CN101568592B - Propylene resin composition and molded body made from the same - Google Patents
Propylene resin composition and molded body made from the same Download PDFInfo
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- CN101568592B CN101568592B CN200780048026.1A CN200780048026A CN101568592B CN 101568592 B CN101568592 B CN 101568592B CN 200780048026 A CN200780048026 A CN 200780048026A CN 101568592 B CN101568592 B CN 101568592B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
Disclosed is a propylene resin composition which contains a propylene resin (I) containing 50-100% by weight of the component (A) described below and 0-50% by weight of the component (B) described below, and 5-400 parts by weight of the component (C) described below per 100 parts by weight of the propylene resin (I). Component (A): a propylene polymer having a molecular weight distribution within the range of 1.0-2.9 and an isotactic pentad fraction within the range of 0.9-1.0. Component (B): a propylene polymer having a molecular weight distribution within the range of 3.0-10 and an isotactic pentad fraction within the range of 0.9-1.0 Component (C): a fiber.
Description
Technical field
The present invention relates to propylene resin composition and the moulded product that comprises this resin combination.In more detail, the present invention relates to propylene resin composition, it can be used as the material for moulded product, its flexural strength and good appearance and only have a small amount of hickie, and relate to the moulded product that comprises this resin combination.
Background technology
As the physical strength that the improves crystalline thermoplastic resin method of rigidity and shock strength for example, conventionally known is with crystalline thermoplastic resin and for example filler and glass fibre blend of material in the art.
For example, JP 3-121146A has disclosed the molding polyolefine resin composition of long fiber reinforcement, and it comprises fortifying fibre and contains polyolefine and the resin Composition of the olefin polymer of modification, and the length of the above-mentioned fiber in the resin is 2mm or longer.
In addition, JP 2005-60678A has disclosed composition, and it comprises: fiber, crystalline thermoplastic resin, and another kind of Tc is than front a kind of thermoplastic resin low 10 ℃ or more crystalline thermoplastic resin.
Summary of the invention
An object of the present invention is to provide propylene resin composition, it can be used as the material for moulded product, its flexural strength and good appearance and only have a small amount of hickie, and the moulded product that comprises this resin combination is provided.
The present invention is propylene resin composition, and it comprises:
The acrylic resin of-100 weight parts (I), it contains the propene polymer (component (A)) of the isotaxy five unit number of componentss of the molecular weight distribution with 1.0-2.9 of 50-100wt% and 0.9-1.0, with the propene polymer (component (B)) of the isotaxy five unit number of componentss of the molecular weight distribution with 3.0-10 of 0-50wt% and 0.9-1.0, component (A) and summation (B) are 100wt%; With
The fiber of-5 to 400 weight parts (component (C)).
Above-mentioned composition can be called as " the first resin combination " hereinafter.
In addition, the present invention is propylene resin composition, and it comprises:
The acrylic resin of-100 weight parts (II), it contains the propene polymer (component (A)) of the isotaxy five unit number of componentss of the molecular weight distribution with 1.0-2.9 of 50-100wt% and 0.9-1.0, the propene polymer of the isotaxy five unit number of componentss of the molecular weight distribution with 3.0-10 of 0-50wt% and 0.9-1.0 (component (B)), the modified polyolefin resin by the modification of unsaturated carboxylic acid or derivatives thereof (component (D)) with the 0.1-70 weight part, component (A) and summation (B) are 100wt%, and are 100 weight parts with respect to the weight part of component (D); With
The fiber of-5 to 400 weight parts (component (C)).
Above-mentioned composition can be called as " the second resin combination " hereinafter.
Further, the present invention is the moulded product that comprises any aforesaid propylene resin combination.
Embodiment
The propene polymer of component (A) has the molecular weight distribution of 1.0-2.9 and the isotaxy five unit number of componentss of 0.9-1.0.
The example of the propene polymer of component (A) is alfon, propylene-ethylene random copolymers, propylene-alpha-olefin random copolymers, and by with propylene homopolymerization and the propylene-based block copolymer that then ethene and copolymerization of propylene obtained.
The example of alpha-olefin is 1-butylene in as the propylene-alpha-olefin random copolymers of component (A), the 2-methyl-1-propylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, the 1-hexene, 2-ethyl-1-butylene, 2,3-dimethyl-1-butylene, the 2-Methyl-1-pentene, the 3-Methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butylene, the 1-heptene, methyl isophthalic acid-hexene, dimethyl-1-amylene, ethyl-1-amylene, trimethylammonium-1-butylene, methylethyl-1-butylene, the 1-octene, Methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl group-1-heptene, methylethyl-1-heptene, trimethylammonium-1-amylene, propyl group-1-amylene, diethyl-1-butylene, the 1-nonene, 1-decene, 1-undecylene and 1-dodecylene.Preferred 1-butylene, 1-amylene, 1-hexene or 1-octene.
From the outward appearance of moulded product and the viewpoint of its manufacturability, the propene polymer of component (A) has 1.0-2.9, preferred 1.2-2.5, and the more preferably molecular weight distribution of 1.5-2.4.
Under the condition of molecular weight distribution in being disclosed in JP 2001-302858A according to gel permeation chromatography measurement.
From the physical strength of the moulded product viewpoint of rigidity and its manufacturability for example, the propene polymer of component (A) has 0.9-1.0, preferred 0.92-1.0, more preferably 0.94-1.0, further preferably 0.94-0.99 and particularly preferably the isotaxy five unit number of componentss of 0.94-0.97.
Isotaxy five unit number of componentss are according to the group unit, Unit five in the propylene molecules chain, are present in the mark of propylene monomer units at the center of isotactic chain.In other words, it is the mark of propylene monomer units that is present in the center of the chain that the meso bonding by 5 continuous propylene monomer units forms.
And these isotaxy five unit number of componentss bases are disclosed in A.Zambelli etc., Macromolecules,
6, the method in 925 (1973) is namely used
13The method of C-NMR is measured.
In this, based on Macromolecules,
8, 687 (1975) point out the NMR absorption peak.
From the physical strength of the outward appearance of moulded product and the moulded product viewpoint of rigidity and shock strength for example, the propene polymer of component (A) has preferred 140-160 ℃, and more preferably 145-160 ℃, and further preferred 145-155 ℃ melt temperature.
Melt temperature is corresponding to the temperature of maximum heat absorption peak in the melting endothermic curve of measuring according to following methods.
The method may further comprise the steps: in nitrogen atmosphere, use the Co. by PerkinElmer, and the differential scanning calorimeter that Ltd. produces, cooling type DSC-7 with 10mg sample heating 5 minutes, makes the sample melting thus under 220 ℃ fast; Under 5 ℃/minute speed, be cooled to 40 ℃; And heat under 5 ℃/minute speed, obtain thus the melting endothermic curve, wherein the temperature corresponding to the maximum heat absorption peak is melt temperature.Incidentally, use above-mentioned monitoring to measure under 5 ℃/minute heating rate, the temperature that indium begins melting is 156.6 ℃.
When component (A) is propylene-ethylene copolymers, propylene-alpha-olefin copolymers or propylene-ethylene-alpha-olefin copolymer, from the physical strength of the outward appearance of moulded product and the moulded product viewpoint of rigidity and shock strength for example, the involved quantity of other monomeric unit except propylene is preferably 0.5wt% or still less, more preferably 0.3wt% or still less, and further preferred 0.1wt% or still less.The above-mentioned amount of other monomeric unit except propylene is used and is disclosed in " New Edition:Kobunshi Bunseki Handbook " (by The Chemical Society Of Japan, TheJapan Society For Polymer Analytical Chemistry edits and by KinokuniyaCo., Ltd. publishes (1995)) in IR method or NMR method measure.
From the physical strength of the outward appearance of moulded product and the moulded product viewpoint of rigidity and shock strength for example, the propene polymer of component (A) contains quantity and is preferably more than 0mol% to 1.2mol% or still less, further preferably more than 0mol% to 1.0mol% or still less, and particularly preferably more than 0mol% to 0.7mol% or still less 2, the 1-bonding.Incidentally, the above-mentioned amount basis of 2,1-bonding is disclosed in Polymer,
30, the method in 1350 (1989) is measured.
Dispersiveness and the outward appearance of moulded product and the viewpoint of shock strength of fiber from moulded product (component (C)), the propene polymer of component (A) had preferred 1-500g/10 minute, more preferably 5-300g/10 minute, further preferred 10-200g/10 minute and further preferred 50-150g/10 minute melt flow rate (MFR) (MFR) still.Incidentally, MFR measures under the 21.2N load at 230 ℃ according to ASTMD1238.
The propene polymer of component (A) can be according to for example solution polymerization process, slurry phase polymerisation process, bulk polymerization and gas phase polymerization process preparation of certain methods.Those polymerization processs use separately or two or more be combined into to exercise and use with it.The specific preparation method's of the propene polymer of component (A) example be disclosed in document for example " Shin Polymer Seizo Process " (edited by Yasuji SAEKI, by Kogyo Chosakai Publishing, Inc. publishes (1994)), the polymerization process among JP4-323207A and the JP61-287917A.
The propene polymer of component (A) preferably uses single-point catalyst, and more preferably metallocene catalyst preparation.The example of metallocene catalyst is to comprise following those: the transition metal complex that contains one or more cyclopentadienyi skeleton of periodictable 4-6 family, can be by forming the aluminum compound (for example methylaluminoxane) of balance anion with above-mentioned transition metal complex reaction, and boron compound (for example trityl group four (pentafluorophenyl group) borate and DMA
Four (pentafluorophenyl group) borate).
The example that uses the preparation method of single-point catalyst is to be disclosed in for example polymerization process among JP6-172414A, JP8-27237A, WO2004/044013, WO2003/040195, WO2003/040201, JP4-323207A, JP5-125112A and the JP5-295022A of document.
The propene polymer of component (B) has the molecular weight distribution of 3.0-10 and the isotaxy five unit number of componentss of 0.9-1.0.
The example of the propene polymer of component (B) is alfon, propylene-ethylene random copolymers, propylene-alpha-olefin random copolymers, and by with propylene homopolymerization and the propylene-based block copolymer that then ethene and copolymerization of propylene obtained.The alpha-olefin in the propylene-alpha-olefin random copolymers of component (A) that the example of alpha-olefin exemplifies above being in as the propylene-alpha-olefin random copolymers of component (B).
From the viewpoint of the manufacturability of moulded product, the propene polymer of component (B) has 3.0-10, preferred 3.2-8, and the more preferably molecular weight distribution of 3.4-6.Incidentally, the molecular weight distribution of the propene polymer of component (B) is according to measuring with the similar method of the top method of mentioning in the propene polymer of component (A).
From the physical strength of the moulded product viewpoint of rigidity and its manufacturability for example, the propene polymer of component (B) has 0.9-1.0, preferred 0.92-1.0, more preferably 0.94-1.0, further preferably 0.94-0.99 and particularly preferably the isotaxy five unit number of componentss of 0.94-0.97.Incidentally, the isotaxy five unit number of componentss of the propene polymer of component (B) have with the top definition of mentioning in the propene polymer of component (A) and similarly define, and according to measuring with the similar method of the top method of in the propene polymer of component (A), mentioning.
From the physical strength of the moulded product viewpoint of rigidity and shock strength for example, the propene polymer of component (B) has preferred 155-180 ℃, and more preferably 160-175 ℃, and further preferred 162-172 ℃ melt temperature.The melt temperature of the propene polymer of component (B) has with the top definition of mentioning in the propene polymer of component (A) and similarly defines, and according to measuring with the similar method of the top method of in the propene polymer of component (A), mentioning.
When the propene polymer of component (B) is propylene-ethylene copolymers, propylene-alpha-olefin copolymers or propylene-ethylene-alpha-olefin copolymer, from the physical strength of the outward appearance of moulded product and the moulded product viewpoint of rigidity and shock strength for example, the involved quantity of other monomeric unit except propylene is preferably 0.5wt% or still less, more preferably 0.3wt% or still less, and further preferred 0.1wt% or still less.The above-mentioned amount of other monomeric unit except propylene is according to measuring with the above mentioned similar method of method of explaining about component (A).
Dispersiveness and the outward appearance of moulded product and the viewpoint of shock strength of fiber from moulded product (component (C)), the propene polymer of component (B) had preferred 1-500g/10 minute, more preferably 5-300g/10 minute, further preferred 10-200g/10 minute and further preferred 50-150g/10 minute melt flow rate (MFR) (MFR) still.Incidentally, MFR measures under the 21.2N load at 230 ℃ according to ASTMD1238.
The propene polymer of component (B) can be according to for example solution polymerization process, slurry phase polymerisation process, bulk polymerization and gas phase polymerization process preparation of certain methods, these methods be disclosed in document for example " Shin Polymer Seizo Process " (edited by Yasuji SAEKI, by KogyoChosakai Publishing, Inc. publishes (1994)), among JP4-323207A and the JP61-287917A.Those polymerization processs use separately or two or more be used in combination with it.
Preferably with the preparation of multiple spot catalyzer, this multiple spot catalyzer uses the ingredient of solid catalyst that contains titanium atom, magnesium atom and halogen atom to obtain to the propene polymer of component (B).
The example that is used as the fiber of component (C) is inorganic fibre, organic fibre and natural fiber.Its object lesson is glass fibre, basalt fibre, carbon fiber, steel fiber (for example copper fiber and Stainless Steel Fibre), Kevlar, aromatic polyester fiber, trevira, nylon fiber, kenaf, bamboo fibers, jute fibre, ramee and cellulosic fibre.In the middle of them, preferred inorganic fibre, and more preferably glass fibre.
From the physical strength of moulded product for example rigidity and shock strength with and the viewpoint of manufacturability, the fiber of component (C) has preferred 2-100mm, more preferably 2-50mm, further preferred 3-20mm and the weight average fiber length of 5-15mm particularly preferably.In this, the weight average fiber length of fiber refers to be contained in the length of the fiber in the said composition, and measures according to the method that is disclosed among the JP2002-5924A.
Can use the fiber of adhesives component (C).The example of tackiness agent is polyolefin resin, urethane resin, vibrin, acrylic resin, Resins, epoxy, starch and vegetables oil.In addition, can blend lubricant, for example polyolefin resin of sour modification, surface treatment agent and paraffin.
In order to improve for example consistency and the cohesiveness between the fiber and propene polymer (being component (A) and/or component (B)), fiber can be processed with surface treatment agent in advance.The example of surface treatment agent is silane coupling agent, titanate coupling agent, aluminum coupling agent, chrome-silicon alkane coupling agent, zirconium coupling agent and borine coupling agent.In the middle of them, preferred silane coupling agent or titanate coupling agent, and silane coupling agent particularly preferably.
The example of above-mentioned silane coupling agent is triethoxyl silane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-aminopropyl triethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ mercaptopropyitrimethoxy silane and γ-r-chloropropyl trimethoxyl silane.In the middle of them, preferred aminosilane, and more preferably γ-aminopropyl triethoxysilane or N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane.
The example of processing the method for fiber with above-mentioned treatment agent is for example aqueous process, organic solvent method and injection method of ordinary method.
The modified polyolefin resin of component (D) is:
(1) by unsaturated carboxylic acid and/or their derivatives graft are aggregated to the modified polyolefin resin that obtains on the olefin homo;
(2) by unsaturated carboxylic acid and/or their derivatives graft are aggregated to the modified polyolefin resin that obtains on two or more olefin copolymers;
(3) by unsaturated carboxylic acid and/or their derivatives graft are aggregated to the modified polyolefin resin that obtains on the segmented copolymer, this segmented copolymer is by with the alkene homopolymerization and then two or more olefin-copolymerizations are obtained; Or
(4) modified polyolefin resin by one or more alkene and unsaturated carboxylic acid and/or their derivative copolymerization are obtained.
Above-mentioned modified polyolefin resin is used alone or two or more be used in combination with it.
The modified polyolefin resin of component (D) can according to be disclosed in document for example " Jitsuyopolymer alloy sekkei " (created by Fumio IDE, by Kogyo Chosakai Publishing, Inc. publish (1996)), Prog.Polym.Sci., 24, method among 81-142 (1999) and the JP2002-308947A prepares, and can use solution methods, bulk process and melt-kneaded method any.And those methods can combination with one another.
Example for the preparation of the unsaturated carboxylic acid of the modified polyolefin resin of component (D) is toxilic acid, fumaric acid, methylene-succinic acid, vinylformic acid and methacrylic acid.
In addition, the example of olefinically unsaturated carboxylic acid derivatives is the ester cpds of above-mentioned unsaturated carboxylic acid, amide compound, imide compound and metal-salt, and its object lesson is maleic anhydride, itaconic anhydride, methyl acrylate, ethyl propenoate, butyl acrylate, glycidyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, glycidyl methacrylate, ethyl maleate, ethyl maleate, monomethyl fumarate, dimethyl fumarate, acrylamide, Methacrylamide, the toxilic acid monoamide, the toxilic acid diamide, the fumaric acid monoamide, maleimide, N-butyl maleimide and sodium methacrylate.
In addition, can use compound for example citric acid and oxysuccinic acid, dehydration forms unsaturated carboxylic acid in its step on being grafted to polypropylene.
The preferred example of unsaturated carboxylic acid and their derivative is vinylformic acid, glycidyl methacrylate and maleic anhydride.
The modified polyolefin resin of component (D) is preferably:
(5) by maleic anhydride graft being aggregated to the modified polyolefin resin that obtains on the polyolefin resin of unit as their primary structure unit that contains derived from ethylene and/or propylene; Or
(6) modified polyolefin resin that will obtain as the alkene of their main ingredient and glycidyl methacrylate or maleic anhydride copolymerization by containing ethene and/or propylene.
From the physical strength of the moulded product viewpoint of shock strength, fatigue property and rigidity for example, the modified polyolefin resin of component (D) contains the structural unit derived from unsaturated carboxylic acid and/or their derivative that quantity is preferably 0.1-10wt%.
When modified polyolefin resin that component (D) is (4) by one or more alkene and unsaturated carboxylic acid and/or their derivative random copolymerization or block copolymerization are obtained, content derived from the unit of unsaturated carboxylic acid and/or their derivative is preferably 0.1-10wt%, more preferably 1-10wt%, and further preferred 3-10wt%.
When component (D) when being following:
(1) by unsaturated carboxylic acid and/or their derivatives graft are aggregated to the modified polyolefin resin that obtains on the olefin homo;
(2) by unsaturated carboxylic acid and/or their derivatives graft are aggregated to the modified polyolefin resin that obtains on two or more olefin copolymers; Or
(3) by unsaturated carboxylic acid and/or their derivatives graft are aggregated to the modified polyolefin resin that obtains on the segmented copolymer, this segmented copolymer is by with the alkene homopolymerization and then two or more olefin-copolymerizations are obtained,
The involved quantity in unit derived from unsaturated carboxylic acid and/or their derivative is preferably 0.1-10wt%, more preferably 0.1-5wt%, and further preferred 0.3-3wt%.
In the first resin combination of the present invention that contains acrylic resin (I) and component (C), acrylic resin (I) contains component (A) and (B), component (A) is contained in the acrylic resin (I) with the amount of 50-100wt%, and component (B) is contained in wherein with the amount of 0-50wt%, and component (A) and summation (B) are 100wt%.
From the physical strength of moulded product for example rigidity and shock strength with and the viewpoint of outward appearance, the quantity that comprises of component (A) is preferably 60-100wt%, and the quantity that comprises of more preferably 80-100wt%, and component (B) is preferably 0-40wt%, and more preferably 0-20wt%.
From the physical strength of moulded product for example rigidity and shock strength with and the viewpoint of manufacturability, the acrylic resin of per 100 weight parts (I), the quantity that contains component (C) is the 5-400 weight part, preferably 10-300 weight part and particularly preferably 10-240 weight part.
In the second resin combination of the present invention that comprises acrylic resin (II) and component (C), acrylic resin (II) contains component (A), (B) and (D), component (A) is contained in the acrylic resin (II) with the amount of 50-100wt%, and component (B) is contained in wherein with the amount of 0-50wt%, and component (A) and summation (B) are 100wt%.
Viewpoint from the outward appearance of moulded product comprises quantity and is preferably 60-100wt%, and the more preferably component of 80-100wt% (A), and comprises quantity and be preferably 0-40wt%, and the more preferably component of 0-20wt% (B).
From the physical strength of the moulded product viewpoint of rigidity and shock strength, fatigue property and its manufacturability for example, comprising quantity is the 0.1-70 weight part, preferred 0.1-25 weight part, more preferably 0.5-25 weight part and the particularly preferably modified polyolefin resin of the component of 1-18 weight part (D), component (A) and summation (B) are 100 weight parts.
Per 100 weight parts comprise component (A), (B) and resin (D) (II), comprise the fiber of the component that quantity is the 5-400 weight part (C).From the physical strength of moulded product for example rigidity and the manufacturability of shock strength and composition and the viewpoint of molded property, comprise quantity and be preferably the 10-300 weight part, and the component of 10-240 weight part (C) particularly preferably.
Propylene resin composition of the present invention can be elastomer blended with one or more.Elastomeric example be ethylene ' alpha '-olefin random copolymers, ethylene ' alpha '-olefin non--conjugated polyene random copolymers, hydrogenated block copolymer, other elastomeric polymers, and their mutually mixed thing.
And, propylene resin composition of the present invention can with common adding propene polymer known in the art in the material blend, for example stablizer such as antioxidant, thermo-stabilizer, neutralizing agent and uv-absorbing agent; Suds suppressor; Fire retardant; Flame retardant; Dispersion agent; Static inhibitor; Lubricant; Antiblocking agent is silicon-dioxide for example; Tinting material is dyestuff and pigment for example; Softening agent; Nucleator and crystallization promoter.
In addition, propylene resin composition of the present invention can with some material blend, for example sheet or particulate inorganic compound are such as glass flake, mica, glass powder, granulated glass sphere, talcum, clay, aluminum oxide, carbon black and wollastonite; And whisker.
Example for the preparation of the method for propylene resin composition of the present invention is the whole bag of tricks for the preparation of fibrous resin combination known in the art.Its example is to comprise each component is mixed simultaneously, and perhaps the combination with some each components mixes separately, prepares thus uniform mixture, and then with the method for the step of mixture melt-kneaded; And pultrusion method.Above-mentioned uniform mixture can be by for example Henschel mixing machine, belt blender and blender are mixed acquisition with device.For example implement by Banbury mixing machine, Plastmil, Brabender plastometer and list or twin screw extruder with device for above-mentioned melt-kneaded.
From the manufacturability of moulded product and the physical strength viewpoint of rigidity and shock strength for example, preferred pultrusion method.Pultrusion method is substantially included in the situation of drawing continuous tow and resin is immersed the intrafascicular step of continuous fibre, and its example is:
(1) comprises and make fibrous bundle by accommodating the steeping vat of resin emulsion, suspension or solution, thus fiber is immersed the method for the step in the fibrous bundle;
(2) comprise with resin-oatmeal jet fiber bundle or make the groove of fibrous bundle by accommodating resin-oatmeal so that resin-oatmeal is transferred on the fibrous bundle, and then with the resin-oatmeal melting, thus resin is immersed the method for the step in the fibrous bundle; With
(3) be included in the situation that makes fibrous bundle pass through Thead off-set die head, for example from forcing machine, resin sent into Thead off-set die head, thus resin is immersed the method for the step in the fibrous bundle.
The method of preferred above-mentioned use Thead off-set die head (3), and particularly preferably use for example method of the Thead off-set die head among the JP3-272830A of document that is disclosed in.
In above-mentioned pultrusion method, in one or more steps, carry out resin-dip treating.And, can be with the pellet that makes according to pultrusion method and the pellet blend that makes according to the melt-kneaded method.
Preferred its of propylene resin composition of the present invention is shaped as pellet, and its length is preferably 2-50mm, and more preferably 3-20mm, and further preferred 5-15mm is because those pellets can advantageously be injection molded into the goods with superior strength.And the fiber and the pellet that are contained in the pellet are preferably mutually the same on their length.
Above-mentioned " fiber and the pellet that are contained in the pellet are mutually the same on their length " refers to measure according to the method that is disclosed among the JP2002-5924A, and the weight average fiber length that is contained in the fiber in the pellet is the 90-110% of pellet length.According to one embodiment of the invention, propylene resin composition of the present invention is pellet form, and is contained in each fiber layout parallel to each other of the component (C) in the described pellet.
Propylene resin composition of the present invention can be molded as goods.The example of molding methods is injection moulding process, injection pressure molding process, auxiliary molding methods and the extruding forming method of gas.
Especially, from the physical strength of moulded product and the viewpoint of weather resistance, the weight average fiber length that is contained in the fiber by the component (C) in the moulded product that propylene resin composition injection moulding of the present invention is obtained is preferably 1-10mm, more preferably 1-5mm, and 1-3mm particularly preferably.
Contain the moulded product that weight average fiber length is the fiber of 1-10mm, can be by under condition of moulding commonly used, propylene resin composition injection moulding of the present invention being made.The example of preferred condition of moulding is as follows:
-molding under low back pressure;
-use is equipped with the mould machine molding with the screw rod of deep trouth;
-molding under low injection speed;
The mould molding of-utilized bandwidth fluid channel; With
-usefulness has the mould machine molding of giant diameter.
Moulded product of the present invention can be used for plastic automotive parts, for example needs the external component (for example splash pan, outstanding splash pan, protective grille, shroud upper panel ventilation hole, wheel cover, vehicle body expand skirtboard, front grid, side pedal, roof rail, rear spoiler and safety lever under bar, door security bar, the side) of the outward appearance that good physical strength, weather resistance become reconciled; The internal part (for example panel board and fringing) that for example at high temperature needs rigidity; In-engine parts (for example pilot beam, cooling fan, fan shroud, lampshade, automobile heating container, fuse unit and air purifier shell) for example.
And moulded product of the present invention can be used for for example parts of the machine casing of power tool, photographic camera, Kamera, microwave oven, electric cooker, kettle, suction cleaner, PC, duplicating machine, printer and FDD or CRT of various electronic products; The parts of various machines are pump case for example; With the parts of buildings for example groove, pipe and building molding box.
[embodiment]
The present invention makes an explanation with following embodiment and comparative example.The sample that is used for estimating that uses in embodiment or the comparative example prepares according to following methods.
(1) preparation method of the pellet of glass fibre enhancing
The pellet that glass fibre strengthens prepares under the speed of drawing of 270 ℃ dipping temperature and 15m/ minute according to the method that is disclosed among the JP3-121146A.
The preparation method of the sample of (2) be used for estimating
Use following by The Japan Steel Works, Ltd. the pellet injection moulding that the mould machine of producing strengthens by the glass fibre that will obtain in above-mentioned (1) under the following conditions is for the preparation of the sample of evaluation, the sample that wherein is used for the measurement hickie has the plate-like shape of 150mm * 150mm * 3mm (thickness), and when the blend parent material, 1 weight part pigment masterbatch (carbon black concentration of 14wt%) is joined in the pellet of 100 weight part glass fibre enhancing, obtains thus the black parent material:
By The Japan Steel Works, the mould machine that Ltd. produces
-mold pressure: 150 tons
-screw rod: with the screw rod of deep trouth
-screw diameter: 46mm
-screw rod L/D:20.3
Condition of moulding
-barrel zone temperature: the sample that is used for measurement mechanical intensity at molding is 250 ℃, and is 200 ℃ at the sample that molding is used for measuring hickie
-die temperature: 50 ℃
-back pressure: 0MPa
Evaluate root in embodiment and comparative example is carried out according to following methods.
(1) flexural strength (unit: MPa)
It is measured under the following conditions according to ASTM D790:
-measurement temperature: 23 ℃,
-thickness of sample: 3.2mm,
-span: 50mm, and
-test speed: 2mm/ minute.
(2) hickie index
It is measured according to the method that may further comprise the steps:
The scanner that-use is produced by EPSON Corp., GT-9600 is in condition---256 grey scale, the resolving power of 50dpi, 20 exposure, 50 gamma, 61 highlight, 60 shade and 110 threshold value---the image scanning of lower 10 flat boards that will obtain according to the sample preparation methods that is used for estimating of mentioning in top (2) is to computer (2,186cm
2The analysis area); With
-use by Asahi Engineering Co., the grain size analysis function of the precise image analysis software (IP-1000PC) of Ltd. producing, area based on the image calculation hickie of above-mentioned scanning, wherein the hickie index is the index of the area of each sample, and condition is that the hickie area of the sample in the comparative example 1 has 100 index.
(3) weight average fiber length (unit: mm)
It uses above-mentioned sample with plate-like shape to measure according to the method that is disclosed among the JP2002-5924A.
(4) molecular weight distribution
It is measured under the following conditions according to gel permeation chromatography:
-device: by the Class1 50CV of Milipore Waters Co. production,
-post: SHODEX M/S 80,
-measurement temperature: 145 ℃,
-solvent: ortho-, meta-or p-dichlorobenzene, and
-sample concentration: 5mg/8mL.
The Application standard polystyrene is made calibration curve.Measure under these conditions, polystyrene standard (NBS 706:Mw/Mn=2.0) has the molecular weight distribution of 1.9-2.0.
(5) isotaxy five unit number of componentss
It uses the solution of 200mg sample in the ortho-, meta-or p-dichlorobenzene mixed solvent (the ortho-, meta-or p-dichlorobenzene of ortho-, meta-or p-dichlorobenzene/deuterate-d=4/1 volume) of the ortho-, meta-or p-dichlorobenzene/deuterate of 3mL, use the device JNM-EX 270 that is produced by JEOL LTD, according to being disclosed in Macromolecules
6, the method in 925 (1973) is measured, and the NMR absorption peak is based on Macromolecules,
8, 687 (1975) point out.
(6) melt temperature (unit: ℃)
It uses by PerkinElmer Co., the differential scanning calorimeter that Ltd. produces, and cooling type DSC-7 measures according to the method that may further comprise the steps fast:
-under nitrogen atmosphere, at 220 ℃ the 10mg sample was heated 5 minutes, make thus the sample melting;
-under 5 ℃/minute speed, be cooled to 40 ℃; With
-under 5 ℃/minute speed, heat, obtain thus the melting endothermic curve, wherein the temperature corresponding to the maximum heat absorption peak is melt temperature.Incidentally, use above-mentioned monitoring to measure under 5 ℃/minute heating rate, the temperature that indium begins melting is 156.6 ℃.
Amount (the unit: mol%) of (7) 2,1-keys
Its basis is disclosed in Polymer,
30, the method in 1350 (1989) is measured.
(8) content (unit: wt%) of ethene and/or alpha-olefin
It is according to being disclosed in " New Edition:Kobunshi Bunseki Handbook " (by TheChemical Society Of Japan, The Japan Society For Polymer AnalyticalChemistry edits and by Kinokuniya Co., Ltd. publishes (1995)) in method use the IR method to measure.
[embodiment 1]
Prepare the pellet that contains the 40wt% glass fibre and have the glass fibre enhancing of 9mm pellet length with the composition amount such as description in the table 2 according to the method that is disclosed among the JP3-121146A.Table 1 shows the measuring result of the acrylic resin of use, for example molecular weight distribution, isotaxy five unit number of componentss, the monomeric unit content, 2 except propylene units, the amount of 1-key and melt temperature.
Further, the pellet injection moulding that the glass fibre that obtains is strengthened.Table 2 shows the measuring result of the sample that obtains, for example the weight average fiber length of fiber in tensile strength, modulus in flexure, flexural strength, IZOD shock strength, the hickie exponential sum moulded product.
[embodiment 2]
Prepare the pellet that contains the 40wt% glass fibre and have the glass fibre enhancing of 9mm pellet length with the composition amount such as description in the table 2 according to the method that is disclosed among the JP3-121146A.Table 1 shows the measuring result of the acrylic resin of use, for example molecular weight distribution, isotaxy five unit number of componentss, the monomeric unit content, 2 except propylene units, the amount of 1-key and melt temperature.
Further, the pellet injection moulding that the glass fibre that obtains is strengthened.Table 2 shows the measuring result of the sample that obtains, for example the weight average fiber length of fiber in tensile strength, modulus in flexure, flexural strength, IZOD shock strength, the hickie exponential sum moulded product.
[comparative example 1]
Repeat embodiment 1, except will changing as the acrylic resin (A-1) of component (A) Co. by Sumitomo Chemical into, the alfon of Ltd production, NOBLENE Z101A (MFR=25g/10 minute), (B-1).
[comparative example 2]
Repeat embodiment 1, except will changing the Chemicals by Atofina into as the acrylic resin (A-1) of component (A), the alfon of Inc production, FINAPLAS 1751 (MFR=25g/10 minute), (E-1).
[comparative example 3]
Repeat embodiment 2, except will changing the Chemicals by Atofina into as the acrylic resin (A-1) of component (A), the alfon of Inc production, FINAPLAS 1751 (MFR=25g/10 minute), (E-1).
[table 1]
| A-1 | B-1 | E-1 | |
| Molecular weight distribution (-) | 2.1 | 3.9 | 2.8 |
| Isotaxy five unit number of componentss (-) | 0.95 | 0.98 | ＜0.3 |
| Monomeric unit content (wt%) except propylene units | 0 | 0 | 0 |
| The amount of 2,1-key (%) | 0.84 | 0 | - |
| Melt temperature (℃) | 148 | 167 | 132 |
A-1: alfon, Metocone HM 562S (MFR=30g/10 minute) is produced by BASELLPOLYOLEFINE GMBH.
B-1: alfon, NOBLENE Z101A (MFR=25g/10 minute), by SumitomoChemical Co., Ltd produces.
E-1: alfon, FINAPLAS 1751 (MFR=25g/10 minute), by AtofinaChemicals, Inc produces.
[table 2]
A-1:Metocone HM 562S (MFR=30g/10 minute) is produced by BASELL POLYOLEFINEGMBH.
B-1:NOBLENE Z101A (MFR=25g/10 minute), by Sumitomo Chemical Co., Ltd produces.
C-1: glass fibre (fiber diameter=17 μ m, Tex=2,310g/km, and the fibre number of bunchy=4,000 fiber together)
D-1: maleic anhydride modified acrylic resin (MFR=60g/10 minute, the amount=0.6wt% of the maleic anhydride of grafting, and according to the method preparation that is disclosed among the JP2002-308947A)
E-1:FINAPLAS 1751 (MFR=25g/10 minute), by Atofina Chemicals, Inc produces.
Moulded product among the embodiment 1 and 2 is considered to their flexural strength and good appearance.
On the other hand, the moulded product in the comparative example 1, its acrylic resin do not meet the molecular weight distribution requirement about component (A), are considered to not enough aspect its outward appearance.In addition, the moulded product in the comparative example 2 and 3, its acrylic resin do not meet the requirement about the isotaxy five unit number of componentss of component (A), and the physical strength that is considered to them is not enough.
Industrial applicibility
The propylene resin composition of the application of the invention can obtain flexural strength and good appearance and have the seldom moulded product of hickie.Because physical strength and the good appearance of those moulded products, so they can be preferably used as parts and the material of construction of trolley part, electronic product.
Claims (5)
1. propylene resin composition, it comprises:
The acrylic resin of-100 weight parts (I), it contains the propene polymer (component (A)) of the isotaxy five unit number of componentss of the molecular weight distribution with 1.0-2.9 of 50-100wt% and 0.9-1.0, with the propene polymer (component (B)) of the isotaxy five unit number of componentss of the molecular weight distribution with 3.0-10 of 0-50wt% and 0.9-1.0, component (A) and summation (B) are 100wt%; With
The fiber of-5 to 400 weight parts (component (C)).
2. propylene resin composition, it comprises:
The acrylic resin of-100 weight parts (II), it contains the propene polymer (component (A)) of the isotaxy five unit number of componentss of the molecular weight distribution with 1.0-2.9 of 50-100wt% and 0.9-1.0, the propene polymer of the isotaxy five unit number of componentss of the molecular weight distribution with 3.0-10 of 0-50wt% and 0.9-1.0 (component (B)), with the modified polyolefin resin by the modification of unsaturated carboxylic acid or derivatives thereof (component (D)) of 0.1-70 weight part, component (A) and summation (B) are 100wt% and are 100 weight parts with respect to the weight part of component (D); With
The fiber of-5 to 400 weight parts (component (C)).
3. according to claim 1 and 2 propylene resin composition, wherein component (A) has 140-160 ℃ melt temperature, and component (B) has 155-180 ℃ melt temperature.
4. according to claim 1 and 2 propylene resin composition, wherein said propylene resin composition is pellet form, and is contained in each fiber layout parallel to each other of the component (C) in the described pellet.
5. the moulded product of being made by claim 1 or 2 described polypropylene resin composite, and this moulded product contains the fiber of the component (C) of the weight average fiber length with 1-10mm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP349242/2006 | 2006-12-26 | ||
| JP2006349242 | 2006-12-26 | ||
| PCT/JP2007/075385 WO2008078839A1 (en) | 2006-12-26 | 2007-12-26 | Propylene resin composition and molded body made from the same |
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| Publication Number | Publication Date |
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| CN101568592A CN101568592A (en) | 2009-10-28 |
| CN101568592B true CN101568592B (en) | 2013-04-24 |
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| JP (1) | JP5446089B2 (en) |
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| US20110178229A1 (en) * | 2008-09-30 | 2011-07-21 | Hirofumi Goda | Fiber-reinforced resin composition and molded body thereof |
| JP2010106263A (en) * | 2008-09-30 | 2010-05-13 | Mitsui Chemicals Inc | Filament-reinforced thermoplastic resin particle |
| JP5350958B2 (en) * | 2008-09-30 | 2013-11-27 | 三井化学株式会社 | Long fiber reinforced particle dry blend and molded product thereof |
| US8530565B2 (en) | 2008-12-25 | 2013-09-10 | Mitsui Chemicals, Inc. | Fiber reinforced propylene resin composition |
| WO2010137305A1 (en) * | 2009-05-29 | 2010-12-02 | 株式会社プライムポリマー | Long-fiber-reinforced resin composition and molded object thereof |
| JP2011241284A (en) * | 2010-05-18 | 2011-12-01 | Sumitomo Chemical Co Ltd | Polypropylene-based resin composition, and film containing the same |
| KR101674609B1 (en) * | 2015-05-07 | 2016-11-09 | 롯데케미칼 주식회사 | Preparing method of polyolefin resin mono chip and polyolefin resin mono chip |
| CN109923167A (en) * | 2016-12-27 | 2019-06-21 | 昭和电工株式会社 | Thermoplastic resin composition, formed body, separator for fuel battery, bipolar plate for redox flow battery and formed body manufacturing method |
| JP2021050270A (en) * | 2019-09-24 | 2021-04-01 | 日本ポリプロ株式会社 | Polypropylene resin composition |
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| JP2000336217A (en) * | 1999-05-26 | 2000-12-05 | Nippon Polyolefin Kk | Polypropylenic resin composition |
| CN1276814A (en) * | 1997-08-19 | 2000-12-13 | 出光石油化学株式会社 | Propylene polymer composition and films made therefrom |
| CN1827677A (en) * | 2004-12-16 | 2006-09-06 | 住友化学株式会社 | Fiber reinforced polypropylene resin composition |
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| JP2883369B2 (en) * | 1989-10-03 | 1999-04-19 | ポリプラスチックス株式会社 | Method for producing polyolefin resin composition for long fiber reinforced molding |
| JP3414548B2 (en) * | 1995-04-27 | 2003-06-09 | 住友化学工業株式会社 | Thermoplastic resin composition and injection molded article thereof |
| JPH09229290A (en) * | 1996-02-28 | 1997-09-05 | Mitsubishi Chem Corp | Composite material for vacuum thermal insulator and manufacture for vacuum thermal insulator |
| JP4201887B2 (en) * | 1997-08-27 | 2008-12-24 | 出光興産株式会社 | Polypropylene resin composition and film thereof |
| JP4007658B2 (en) * | 1997-11-28 | 2007-11-14 | 花王株式会社 | Moisture permeable film and absorbent article using the same |
| JP2004204224A (en) * | 2002-12-10 | 2004-07-22 | Sumitomo Chem Co Ltd | Long fiber-reinforced resin pellet and molded article of the same |
| JP4951848B2 (en) * | 2003-07-30 | 2012-06-13 | 住友化学株式会社 | Fiber-reinforced crystalline thermoplastic resin composition and pellets thereof |
| JP4904801B2 (en) * | 2004-12-16 | 2012-03-28 | 住友化学株式会社 | Fiber reinforced polypropylene resin composition |
| JP4894255B2 (en) * | 2004-12-16 | 2012-03-14 | 住友化学株式会社 | Fiber reinforced polypropylene resin composition |
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|---|---|---|---|---|
| CN1276814A (en) * | 1997-08-19 | 2000-12-13 | 出光石油化学株式会社 | Propylene polymer composition and films made therefrom |
| JP2000336217A (en) * | 1999-05-26 | 2000-12-05 | Nippon Polyolefin Kk | Polypropylenic resin composition |
| CN1827677A (en) * | 2004-12-16 | 2006-09-06 | 住友化学株式会社 | Fiber reinforced polypropylene resin composition |
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| CN101568592A (en) | 2009-10-28 |
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