CN101365738B - Method for producing long fiber-reinforced polyolefin resin molding material - Google Patents
Method for producing long fiber-reinforced polyolefin resin molding material Download PDFInfo
- Publication number
- CN101365738B CN101365738B CN2006800495934A CN200680049593A CN101365738B CN 101365738 B CN101365738 B CN 101365738B CN 2006800495934 A CN2006800495934 A CN 2006800495934A CN 200680049593 A CN200680049593 A CN 200680049593A CN 101365738 B CN101365738 B CN 101365738B
- Authority
- CN
- China
- Prior art keywords
- polyolefin resin
- resin
- long fiber
- additive
- masterbatch
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Disclosed is a method for production of a long fiber-reinforced polyolefin resin molding material having excellent mechanical strength and durability, which can achieve the charge/feeding of a matrix resin into an immersion die by means of a single-screw extruder in a stable manner. The method comprises the steps of: plasticizing/melting a composition comprising a base resin and a master batch in a single-screw extruder; charging the resulting composition into an immersion die; passing a reinforcing fiber through the immersion die; and cutting a long fiber-reinforced polyolefin resin rod thus produced into pieces each having a predetermined length, wherein the base resin comprises a polyolefin resin, and the master batch is prepared by previously melting/dispersing an additive comprising a low-melting-point additive having a melting point of 125 DEG C or lower (i.e., a master batch component other than a polyolefin resin) into a polyolefin resin.
Description
Technical field
The present invention relates to be used to obtain the method for manufacture of the long fiber-reinforced polyolefin resin molding material of the good molding of physical strength excellence and outward appearance.
Background technology
Polyolefin resines such as acrylic resin are cheap light materials, because of its processing that is easy to be shaped is widely used as phenol resin molding material.In order to improve its mechanical properties, especially shock-resistance, known have a resulting long fiber-reinforced polyolefin resin molding material of infiltration polyolefin resin in fortifying fibres such as spun glass.
The for example available following method of this long fiber-reinforced polyolefin resin molding material is made: make the polyolefin resin plasticising and the fusion in forcing machine that become the matrix resin raw material; The fused polyolefin resin is filled into dipping former; Make simultaneously from the fortifying fibre of extractions such as coiling body and pass through to make the resin that infiltrates in the fortifying fibre the dipping former, when making this fortifying fibre it is carried out drawing through nozzle; Thereby give the shape of regulation, more continuous fortifying fibre is cut off.
On the other hand, polyolefin resin is prone under the effect of oxygen, heat, light deterioration etc. takes place, and influenced by it and is prone to cause quality to descend.Therefore, described in the for example following patent documentation 1, in the polyolefin resin molding, except that polyolefin resin, also add oxidation inhibitor, photostabilizer, UV light absorber etc., weather resistance such as antioxidant deterioration, thermotolerance, weathering resistance are improved.
Patent documentation 1: japanese patent laid-open 9-207233 communique
The announcement of invention
As the forcing machine of employed matrix resin in the manufacturing process of long fiber-reinforced polyolefin shaped material, general known have single shaft forcing machine and biaxial extruder.And when dipping former provided the fusion matrix resin of equivalent, the single shaft forcing machine was compared with biaxial extruder, and have following advantage: equipment price is cheap, and because screw-rod structure is uncomplicated, the cleaning when therefore changing molten resin material is extremely simple.
But in the manufacturing of long fiber-reinforced polyolefin resin molding material; When using the single shaft forcing machine as forcing machine; When in dipping former, filling plasticising and fused matrix resin; Have following problem: can not stably to dipping former matrix resin be provided, easy generation filling is bad etc., the feed rate that is difficult to regulate the matrix resin that provides to dipping former.Therefore, the resin feed rate that provides to dipping former is unstable, and resin can not spread all over out fine with rod etc. sometimes, is prone to produce fortifying fibre broken string etc., causes the productivity decline of long fiber-reinforced polyolefin resin molding material.
Therefore, the object of the present invention is to provide and to utilize the single shaft forcing machine stably to provide and fill the method for manufacture that matrix resin comes the long fiber-reinforced polyolefin resin molding material of manufacturing machine rerum natura and excellent in te pins of durability to dipping former.
The present inventor in order to achieve the above object; Carried out research and thought causing said resin feed rate to descend or unsettled reason is to use additives such as powder shaped oxidation inhibitor, photostabilizer, UV light absorber, and caused that the situation of the problems referred to above is many especially when finding to state the lower melting point additive in the additive in the use.
On the other hand; Even used the higher above-mentioned various additives of fusing point; But since liken to into the low-melting additive of the polyolefin resin of main raw material more; Though, still be easy to generate matrix resin and in dipping former, fill condition of poor so resin is supplied with stable slightly raising but be also insufficient.
In addition; For weather resistance such as the thermotolerance that improves rosin products, antioxidant deterioration, combination uses the method for multiple additives very effective, therefore if can not use low-melting additive; Then the kind of selectable additive is restricted; Thereby aspect effect, receive remarkably influenced, and can't fully obtain necessary performance sometimes, therefore unrealistic.
Also can consider to make long fiber-reinforced polyolefin resin molding material with the matrix resin that does not contain additive; But in order to obtain the molding of excellent in te pins of durability such as antioxidant deterioration, thermotolerance, weathering resistance; When long fibre enhanced polypropylene olefine resin shaped material is processed molding with the dilution that does not contain fortifying fibre with acrylic resin hybrid shaping, be necessary to mix necessary additive.But, hope because the difference of particle diameter etc. makes the easy classification of additive, to have the problem of the productivity that diminishes molding with long fibre enhanced polypropylene olefine resin shaped material, when diluting with acrylic resin and additive mixing and shaping.
Therefore; The present inventor has carried out various researchs; The result finds: through in advance the fusion in polyolefin resin of additives such as oxidation inhibitor, photostabilizer, UV light absorber being disperseed to process masterbatch; Then it is mixed use with the polyolefin resin that becomes matrix, can use above-mentioned single shaft forcing machine in dipping former, to fill the fusion matrix resin highly stablely, thereby accomplish the present invention.
Promptly; The method of manufacture of long fiber-reinforced polyolefin resin molding material of the present invention is that polyolefine resin composition is filled in the dipping former after with single shaft forcing machine plasticising fusion; Make fortifying fibre pass through this dipping former; And the long fiber-reinforced polyolefin resin bar that obtains is cut into the method for manufacture of the long fiber-reinforced polyolefin resin molding material of specified length; It is characterized in that; As the said polyolefins resin combination, adopt and to contain the matrix resin that forms by polyolefin resin and through will be as the compsn that fusing point is the additive masterbatch that the fusion dispersion obtains in polyolefin resin in advance of the lower melting point additive below 125 ℃ that contains of the composition (except the polyolefin resin) of masterbatch.
In the present invention, the MFR of the polyolefin resin of above-mentioned masterbatch better is 5～40 (g/10min).Take this, the mixing property of additive and polyolefin resin is good, thereby can improve the content of additive in the masterbatch.And, utilize tablets press etc. can fully integrate the shape of masterbatch, size etc., make matrix resin and masterbatch be easy to mix, stably fill the fusion master batch resin to dipping former.In addition, so-called here MFR refers to the melt flow rate value stipulated among the JIS-K-7210, is illustrated under 230 ℃, load 2.16kgf per 10 minutes from the effusive amount of resin of cylindrical drum.If this MFR is high, represent that then the viscosity of resin is low.
The MFR of the polyolefin resin of above-mentioned matrix resin is preferably 20～200 (g/10min).Take this, its infiltration property in fortifying fibre is good, can obtain the excellent long fiber-reinforced polyolefin resin molding material of physical strength.
The polyolefin resin of above-mentioned matrix resin and the polyolefin resin of above-mentioned masterbatch are preferably polypropylene-based resin.Polypropylene-based resin has economy and versatility, and the polyolefin resin through making above-mentioned matrix resin and the polyolefin resin of above-mentioned masterbatch be resin of the same race, makes matrix resin and masterbatch be easy to mix, and stably fills the fusion matrix resin to dipping former.
In addition, above-mentioned additive preferably is selected from least a in oxidation inhibitor, photostabilizer and the UV light absorber.Through the above-mentioned additive of fusion in long fiber-reinforced polyolefin resin molding material, can improve the weather resistance such as thermotolerance, antioxidant deterioration of the polyolefin resin molding that makes as the finished product.
And above-mentioned masterbatch preferably contains the additive except that the said polyolefins resin of 15～50 quality %.In addition, the additive of above-mentioned masterbatch preferably contains the above-mentioned lower melting point additive of 30～100 quality %.In addition, the said polyolefins resin combination above-mentioned masterbatch that preferably to contain with respect to above-mentioned matrix resin 100 mass parts be 2～35 mass parts.
According to the present invention, when making long fiber-reinforced polyolefin resin molding material, can to dipping former matrix resin be provided stably with the single shaft forcing machine, can reduce the manufacturing cost and the maintenance cost of long fiber-reinforced polyolefin resin molding material.
And; The long fiber-reinforced polyolefin resin molding material that obtains according to the present invention is the shaped material that contains additives such as oxidation inhibitor, photostabilizer, UV light absorber; When therefore adopting this shaped material to process resin forming product; Except the dilution that do not contain fortifying fibre with the polyolefin resin, need not to mix above-mentioned additive.That is to say; When processing resin forming product in that long fiber-reinforced polyolefin resin molding material, dilution are mixed with polyolefin resin and additive fusion, since the difference of particle diameter etc., additive classification sometimes; But if adopt the present invention; Even then blast blending not through above-mentioned long fiber-reinforced polyolefin resin molding material and dilution are mixed and are shaped with polyolefin resin, also can be processed the good resin forming products of weather resistance such as antioxidant deterioration, thermotolerance, weathering resistance; Be difficult for classification, and can not reduce the physical strength of resin forming product.
The simple declaration of accompanying drawing
Fig. 1 is the basic comprising figure of the manufacturing process of expression long fiber-reinforced polyolefin resin molding material.
Nomenclature
1: fortifying fibre
2: the molten resin supplying path
3: the single shaft forcing machine
4: hopper
5: dipping former
6: nozzle
7: the long fiber-reinforced polyolefin resin bar
8: cooling tank
9: the extraction machine
10: tablets press
11: long fiber-reinforced polyolefin resin molding material
The best mode that carries out an invention
The method of manufacture of long fiber-reinforced polyolefin resin molding material of the present invention is following: the polyolefine resin composition that becomes matrix resin is filled in the dipping former after the plasticising fusion in the single shaft forcing machine; Make fortifying fibre pass through this dipping former; Thereby in fortifying fibre, infiltrate polyolefine resin composition, the long fiber-reinforced polyolefin resin bar that obtains is cut into specified length.
As fortifying fibre, can use in high-melting fibres such as spun glass, thomel, steel fiber, aromatic polyamide fibre etc. any.These fortifying fibres through with generally well-known collecting agent with 100～10000, preferably 400～6000 single strand boundlings are processed fibrous bundle and are used.In the above-mentioned fortifying fibre, consider intensity and price of the long fiber-reinforced polyolefin resin molding material that obtains etc., preferred glass fibers.In addition, the filamentary diameter of fortifying fibre is preferably 6～30 μ m, more preferably 9～23 μ m.
The said polyolefins resin combination that uses as the matrix resin of fortifying fibre of the present invention (below be called " matrix resin ") is to contain the matrix resin that formed by polyolefin resin and through being preferably the compsn that contains 2～35 mass parts masterbatch with respect to matrix resin 100 mass parts as the compsn that fusing point is the additive masterbatch that the fusion dispersion obtains in polyolefin resin in advance of the lower melting point additive below 125 ℃ that contains of masterbatch composition (except the polyolefin resin).If the content of masterbatch does not reach 2 in above-mentioned value, then be difficult to obtain the effectiveness of additive, the additive containing ratio that must increase in the masterbatch is renderd a service with acquisition, but owing to be difficult to form masterbatch, therefore not preferred.When the content of masterbatch surpassed 35 mass parts in above-mentioned value, material cost might increase, and was therefore not preferred.Wherein, the compsn that more preferably contains 4～30 mass parts masterbatch with respect to matrix resin 100 mass parts.
As the polyolefin resin of above-mentioned matrix resin (below be called " matrix polyolefin resin "); Can enumerate the homopolymer or the multipolymer of ethene, propylene, butylene, 4-methylpentene etc., with monomeric random, the block of vinyl-acetic ester, vinylformic acid, propenoate, maleic anhydride isopolarity or graft copolymer etc.Wherein, consider economy and versatility, the graftomer of homopolymer, acrylic resin and the maleic anhydride of preferred propylene.
The MFR of matrix polyolefin resin is preferably 20～200 (g/10min).If MFR less than 20 (g/10min), then the infiltration property in fortifying fibre is poor, if surpass 200 (g/10min); Though then infiltration property is good; But owing to molecular weight and molecular weight causes the strength degradation of resin self, the intensity difference of gained long fiber-reinforced polyolefin resin molding material, thereby not preferred.The MFR of matrix polyolefin resin is 50～150 (g/10min) more preferably.
As the masterbatch that uses in the matrix resin of the present invention, adopt through will be as the additive masterbatch that the fusion dispersion obtains in polyolefin resin in advance that fusing point is the lower melting point additive below 125 ℃ that contains of masterbatch composition (except the polyolefin resin).
Polyolefin resin when making above-mentioned masterbatch (below be called " MB polyolefin resin "), no particular restriction can be used the resin identical with the matrix polyolefin resin.Preferably with the congener resin of matrix polyolefin resin, matrix polyolefin resin and MB polyolefin resin be polypropylene-based resin more preferably.Polypropylene-based resin has economy and versatility, and the range of choice of processing temperature condition, MFR is wide, therefore when making above-mentioned masterbatch, is prone to extrude and mixes.Through making matrix polyolefin resin and MB polyolefin resin is congener resin, and it is mixed that matrix resin and masterbatch are prone to, and stably fills the fusion matrix resin to dipping former.Here, as polypropylene-based resin, can enumerate the multipolymer etc. of graft copolymer, propylene and ethene of homopolymer, acrylic resin and the maleic anhydride of propylene.
In addition, the MFR of MB polyolefin resin is preferably 5～40 (g/10min), more preferably 10～30 (g/10min).If the MFR less than 5 (g/10min) of above-mentioned MB polyolefin resin; Then the difference with the MFR value of matrix polyolefin resin increases; Masterbatch is difficult in the matrix polyolefin resin, disperse, and the additive that contains in the masterbatch is difficult to homodisperse in long fiber-reinforced polyolefin resin molding material.If MFR surpasses 40 (g/10min), practice when mixing during then masterbatch is made and close insufficiently, thereby can't improve additive level.Consequently, must increase the usage quantity of masterbatch so that contain the additive of aequum in the long fiber-reinforced polyolefin resin molding material, thus unfavorable aspect cost.In addition, extrude when mixing for making masterbatch, uneven from the thickness that melt extrudes bar of the mould of making masterbatch; Or it is meticulous and can't fully carry out granulation (cut-out); The size of masterbatch becomes uneven easily with forming, and therefore metering property is poor, and if shape is uneven, the difference of shape becomes big; Then with the miscibility variation of matrix polyolefin resin, inequality appears in additive level easily in the gained long fiber-reinforced polyolefin resin molding material.
The additive that uses in the masterbatch of the present invention refers to oxidation inhibitor, photostabilizer, UV light absorber etc.; Must contain fusing point in these additives below 125 ℃, more preferably fusing point below 100 ℃, preferred especially 40～80 ℃ lower melting point additive (below be also referred to as " lower melting point additive "); Except that the lower melting point additive, also can surpass 125 ℃, more preferably fusing point is the HMP additive (below be also referred to as " HMP additive ") more than 150 ℃ and uses with fusing point.Use multiple oxidation inhibitor through combination, can improve the weather resistance such as antioxidant deterioration of polyolefin resin molding effectively with different melting points.
The additive that uses in the masterbatch preferably contains 30～100 quality %, further is preferably 30～90 quality %, the lower melting point additive of 30～70 quality % more preferably.If lower melting point content of additive less than 30 quality %, then be difficult to obtain with the HMP additive and use the effects such as weather resistance raising that produced, the effect of additive is insufficient sometimes.
And the above-mentioned additive containing ratio of masterbatch is preferably 15～50 quality %, more preferably 20～40 quality %.If the additive containing ratio less than 15 quality % of masterbatch then because the usage quantity of masterbatch increases, and material cost might increase, if surpass 50 quality %, then are difficult to form masterbatch, and the bad stability of masterbatch, thereby not preferred.
As the oxidation inhibitor (fusing point is below 125 ℃) of lower melting point additive, can enumerate DBPC 2,6 ditertiary butyl p cresol, 2; 2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2,6-di-t-butyl-4-ethylphenol, [methylene radical-3-(3 for propionic ester, four for Octadecane base-3-(3, the 5-di-tert-butyl-hydroxy phenyl); The 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane, triethylene glycol two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], [3-(3 for tetramethylolmethane four; The 5-di-tert-butyl-hydroxy phenyl) propionic ester], sulfo-diethylidene-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 2,4-dimethyl--6-(1-methyl pentadecyl) phenol, 4; Two (octylsulfo methyl) ortho-cresols of 6-, ethylenebis (ethylene oxide) two [3-(tolyl between the 5-tertiary butyl-4-hydroxy) propionic esters], hexa-methylene are two, and [3-(3; The 5-di-tert-butyl-hydroxy phenyl)] propionic ester, 2, and 6-di-t-butyl-4-(4, two (octylsulfo)-1 of 6-; 3; 5-triazine-2 base amino) Hinered phenols antioxidant such as phenol, diethylammonium [(3, two (1, the 1-the dimethyl ethyl)-4-hydroxy phenyls of 5-) methyl] phosphonic acid ester; Thioether kind antioxidants such as dilauryl thiopropionate, distearyl thiodipropionate, myristyl thiodipropionate, double tridecyl thiodipropionate; Phosphorus oxidation inhibitor such as phosphorous acid two [2, two (1, the 1-the dimethyl ethyl)-6-aminomethyl phenyls of 4-] ethyl ester, four (2, the 4-di-tert-butyl-phenyl) [1, the 1-xenyl]-4,4 '-two basic bis-phosphites, three nonyl phenyl phosphites, triphenyl phosphorous acid ester; Two dodecyls-3,3 '-thiodipropionate, two tetradecyl-3,3 '-thiodipropionate, two octadecyl-3, sulfur type antioxidants such as 3 '-thiodipropionate.Wherein, With Hinered phenols antioxidant and time spent; Because of effective preferred thioether kind antioxidant such as the raising of the synergistic effect of thermostability and weather resistance etc., preferred especially myristyl-3,3 '-thiodipropionate, dilauryl-3; 3 '-thiodipropionate and distearyl-3,3 '-thiodipropionate.
As the UV light absorber (fusing point is below 125 ℃) of lower melting point additive, can enumerate 2-(3,5-two tert-pentyls-2-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole etc.
As the photostabilizer (fusing point is below 125 ℃) of lower melting point additive, can enumerate two (2,2,6,6-tetramethyl--4-piperidyl) sebates etc.
As the oxidation inhibitor (fusing point is above 125 ℃) of HMP additive, can enumerate 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol), 4,4 '-butylidene two (the 6-tertiary butyl-3-methylphenol), 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 1,1; 3 '-three (2-methyl-4-hydroxyl-5-tert.-butyl phenol) butane, N, N '-hexane-1,6 '-two bases two [3-(3,5-di-tert-butyl-hydroxy phenyl propionic acid amide)], 3,3 ', 3 "; 5,5 ', 5 "-six tertiary butyls-a, a ', a "-(mesitylene-2,4; 6-three bases) three p-cresol, 1,3,5-three [3, the 5-di-tert-butyl-4-hydroxyl benzyl]-1,3,5-triazines-2; 4,6 (1H, 3H, 5H)-and triketone, 1,3; 5-three [(the 4-tertiary butyl-3-hydroxyl-2,6-xylyl) methyl]-1,3,5-triazines-2,4; 6 (1H, 3H, 5H)-and triketone, 2 ', Hinered phenols antioxidants such as two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl group] the propionyl hydrazines of 3-; Phosphorus oxidation inhibitor such as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites.Wherein, the combination of preferred Hinered phenols antioxidant and Phosphorus oxidation inhibitor.
UV light absorber (fusing point is above 125 ℃) as the HMP additive; Can enumerate 2-(5-methyl-2-hydroxy phenyl) benzotriazole, 2-[2-hydroxyl-3; Two (the α of 5-; α-Er Jiajibianji) phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxy phenyl) benzotriazole, 2-(the 3-tertiary butyl-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxy phenyl)-5-chlorobenzotriazole etc.
As the photostabilizer (fusing point is above 125 ℃) of HMP additive, can enumerate 2-(3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2-n-butylmalonic acid two (1; 2,2,6; 6-pentamethyl--4-piperidyl) ester, 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester etc.
In addition, as the additive beyond oxidation inhibitor, UV light absorber, the photostabilizer, for example can enumerate fire retardant; Metal passivator; Metallic soaps such as Magnesium Stearate, calcium stearate, Zinic stearas, barium stearate, StAl, lithium stearate, zinc laurate, barium laurate, p-tert-butyl benzoic acid barium, p-tert-butyl benzoic acid zinc; Acid neutralizing agents such as hydrotalcite; Dispersion agent; Lubricant; The anti-electrostatic agent interfering; Softening agent; Releasing agent; Crystallization promotor (nucleator); Antifogging agent; Alkali earth metallic compound such as Marinco H, white lake; Whipping agent; Linking agent; Antiseptic-germicide; Anti-algae agent; Modifiers such as mould inhibitor; Tinting materials such as carbon black, zinc sulphide, pigment, dyestuff; Titanium oxide, talcum powder, lime carbonate, mica, clay, graphite, glass flake even-granular weighting agent; Organic filling agents such as fiber, bamboo fibers, aramid fiber; Whiskers such as potassium titanate etc. can suitably select fusing point to use at additive below 125 ℃ and the additive above 125 ℃.
Except that above-mentioned matrix resin and above-mentioned masterbatch, can also further contain the lower melting point additive that do not form masterbatch and HMP additive etc. in the matrix resin that the present invention uses, be preferably the resin combination that forms by above-mentioned matrix resin and above-mentioned masterbatch.
In the present invention, long fiber-reinforced polyolefin resin molding material for example can be made through operation shown in Figure 1.
At first, in the continuous fortifying fibre 1 importing dipping former 5 that never illustrated coiling body is extracted out, infiltration fortifying fibre 1 in the melts of the matrix resin with above-mentioned composition (polyolefine resin composition) that single shaft forcing machine 3 provides.Here, in single shaft forcing machine 3, from hopper 4 a certain amount of matrix resin is provided, the matrix resin that provides fusion therein mixes, and from molten resin supplying path 2 the fusion matrix resin is supplied with and is filled into the dipping former 5.When having a matrix resin of above-mentioned composition fusion being mixed in single shaft forcing machine 3, because the good fluidity of molten resin, so dipping former 5 stably supplied with and be filled in to single shaft forcing machine 3 can with molten resin.
The fortifying fibre 1 that will in the fusion matrix resin, infiltrate then, is extracted out through nozzle 6.Thereby remove the unnecessary matrix resin that is attached to fortifying fibre 1, can obtain the required long fiber-reinforced polyolefin resin bar 7 that has stable fiber containing ratio and formed the regulation cross-sectional shape.This long fiber-reinforced polyolefin resin bar 7 is cooled off in cooling tank 8, extract with extraction machine 9.The tablets press 10 that the long fiber-reinforced polyolefin resin bar 7 that extracts is had rotary cutting knife is cut into specified length, obtains long fiber-reinforced polyolefin resin molding material 11.
The long fiber-reinforced polyolefin resin molding material that makes as stated above, fortifying fibre is arranged in parallel with same length and along same direction in fact in as the polyolefin resin of matrix resin.As the shape of long fiber-reinforced polyolefin resin molding material, preferred wire rod shape or particulate state.Here, be arranged in parallel with same length and along same direction in fact that to contain major part that fortifying fibre is meant fortifying fibre serve as along same direction side by side and the state arranged of almost parallel, and a part of fiber can be the local bending or the state of complexing each other.
The fiber containing ratio of long fiber-reinforced polyolefin resin molding material does not have particular restriction, is preferably 20～80 quality %, more preferably 30～75 quality %.If fiber containing ratio less than 20 quality %; Then can not fully obtain reinforced effects, if surpass 80 quality %, the then easy variation of the infiltration property of matrix resin by the fortifying fibre generation; After state and be prone to produce burr and broken string etc. in the drawing procedure of nozzle, cause productivity decline.
The mean diameter of long fiber-reinforced polyolefin resin molding material is preferably 0.3～3.5mm, more preferably 0.4～3mm.If the not enough 0.3mm of mean diameter, then the volume density of above-mentioned shaped material diminishes, and carries property supplied with so variation, surpasses 3.5mm as if mean diameter, then the dispersed variation easily of fortifying fibre when forming through injection molding.
In addition, the length of long fiber-reinforced polyolefin resin molding material does not have particular restriction, is preferably 3～25mm, more preferably 4～20mm.If curtailment 3mm when then cutting with tablets press 10 grades, is prone to produce the crack; And be difficult for manifesting fibre-reinforced effect, if length surpasses 25mm, then when forming through injection molding; Be difficult to supply with, might cause the dispersiveness of fortifying fibre to descend with mobile to forming mill.
Embodiment
Enumerate embodiment below and specify the present invention.But these embodiment only are used to specify embodiment of the present invention, and unrestricted scope of the present invention.
[embodiment 1]
Use the screw rod footpath under screw speed is 50rpm, 280 ℃, to melt the matrix resin of blending example 1 that adopts the raw material shown in the below table 1 and press the proportioning preparation of table 2 as the single shaft forcing machine of 65mm; The fusion matrix resin is offered dipping former, observe the supply stability of matrix resin.In addition, in embodiment 1, oxidation inhibitor A, B are using as masterbatch (content of oxidation inhibitor is 25 quality %) after the fusion dispersion in acrylic resin B under 200 ℃.
Resin is supplied with stability and is estimated by following three ranks.Zero: [to dipping former certain resin being provided], △ from the single shaft forcing machine: [the single shaft forcing machine with zero same rotational speed under the resin feed rate few, or rare for a long time change during the resin feed rate], *: [the single shaft forcing machine does not provide resin fully].Evaluation result is as shown in table 2.
[embodiment 2]
Use with the raw material shown in the table 1 and press the matrix resin of blending example 2 of the proportioning preparation of table 2, in addition all operate equally with embodiment 1, the supply of observation matrix resin is stable.In addition, in embodiment 2, oxidation inhibitor B, C are using as masterbatch after the fusion dispersion in acrylic resin B under 200 ℃.
[comparative example 1]
Oxidation inhibitor A, B are not processed masterbatch; Directly add among the acrylic resin A as matrix resin, use the matrix resin of the blending example 3 of the proportioning preparation of pressing table 2, in addition all operate equally with embodiment 1; To dipping former the fusion matrix resin is provided, observes the supply stability of matrix resin.
[comparative example 2]
Oxidation inhibitor B, C are not processed masterbatch, directly add among the acrylic resin A as matrix resin, use the matrix resin of the blending example 4 of the proportioning preparation of pressing table 2, in addition all operate equally, observe the supply stability of matrix resin with embodiment 2.
[table 1]
| Raw material | Compound title etc. | Fusing point (℃) | MFR(g/10min) |
| Acrylic resin A (matrix resin) | Acrylic resin (maleic anhydride modified PP) | 165 | 120 |
| Acrylic resin B | Acrylic resin | 165 | 15 |
| Oxidation inhibitor A | Myristyl-3,3 '-thiodipropionate | 52 | - |
| Oxidation inhibitor B | Tetramethylolmethane four [3-(3,5-di-t-butyl-4-hydroxy phenyl) propionic ester] | 117 | - |
| Oxidation inhibitor C | Three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester | 184 | - |
[table 2]
* 1The masterbatch use that the additive containing ratio is 25 quality % is processed in fusion in acrylic resin B
Can know by The above results; Will contain fusing point be the fusion in acrylic resin of the oxidation inhibitor of the oxidation inhibitor below 125 ℃ disperse among the embodiment 1 that the back uses as masterbatch and with fusing point be oxidation inhibitor and fusing point below 125 ℃ surpass 125 ℃ oxidation inhibitor as oxidation inhibitor and with and the fusion in acrylic resin of these oxidation inhibitor disperseed among the embodiment 2 of back as the masterbatch use, the single shaft forcing machine is stably supplied with the fusion matrix resin to dipping former.
On the other hand, be that oxidation inhibitor below 125 ℃ is not processed masterbatch and directly added in the comparative example 1 that uses in the acrylic resin as matrix resin with fusing point, the single shaft forcing machine fails to supply with resin to dipping former.
In addition; With fusing point be oxidation inhibitor and fusing point below 125 ℃ surpass 125 ℃ oxidation inhibitor as oxidation inhibitor and with but these oxidation inhibitor are not processed masterbatch and directly add in the comparative example 2 that uses in the acrylic resin as matrix resin; Although the amount of lower melting point additive seldom, can not resin stably be provided to dipping former.
The possibility of utilizing on the industry
The present invention can utilize the single shaft forcing machine stably to supply with and fill matrix resin to dipping former, is applicable to the manufacturing of the long fiber-reinforced polyolefin resin molding material of physical strength with good productivity and excellent in te pins of durability.
Quote of the announcement of the full content of Japanese patent application 2005-375302 specification sheets, claims, accompanying drawing and the summary of filing an application on December 27th, 2005 at this as specification sheets of the present invention.
Claims (7)
1. the method for manufacture of long fiber-reinforced polyolefin resin molding material; It is that polyolefine resin composition is filled in the dipping former after with single shaft forcing machine plasticising fusion; Make fortifying fibre pass through said dipping former; And the long fiber-reinforced polyolefin resin bar that obtains is cut into the method for manufacture of the long fiber-reinforced polyolefin resin molding material of specified length, it is characterized in that
As said polyolefine resin composition; Employing contains the matrix resin that formed by polyolefin resin and through will be as the compsn that fusing point is the additive masterbatch that fusion disperses to obtain in polyolefin resin in advance of the lower melting point additive below 125 ℃ that contains of the composition of masterbatch; The MFR of the polyolefin resin of said masterbatch is 5～40 (g/10min); Said MFR refers to the melt flow rate value stipulated among the JIS-K-7210; Be illustrated in 230 ℃, the load 2.16kgf under per 10 minutes from the effusive amount of resin of cylindrical drum; Said masterbatch contains the said additive of 15～50 quality %, and this additive is be selected from oxidation inhibitor, photostabilizer and UV light absorber at least a.
2. the method for manufacture of long fiber-reinforced polyolefin resin molding material as claimed in claim 1; Wherein, The MFR of the polyolefin resin of said matrix resin is 20～200 (g/10min); Said MFR refers to the melt flow rate value stipulated among the JIS-K-7210, is illustrated under 230 ℃, load 2.16kgf per 10 minutes from the effusive amount of resin of cylindrical drum.
3. according to claim 1 or claim 2 the method for manufacture of long fiber-reinforced polyolefin resin molding material, wherein, the polyolefin resin of said matrix resin and the polyolefin resin of said masterbatch are polypropylene-based resins.
4. according to claim 1 or claim 2 the method for manufacture of long fiber-reinforced polyolefin resin molding material, wherein, said additive contains the said lower melting point additive of 30～100 quality %.
5. the method for manufacture of long fiber-reinforced polyolefin resin molding material as claimed in claim 3, wherein, said additive contains the said lower melting point additive of 30～100 quality %.
6. according to claim 1 or claim 2 the method for manufacture of long fiber-reinforced polyolefin resin molding material, wherein, the said masterbatch that it is 2～35 mass parts that said polyolefine resin composition contains with respect to said matrix resin 100 mass parts.
7. the method for manufacture of long fiber-reinforced polyolefin resin molding material as claimed in claim 3, wherein, the said masterbatch that it is 2～35 mass parts that said polyolefine resin composition contains with respect to said matrix resin 100 mass parts.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005375302A JP5037820B2 (en) | 2005-12-27 | 2005-12-27 | Manufacturing method of long fiber reinforced polyolefin resin molding material |
| JP375302/2005 | 2005-12-27 | ||
| PCT/JP2006/326110 WO2007074877A1 (en) | 2005-12-27 | 2006-12-27 | Method for production of long fiber-reinforced polyolefin resin molding material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101365738A CN101365738A (en) | 2009-02-11 |
| CN101365738B true CN101365738B (en) | 2012-01-25 |
Family
ID=38218099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800495934A Expired - Fee Related CN101365738B (en) | 2005-12-27 | 2006-12-27 | Method for producing long fiber-reinforced polyolefin resin molding material |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5037820B2 (en) |
| CN (1) | CN101365738B (en) |
| WO (1) | WO2007074877A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3568430A4 (en) | 2017-01-10 | 2020-07-01 | Celanese International Corporation | Long fiber-reinforced propylene composition for use in a thin part |
| CN110291140A (en) | 2017-01-10 | 2019-09-27 | 国际人造丝公司 | The propylene compositions of high flow fiber enhancing with low emission |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056505A (en) * | 1990-05-14 | 1991-11-27 | 希蒙特公司 | The Nonextruded concentrates of additive, filler or pigment |
| CN1282288A (en) * | 1997-10-17 | 2001-01-31 | 智索股份有限公司 | Process for preparation of fiber-filled thermoplastic resin composition |
| CN1435313A (en) * | 2002-01-30 | 2003-08-13 | 玛志达株式会社 | Glass filament reinforced resin material for shaping, resin shaped article shaping method and said resin shaped article |
| CN1506214A (en) * | 2002-12-10 | 2004-06-23 | 住友化学工业株式会社 | Fiber/resin composite material and moulded products formed thereof |
| CN1523054A (en) * | 2003-02-07 | 2004-08-25 | 住友化学工业株式会社 | Fiber-polypropylene resin composite material and particle, and fiber reinforced resin product produced thereby |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10230517A (en) * | 1997-02-19 | 1998-09-02 | Kawasaki Steel Corp | Manufacture of long fiber reinforced polyolefin resin composition |
| JP3383603B2 (en) * | 1999-02-09 | 2003-03-04 | 出光石油化学株式会社 | Automotive door panel or pillar and method of manufacturing the same |
| DE19952461C1 (en) * | 1999-10-29 | 2001-10-18 | Ticona Gmbh | Colored long fiber reinforced polyolefin plastic structure and molded body made from it |
-
2005
- 2005-12-27 JP JP2005375302A patent/JP5037820B2/en not_active Expired - Fee Related
-
2006
- 2006-12-27 CN CN2006800495934A patent/CN101365738B/en not_active Expired - Fee Related
- 2006-12-27 WO PCT/JP2006/326110 patent/WO2007074877A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056505A (en) * | 1990-05-14 | 1991-11-27 | 希蒙特公司 | The Nonextruded concentrates of additive, filler or pigment |
| CN1282288A (en) * | 1997-10-17 | 2001-01-31 | 智索股份有限公司 | Process for preparation of fiber-filled thermoplastic resin composition |
| CN1435313A (en) * | 2002-01-30 | 2003-08-13 | 玛志达株式会社 | Glass filament reinforced resin material for shaping, resin shaped article shaping method and said resin shaped article |
| CN1506214A (en) * | 2002-12-10 | 2004-06-23 | 住友化学工业株式会社 | Fiber/resin composite material and moulded products formed thereof |
| CN1523054A (en) * | 2003-02-07 | 2004-08-25 | 住友化学工业株式会社 | Fiber-polypropylene resin composite material and particle, and fiber reinforced resin product produced thereby |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2001-172399A 2001.06.26 |
| JP特开平10-230517A 1998.09.02 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007177028A (en) | 2007-07-12 |
| CN101365738A (en) | 2009-02-11 |
| WO2007074877A1 (en) | 2007-07-05 |
| JP5037820B2 (en) | 2012-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103342858B (en) | A kind of short glass fiber reinforced polypropylene compound material and its preparation method and application | |
| CN102477185B (en) | Continuous fiber reinforced polypropylene material and preparation method thereof | |
| CN101875740B (en) | Preparation method of continuous glass fiber reinforced polypropylene composite material | |
| CN108690352B (en) | Method for producing glass fiber-reinforced thermoplastic resin molded article and product thereof | |
| CN101531787A (en) | Halogen-free flame-retardant long glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN102558791A (en) | High heat resistance, high gloss, low volatility and rapid prototyping polybutylene terephthalate and preparation method thereof | |
| CN108102222B (en) | Stress whitening resistant master batch, stress whitening resistant halogen-free expansion flame-retardant polypropylene composite material and preparation method thereof | |
| CN109486013A (en) | A kind of polypropylene direct injection molding efficient enhanced halogen-free flameproof functional agglomerate and preparation method thereof | |
| CN101759912B (en) | High-rigidity and high-heat resistance polypropylene composite material and preparation method thereof | |
| CN101365738B (en) | Method for producing long fiber-reinforced polyolefin resin molding material | |
| CN102408707A (en) | Glass fiber strengthened poly-hexamethylene terephthalamide material and preparation method thereof | |
| EP2511323A1 (en) | Composite and a process for making such composite | |
| CN103013099A (en) | High-flowability long glass fiber reinforced nylon 6 material and preparation method thereof | |
| US5973013A (en) | Polyamide/polyurethane micro-blend and process | |
| CN104387662A (en) | Low-cost scratch-resistant PP/PET (propene polymer/polyethylene terephthalate) alloy material and preparation method thereof | |
| CN112552586B (en) | Glass fiber reinforced polypropylene composition and preparation method thereof | |
| CN112126190A (en) | Polyketone halogen-free flame-retardant reinforced material and preparation method thereof | |
| CN104277333A (en) | Low-temperature-resistant and flame-retardant modified geogrid and preparation method thereof | |
| CN102850786B (en) | Nylon 66 material and preparation method thereof | |
| JP4700241B2 (en) | Method for producing thermoplastic resin composition | |
| CN114369359A (en) | High-wear-resistance and good-appearance long glass fiber reinforced polyamide composite material and preparation method thereof | |
| JP4514531B2 (en) | A composition for molding a long fiber reinforced polyamide resin and a method for producing a molded body. | |
| CN101759916A (en) | Mica filled modified polypropylene composite and preparation method thereof | |
| DE102004061767A1 (en) | Thermoplastic composite material, useful to prepare molded part, comprises a thermoplastic polymer as matrix | |
| CN115505207B (en) | Short glass fiber reinforced flame-retardant polypropylene material, application and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120125 Termination date: 20201227 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |