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CN100575029C - Be mixed with the preparation method and the resin composition pellet of resin combination of the fibrous filler of high concentration - Google Patents

Be mixed with the preparation method and the resin composition pellet of resin combination of the fibrous filler of high concentration Download PDF

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Publication number
CN100575029C
CN100575029C CN200680017146A CN200680017146A CN100575029C CN 100575029 C CN100575029 C CN 100575029C CN 200680017146 A CN200680017146 A CN 200680017146A CN 200680017146 A CN200680017146 A CN 200680017146A CN 100575029 C CN100575029 C CN 100575029C
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China
Prior art keywords
resin
fibrous filler
extruder
resin composition
composition pellet
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CN200680017146A
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CN101175619A (en
Inventor
青木启
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Polyplastics Co Ltd
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Polyplastics Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/80Component parts, details or accessories; Auxiliary operations
    • B29B7/88Adding charges, i.e. additives
    • B29B7/90Fillers or reinforcements, e.g. fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B29B7/482Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws provided with screw parts in addition to other mixing parts, e.g. paddles, gears, discs
    • B29B7/483Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws provided with screw parts in addition to other mixing parts, e.g. paddles, gears, discs the other mixing parts being discs perpendicular to the screw axis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58Component parts, details or accessories; Auxiliary operations
    • B29B7/72Measuring, controlling or regulating
    • B29B7/726Measuring properties of mixture, e.g. temperature or density
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58Component parts, details or accessories; Auxiliary operations
    • B29B7/72Measuring, controlling or regulating
    • B29B7/728Measuring data of the driving system, e.g. torque, speed, power, vibration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/12Making granules characterised by structure or composition
    • B29B9/14Making granules characterised by structure or composition fibre-reinforced
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/285Feeding the extrusion material to the extruder
    • B29C48/286Raw material dosing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/285Feeding the extrusion material to the extruder
    • B29C48/29Feeding the extrusion material to the extruder in liquid form
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/285Feeding the extrusion material to the extruder
    • B29C48/297Feeding the extrusion material to the extruder at several locations, e.g. using several hoppers or using a separate additive feeding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50Details of extruders
    • B29C48/505Screws
    • B29C48/535Screws with thread pitch varying along the longitudinal axis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50Details of extruders
    • B29C48/505Screws
    • B29C48/54Screws with additional forward-feeding elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50Details of extruders
    • B29C48/505Screws
    • B29C48/55Screws having reverse-feeding elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50Details of extruders
    • B29C48/505Screws
    • B29C48/57Screws provided with kneading disc-like elements, e.g. with oval-shaped elements
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

The invention provides mixing, evenly disperse the long fibrous filler of high concentration and the resin composition pellet that obtains.Be that fibrous filler (B) 45~80 weight % (wherein the total amount of resin (A) and fibrous filler (B) is 100 weight %) more than the 1mm supply in the extruder and from mould and extrude with thermoplastic resin (A) 55~20 weight % and length, during the preparation resin composition pellet, give the part (x) of resin (A) from the resin feeding confession of extruder, from being 97/3~50/50 to supply with the remainder (1-x) of fibrous filler (B) and resin (A) with quality ratio x/ (1-x), make particle along extruding the side charging aperture that direction is arranged at the rear of resin feeding mouth.

Description

Be mixed with the preparation method and the resin composition pellet of resin combination of the fibrous filler of high concentration
Technical field
The present invention relates to the low resin of melt viscosity, supply with long fibrous filler high concentration, composite fibre shape filler and the preparation method of the resin combination that obtains and the resin composition pellet that obtains by this method equably from the resin side charging aperture of extruder.
Background technology
In the past; use extruder to be fed to long sides such as glass fibre in the resin and carry out when mixing; under the extremely low situation of the melt viscosity of resin; if it is extremely unstable to supply with flowing of molten resin composition that fiber then spues from extruder with high concentration; make in the step of particle being extruded into wire rod; between extruder and strand pelletizing machine, wire rod is often lost, and produces a large amount of substandard products.In addition, if it is then mobile poor to use such particle to carry out moulding, there is the problem of the bad or dimensional accuracy variation of the outward appearance of moulding product in easily generation bubble or expansion on moulding product surface.
Therefore, though make the structure of screw rod become complicated, so also may not be abundant.
Side charging extrusion method is disclosed among the JP-A 10-180841, in this method, make from the screw-rod structure in the initial mixing zone of side charger and be following (A) and combination (B) and make (A) be positioned at upstream and downstream, wherein (A) for the thickness La/D of per 1 blade is 0.05~2.0, torsion angle β is the kneading disks of 25~75 degree, (B) for 1 helical pitch of screw flight portion is 0.05~2.0 at the thickness La/D of 5~15 position mixing screws jaggy or per 1 blade, torsion angle β is the kneading disks of 80~110 degree.
But it is when utilizing this technology, when in the extremely low resin of melt viscosities such as liquid crystal polymer, mixing the long glass fibres of high concentration, insufficient or uneconomical.
Summary of the invention
The invention provides from the side charging aperture of extruder and supply with long fibrous filler, mix the fibrous filler of high concentration and the preparation method of the economy of the resin combination that obtains and the resin composition pellet that obtains with high concentration uniformly dispersing fibre shape filler.
The inventor finds, the specific part amount by giving resin from the resin feeding confession of the upstream that is positioned at extruder with the remaining amount side charging of specific long fibre shape filler and resin, can address the above problem, thereby finish the present invention.
Promptly, the 1st scheme of the present invention provides the preparation method of resin combination, the method is characterized in that, be that (wherein, the total amount of resin (A) and fibrous filler (B) is 100 weight % for fibrous filler (B) 45~80 weight % more than the 1mm with thermoplastic resin (A) 55~20 weight % and length.) supply in the extruder and from die head and extrude, during the preparation resin composition pellet, a part (x) of giving resin (A) from the resin feeding confession of extruder is from being 97/3~50/50 to supply with the remainder (1-x) of fibrous filler (B) and resin (A) along extruding the side charging aperture that direction is arranged at the rear of resin feeding mouth with quality ratio x/ (1-x).
The 2nd scheme of the present invention provides the preparation method as the described resin combination of the 1st scheme of the present invention, the method is characterized in that, supplies with the part of the resin combination of being extruded by extruder die head from the side charging aperture.
The 3rd scheme of the present invention provides as the of the present invention the 1st or the preparation method of the described resin combination of 2 schemes, and wherein, resin (A) is a liquid crystal polymer.
The 4th scheme of the present invention provides the preparation method as any described resin combination in the 1st~3 scheme of the present invention, and wherein, fibrous filler (B) is glass fibre and/or carbon fiber.
The 5th scheme of the present invention provides as any described resin composition pellet in the 1st~4 scheme of the present invention, and wherein, the weight average length of the fibrous filler in the particle (B) is 100~500 μ m.
By the present invention, obtain economically supplying with long fibrous filler, mixing the resin composition pellet that the fibrous filler of high concentration forms from the side charging aperture of extruder, if it then obtain required rerum natura with raw material and do not have dysgenic moulding product such as expansion as moulding.
Description of drawings
Fig. 1 is a figure that example describes to employed extruder among the present invention.Symbol 1 expression resin feeding mouth among the figure, 2 expression plasticizing portions, 3 expression side charging apertures, 4 expression kneading parts, 5 expression die heads, 6 expression screw rods, 7 expression barrels, 8 expression exhaust outlets, 9 expression decompressors.
The specific embodiment
Extruder
The extruder that the present invention relates to has extrusion die 5, screw rod 6, the barrel 7 of resin feeding mouth 1, plasticizing portion 2, kneading part 4, fibrous filler (hereinafter referred is a filler) and the side charging aperture 3 of resin, resulting resin combination and exhaust outlet 8 and the decompressor 9 that is provided with as required.
Side charging aperture 3 can be arranged on 1 position or a plurality of position.In order to improve the combined amount of the filler in the resin combination, can be arranged on 2 positions.
As extruder, there is no need to use the extruder of special structure, for example, can directly use employed in the past extruder.Specifically, can be any one of single-bolt type, double-screw type, when utilizing double-screw type, the extruder from extruder to 3 screw rod of 1 screw rod of equidirectional rotation can be used, also the parallel screw of different directions rotation or tiltedly screw rod, incomplete engagement type can be.
Screw diameter, the ratio (L/D) of spiro rod length/screw diameter, screw rod design, screw rod rotary speed, same driving force (with driving Move power), heating cooling capacity to extruder do not limit especially, can select to implement condition of the present invention.
Usually, as the screw rod part of decision screw rod design, comprise the carrying part, plasticizing portion part and the kneading part part that contain along screw thread, among the present invention, plasticizing portion in the extruder and the design of the screw rod of kneading part should suitably design according to the character of resin or the kind of filler.
For double screw extruder, plasticizing portion or kneading part are generally constituted by screw rod parts such as minus thread, sealer, suitable kneading disk, contrary kneading disks.
In addition, when exhaust outlet being set carrying out decompression exhaust, the sealing that the resin combination of fusion is full of fully is set preferably in extruder.For the screw rod shape of formation sealing, under the situation of double screw extruder, except minus thread, also suitable use sealing, contrary kneading etc. are being rotated the part with boost capability to screw rod geometrically.In addition, as required, can constitute by parts such as kneading disks.
Usually, carry out decompression exhaust, kneading part double as sealing in the kneading part downstream.Dropping into before the fibrous filler, preferably between exhaust outlet and side charging aperture, sealing is set to giving from the resin feeding confession and plasticized resin when carrying out decompression exhaust.
The L/D of extruder (spiro rod length/screw diameter) is more than 20, is preferably 20~80, more preferably 25~60.
Though the L/D of plasticizing portion depends on the design or the operating condition of screw rod, is preferably 2~15, more preferably 3~10.If the plasticizing of the too short then resin of length of plasticizing portion is insufficient, the fibrous filler of side charging is excessively lost, thus not preferred, if the long then resin of the length of plasticizing portion decomposes, there are bad problems such as rerum natura reduction or generation gas.
Though the L/D of kneading part depends on the design or the operating condition of screw rod, is preferably 2~25, more preferably 5~15.If fractureing of the too short then fibrous filler of length of kneading part is insufficient, the result is mobile to be reduced, thus not preferred, if long then heat release increases, there are the decomposition or the bad problems such as carbonization, generation gas of resin.
Supply with resin and supply with fillers and remaining resin respectively or mix the back to resin feeding mouth 1 by deciding quality or the constant volume feedway carries out to side charging aperture 3.As weigh feeder, can for belt, screw, oscillatory type etc. any one.
Use said apparatus, supply with filler and resin, preferably use weigh feeder to carry out respectively at side charging aperture 3.Specifically, use the side-fed method supplied with by screw feeder from the side of the barrel bucket of extruder, supply to method the extruder, make auxiliary material directly drop to the method etc. of charging aperture from barrel top with the vertical screw charger.
Offside charging aperture 3 does not limit especially, can have the water cooling sleeve pipe to suppress the variation of resin or filler as required.
Resin
Among the present invention, though employed resin (A) is not limited especially, preferred under the temperature higher 10 ℃ than fusing point, convert by shear rate 100/s, apparent melt viscosity is below the 1000Pas, more preferably 50~500Pas, be preferably the resin (A) of 10~100Pas especially.
As resin (A), can enumerate liquid-crystalline polymer, straight chain PPS, nylon 6, nylon 66, NYLON610 etc., be preferably liquid-crystalline polymer.
As liquid-crystalline polymer, can enumerate liquid crystal polyester or liquid crystal polyester acid amides, specifically, can enumerate P-hydroxybenzoic acid residue/2, the combination of 6-hydroxynaphthoic acid residue; The combination of aromatic binary carboxylic acid residues such as aromatic series divalence hydroxy compounds residue/terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid such as P-hydroxybenzoic acid residue/bis-phenol or hydroquinones; The combination of P-hydroxybenzoic acid residue/aliphatic dihydroxy alcohol residue/aromatic binary carboxylic acid residue; And in them, add the combination that para-aminophenol residue etc. forms; Or have the PETG of a part of aliphatic group and product that the P-hydroxybenzoic acid copolymerization forms etc.
In case this resin is because if quilt is plastified then melt viscosity is extremely low in extruder, during with long in a large number fibrous filler side charging, because the losing and disperse insufficient of fibrous filler, can not get from the stability that spues of the stable molten resin composition that spues of extruder die head, the productivity of resin composition pellet significantly reduces.
At least the resin of supplying with from side charging aperture 3 (A) is that particle diameter is the powder more than the 50 μ m, is preferably the above powder of 500 μ m, and more preferably the length of minimum edge or diameter are the above particle of 1mm.If particle diameter etc. is much smaller than above-mentioned scope, then fusion immediately when the side charging, being difficult to length is fibrous filler charging, evenly mixing more than the 1mm, can not obtain from the stable stability that spues that spues of extruder die head.
In addition, when resin (A) was the mixture of material more than 2 kinds, the kind of resin of supplying with from main charging aperture 1 and the resin supplied with from side charging aperture 3 can be identical or different.For example, when resin (A) is the mixture of liquid-crystalline polymer 1 and liquid-crystalline polymer 2, can supplies with liquid-crystalline polymer 1, supply with liquid-crystalline polymer 2 and fibrous filler etc. from main charging aperture 1 from side charging aperture 3.
Fibrous filler
As the kind of fibrous filler (B), can enumerate glass fibre, carbon fiber, polyethylene fibre, polypropylene fibre, polyester fiber, Fypro, fluorine fiber etc., be preferably glass fibre, carbon fiber.They can be at least 2 kinds mixture.
These fibrous fillers (B) can carry out preliminary treatment with various coupling agents such as silanes or titanium class etc. in advance.
As glass fibre, can handle with linings such as epoxies, polyurethanes, acrylic compounds or with collecting agent.
The length of fibrous filler (B) before the side charging is more than the 1mm, to be preferably 1~10mm, more preferably 2~10mm.
The diameter of fiber uses common diameter, for example is 3~15 μ m.If the average diameter of fiber is then little as the effect of reinforcing material anisotropy alleviation effects little or liquid-crystalline polymer less than 3 μ m.On the other hand, if greater than then mouldability reduction of 15 μ m, appearance is variation also.
In addition, the preferred distribution-free of length of the fibrous filler (B) before the side charging, be certain short chopping.
Resin combination forms wire rod by extruder, further cuts off forming particle with comminutor.
The quality ratio of resin in the resin composition pellet (A) and filler (B) is resin (A) 55~20 weight % and fibrous filler (B) 45~80 weight %, be preferably (A) 50~30 weight % and (B) 50~70 weight % (wherein, the total amount of resin (A) and filler (B) is 100 weight %).
The weight average fiber length of the fibrous filler when making particle (B) is 100~500 μ m, is preferably 200~300 μ m.
Be shorter than above-mentioned scope if the weight average fiber in the particle is long-range, when then making the moulding product, can not get sufficient mechanical property, for example, can not show high temperature rigid, if be longer than above-mentioned scope, then not only be difficult to the resin combination of fusion is stably extruded from the extruder die head, and the concentration difference of the fibrous filler of each particle (B), when making the moulding product, flowability or mechanical property instability maybe might exist in bad problems such as producing expansion on the surface of moulding product.
Weight average fiber is long, can the resin in the particle is burnt or dissolution process after, the image that the method for quality by measuring residue or adjust the telescope to one's eyes is observed carries out Computer Processing to be waited and obtains.
Among the present invention, supply with the part (x) of resin (A), from supplying with the remainder (1-x) of fibrous fillers (B) and resin (A) along extruding side charging aperture 3 that direction is arranged at the rear of resin feeding mouth from resin feeding mouth 1.At this moment, the mass ratio x/1-x of the resin of being supplied with (A) is 97/3~50/50, is preferably 95/5~60/40, more preferably 92/8~70/30.
If with respect to filler (B), the ratio that adds remaining resin (A) much smaller than above-mentioned scope then filler (B) can not get mixing fully, if then the weight average fiber of filler (B) is long shortens too much far more than above-mentioned scope, can not show required mechanical property, for example high temperature rigid fully.
A plurality of side charging apertures are set, during with filler (B) and the charging of remaining resin (A) side,, preferably satisfy above-mentioned quality ratio at each side charging aperture though the above-mentioned quality ratio that on average satisfies of a plurality of side charging aperture gets final product.
As the residual resin (A) of side charging part or all, also can use the resin of having extruded, formed particle from extruder die head 5.At this moment, for the filler side charging that fibre length is short, the relation of the part of part or all of the residual resin of supplying with from the side charging aperture (A), fibrous filler (B) and resin composition pellet (C) is: the quality ratio of (part of part or all of residual resin (A)+resin composition pellet (C))/filler (B) is 3/97~30/70, is preferably 5/95~20/80.
Can the hybrid resin additive in above-mentioned resin etc. as auxiliary material.As resin additive, can enumerate plasticizer outside the low bulk density powder described later, heat stabilizer, lubricant, antiblocking agent, crystallization nucleating agent, antioxidant, ultra-violet stabilizer, antistatic additive, fire retardant, drip agent, anti-hydrated agent, antiseptic, deodorant, deodorant, other filler (inorganic additive or organic additive), extender, colouring agent etc. or their mixture.
According to the present invention, not only can make the discharge-amount of the molten resin composition that contains fibrous filler (B) stable, productivity improves, and can easily control fiber progress row by the amount of resin of change side charging in specific scope.Can easily design the rerum natura of moulding product thus.
The moulding of resin combination
The above-mentioned resin composition pellet that obtains can be used for injection moulding, extrusion molding, blow molding, compression forming, sheet moulding etc.
Embodiment
Hereinafter the present invention is carried out specific description, but the invention is not restricted to these embodiment by embodiment.
(embodiment 1~4 and comparative example 1~3)
(1) uses raw material
Resin (A)
Liquid-crystalline polymer particle: Port リ プ ラ ス チ Star Network ス (strain) produces, ベ Network ト ラ C950: aromatic polyester (335 ℃ of fusing points, apparent melt viscosity 30Pas (345 ℃, shear rate 100/s), particle size: about 5~3mm * about 3~2mm * about 3~1mm)
Fibrous filler (B)
Glass fibre (abbreviating GF as): rising sun Off ア イ バ one グ ラ ス company produces, CS03JA419 (the short chopping of fibre diameter 10 μ m, the long 3mm of fiber)
(2) extruder
Mitsubishi Heavy Industries Ltd's industries (strain) are produced, double screw extruder PTE65 (screw diameter 65mm, L/D36.8)
The overview of the screw rod of extruder as shown in Figure 1.
Main charging aperture 1:C1
Plasticizing portion: C4~C5 (structure: one side is along kneading, contrary kneading, length 300mm from the upstream)
Side charging aperture 3:C7
Kneading part 4:C8~C11 (structure: from the upstream one side along mediate, contraryly mediate, along mediate, contrary kneading, minus thread, along mediate, contrary kneading, minus thread, length 520mm)
The charger that leads to main throat-fed: the screw weight-loss type charger that Network ボ company produces
The charger that leads to the side throat-fed
Particulate resin is used: the twin-screw side charger that Network ボ company produces
Glass fibre is used: the belt weight-loss type charger that the long containing of sickle society produces
(3) extrusion condition
Barrel temperature: the barrel C1 that only is provided with main charging aperture 1 is that 200 ℃, other barrel temperature all are 350 ℃.
Die head temperature: 350 ℃.
(4) the mixing and extrusion method of resin combination
Use above-mentioned double screw extruder,, supply with glass fibres from side charging aperture 3 from the particle of resin feeding mouth 1 and side charging aperture 3 supply liquid-crystalline polymers.At the side charging aperture, use twin shaft side charger to supply with, the operating weight charger is controlled to become the ratio of table 1 quantity delivered of liquid-crystalline polymer particle, glass fibre.
Setting screw rod rotary speed as shown in table 1 and extrusion capacity, after cooling off by the spraying spray water when will make the wired belt conveyer carrying of being produced with Na カ from the molten resin composition that die head 5 spues with wire, cut off, obtaining diameter is that 2~3mm, length are the particle of 2~4mm.
(the apparent melt viscosity of resin combination)
Use the capillary type rheometer (the キ ヤ ピ ロ グ ラ Off 1B type that the smart machine of (strain) Japan is produced) of L=20mm, d=1mm, under 350 ℃ of temperature, shear rate 1000/s,, measure apparent melt viscosity according to ISO 11443.
But embodiment 5 and 6 measures under 380 ℃ temperature.
(mensuration of the weight average length of the glass fibre in the particle)
With 5g resin composition pellet heating 2 hours, make its ashing under 600 ℃.After being well dispersed in ash residue in the 5% polyethylene glycol aqueous solution, be transferred in the ware, use the microscopic examination glass fibre with suction pipe.Use image analysis apparatus (LUZEXFS that (strain) ニ レ コ produces) to measure the weight average length of glass fibre simultaneously.When carrying out graphical analysis, the fiber separation that overlaps is become single fiber, be suitable for the subprogram of the length of obtaining each fiber.And, get rid of the following glass fibre of 50 μ m and measure.
(the fracture frequency of wire rod)
By extruder, compound formed under the state of stable state, to the number of times mensuration of the resin combination fracture that is expressed into the wire of institute on the wired belt conveyer 3 minutes.The wire rod breaks are as shown in table 1.
(bad numbers of particles)
Vibratory sieve with the pressed sheet that is equipped with diameter 5mm (パ Application チ Application グ プ レ one ト) sieves the 10kg particle, and the bulky grain that residues on the sieve is carried out weighing.Grain amount is as shown in table 1 on the sieve.
(crooked elastic rate)
(JSW produces, and J75SSII-A) resulting granules is made test film (125mm * 12.7mm * 0.8mm), measure crooked elastic rate according to ASTM D790 by injection (mo(u)lding) machine.
(moulding product outward appearance)
To carrying out visual valuation for the outward appearance of the test film before the mensuration of crooked elastic rate.
(embodiment 5)
Supply with the part of the particle that obtains by extruder from the side charging aperture.Be 90/10 from the quantity delivered of the resin of resin feeding mouth 1/from the quality ratio of the quantity delivered of the resin of side charging aperture 3 this moment.At this moment, supply with 10 weight % with the form of particle.
(embodiment 6)
Resin (A), extrusion condition that following change is raw materials used.From the quantity delivered of the resin of resin feeding mouth 1/from the quality ratio of the quantity delivered of the resin of side charging aperture 3 is 80/20.Screw rod rotary speed and extrusion capacity are set as table 1.In addition condition is the condition identical with embodiment 1.
(1) raw materials used
Resin (A)
Liquid-crystalline polymer particle: Port リ プ ラ ス チ Star Network ス (strain) produces, ベ Network ト ラ T950: aromatic polyester acid amides (370 ℃ of fusing points, apparent melt viscosity 40Pas (380 ℃, shear rate 100/s), particle size: about 5~3mm * about 3~2mm * about 3~1mm)
(3) extrusion condition
Barrel temperature: the barrel C1 that only is provided with main charging aperture 1 is that 200 ℃, other barrel temperature all are 360 ℃.
Die head temperature: 360 ℃
Embodiment 7
Resin (A), the extrusion condition of raw material used in following change.Screw rod rotary speed and extrusion capacity are set as table 1.In addition condition is the condition identical with embodiment 1.
(1) uses raw material
Resin (A)
Liquid-crystalline polymer particle: Port リ プ ラ ス チ Star Network ス (strain) produces, ベ Network ト ラ S950: aromatic polyester (355 ℃ of fusing points, apparent melt viscosity 33Pas (380 ℃, shear rate 100/s), particle size: about 5~3mm * about 3~2mm * about 3~1mm)
(3) extrusion condition
Barrel temperature: the barrel C1 that only is provided with main charging aperture 1 is that 200 ℃, other barrel temperature all are 365 ℃.
Die head temperature: 365 ℃
Carry out compounding under the conditions shown in Table 1, evaluation result is as shown in table 1.
Table 1 (feed process, composition and extrusion condition)
Figure C20068001714600121
Make test film by the particle that above-mentioned extrusion molding obtains by injection (mo(u)lding) machine, evaluation result is as shown in table 2.
Table 2 (rerum natura of resin combination, its particle, injection-molded article etc.)
Wire rod breaks (inferior/3 minute) Weight average fiber long (μ m) Grain amount on the sieve (g/10kg) Apparent melt viscosity (Pas) Crooked elastic rate (GPa) Moulding product outward appearance
Embodiment 1 0 231 0.3 74 17.6 Well
Embodiment
2 4 256 2.1 76 17.9 Well
Embodiment 3 0 168 0.2 79 16.2 Well
Embodiment 4 7 183 4.8 80 16.7 Well
Embodiment
5 0 214 0.2 72 17.4 Well
Comparative example 1 97 281 274 93 18.9 Expansion is arranged
Comparative example 2 Produce off and on - Can not make particle - - -
Comparative example 3 0 143 0.2 78 14.2 Well
Embodiment
6 0 269 0.2 58 19.5 Well
Embodiment 7 0 264 0.2 39 20.4 Well

Claims (6)

1. the preparation method of resin composition pellet, it is characterized in that, at total amount 100 weight % with respect to thermoplastic resin (A) and fibrous filler (B), with thermoplastic resin (A) 55~20 weight % and length is that above fibrous filler (B) 45~80 weight % of 1mm supply in the extruder and from die head and extrude, thereby during the preparation resin composition pellet, supply with a part of x of resin (A) from the charging aperture of the resin of extruder, from being 97/3~50/50 to supply with the remainder (1-x) of fibrous filler (B) and resin (A) with quality ratio x/ (1-x) along extruding the side charging aperture that direction is arranged at the rear of resin feeding mouth.
2. the preparation method of resin composition pellet as claimed in claim 1 is characterized in that, supplies with the part of the resin combination of being extruded by extruder die head from the side charging aperture.
3. the preparation method of resin composition pellet as claimed in claim 1 or 2, wherein, resin (A) is a liquid crystal polymer.
4. the preparation method of resin composition pellet as claimed in claim 1 or 2, wherein, fibrous filler (B) is glass fibre and/or carbon fiber.
5. the preparation method of resin composition pellet as claimed in claim 3, wherein, fibrous filler (B) is glass fibre and/or carbon fiber.
6. by any resin composition pellet that described preparation method obtains in the claim 1~5, wherein, the weight average length of the fibrous filler in the particle (B) is 100~500 μ m.
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