |
WO2023112857A1 (ja) | ポリプロピレン系樹脂組成物およびその用途 | |
JP7186594B2 (ja) | プロピレン系重合体の製造方法 | |
JP6348422B2 (ja) | プロピレン系重合体組成物およびこれを用いた射出成形体 | |
JP2020084134A (ja) | プロピレン系樹脂組成物および成形体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13838615 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014536857 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2015/003366 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14428572 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112015005907 Country of ref document: BR |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13838615 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 112015005907 Country of ref document: BR Kind code of ref document: A2 Effective date: 20150317 |