Classifications

• • 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
  • 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
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/285—Feeding the extrusion material to the extruder
  • B29C48/29—Feeding the extrusion material to the extruder in liquid form
• • 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
  • C08J3/201—Pre-melted polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/07—Flat, e.g. panels
  • B29C48/08—Flat, e.g. panels flexible, e.g. films
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/285—Feeding the extrusion material to the extruder
  • B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
  • B29C48/50—Details of extruders
  • B29C48/76—Venting, drying means; Degassing means
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
  • B29K2023/04—Polymers of ethylene
  • B29K2023/06—PE, i.e. polyethylene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
  • B29K2023/04—Polymers of ethylene
  • B29K2023/08—Copolymers of ethylene
  • B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
  • B29K2023/10—Polymers of propylene
  • B29K2023/12—PP, i.e. polypropylene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
  • B29K2105/0038—Plasticisers

Definitions

• the present invention is in the field of pigment concentrates in thermoplastic polymers.
• thermoplastic polymers or pigment masterbatches for short
• the thermoplastic polymer (carrier) is tailored to the respective end product.
• the pigment is usually used in powder form in all known processes, which has process engineering disadvantages, such as complex pre-treatment steps (drying, grinding, additives, premixes) and possibly additional upstream dispersion steps.
• dispersing aids such as waxes, oils or stearates are usually added.
• the addition of the dispersing agents can be up to 40% by weight or more.
• these substances are undesirable in the masterbatch, since they can lead to problems during processing or to quality losses in the end product.
• even adding these auxiliaries cannot always ensure that optimum dispersion is achieved.
• powder pigments for the production of highly pigmented pigment masterbatches their low bulk density is disadvantageous in direct processing in the extruder.
• the object of the present invention was to provide a continuous, inexpensive process for the production of pigment masterbatches which avoids the process engineering disadvantages described above, can do without the use of large amounts of dispersing auxiliaries and delivers particularly homogeneous products. This task could be solved by a special extrusion process as defined below.
• the invention relates to a process for producing a pigment masterbatch by extrusion, characterized in that a) a thermoplastic polymer in granular or powder form is metered continuously into a preferably co-rotating twin-screw extruder; b) the metered polymer is melted in the extruder; c) a pumpable pigment press cake, preferably containing 5 to 35% by weight of pigment, water and / or organic solvent, is metered continuously into the molten polymer under increased pressure through an inlet opening of the extruder, the pressure being so high that the boiling temperature of the water and / or organic solvent is higher than the internal temperature of the extruder in the region of this inlet opening; d) if necessary, a flow improver is added to optimize the dosage; e) the pigment from the press cake is dispersed into the molten polymer by the action of shear forces; f) the water and / or organic solvent is removed through at least one outlet opening of the extruder, which is preferably combined with
• the process according to the invention is expediently controlled and regulated by a fully automatic measuring and regulating device. It is a continuous process which, in contrast to the known batch processes (e.g. flushing on a kneader at atmospheric pressure and temperatures below the normal boiling point of water), enables economic throughput rates at higher pressure and elevated temperature.
• a twin-screw extruder with a length / diameter ratio of 25 or greater is suitable for carrying out the method according to the invention, which has a device for introducing the thermoplastic polymer, then an extrusion section for melting the thermoplastic polymer, and then an inlet opening for metering in the pigment press cake under increased pressure Pressure, followed by an extrusion line for dispersing the pigment particles into the molten polymer by the action of shear forces, and then one or more outlet device (s) for removing the water and / or organic solvent from the pigment press cake under increased pressure.
• the process parameters are preferably controlled via a process control system.
• Suitable thermoplastics are the plastics typically suitable for masterbatch production, in particular polyethylene, polypropylene, polystyrene and its modifications, and EVA.
• Organic pigments are particularly suitable as pigments.
• organic pigments in the context of the invention are monoazo pigments, Disazo pigments, disazo condensation pigments, laked azo pigments, triphenylmethane pigments, thioindigo pigments, thiazine indigo pigments, perylene pigments, perinone pigments, anthanthrone pigments, diketopyrrolopyrrole pigment pigments, dioxazine pigments, dioxazine pigments, dioxazine pigments, dioxazine pigments
• Benzimidazolone pigments Benzimidazolone pigments, naphthol pigments and quinophthalone pigments.
• the plastic powder or granulate expediently gets into the extruder from a storage container by gravimetric metering by means of a screw conveyor.
• the shear forces of the twin-screw extruder in operation which act on the metered-in plastic particles, as well as the heat caused by electrical heaters installed on the outside of the extruder barrel, plasticize the plastic.
• the pigment press cake expediently contains between 5 and 35% by weight of pigment in order to be easily pumpable.
• a conventional flow improver can also be added, preferably surface-active substances, such as oxalkylates or functionalized polymers.
• the pigment press cake is preferably aqueous, but organic solvents, such as chlorobenzenes, mono- or polyhydric alcohols, their ethers and esters, for example alkanols, in particular with 1 to 6 C atoms, such as methanol, ethanol, propanol, isopropanol, butanol, can also be used , Isobutanol, amyl alcohol; di- or trihydric alcohols, in particular with 2 to 5 carbon atoms, for example ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 2,6- Hexanetriol, glycerin, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, tripropylene glycol, polypropylene glycol; lower alkyl ethers of polyhydric alcohols, such as, for example,
• the pigment press cake is metered into the extruder under increased pressure, preferably by a pump (for example an eccentric screw pump) at a pressure between 1 and 30 bar. So that the polymer melted in the extruder remains flowable, it is expedient to heat the pigment presscake to be metered in shortly before entering the extruder to a temperature between 20 and 220 ° C., preferably 60 to 180 ° C.
• the proportions between the polymer and the pigment press cake should be chosen so that the resulting pigment masterbatch is about 10 to 70% by weight, preferably 30 to 50% by weight, pigment and about 30 to 90% by weight, preferably Contains 50 to 70 wt .-%, thermoplastic polymer.
• the transition of the pigment into the polymer takes place in the subsequent extrusion section.
• a suitable screw design inside the extruder causes the phase transition of the pigment from the pigment press cake into the plastic melt and an effective dispersion of the pigment particles in the polymer.
• the removal of the water and / or solvent usually takes place at temperatures above 100 ° C., preferably 120 ° C. to 240 ° C. and under increased pressure (value depending on the type of liquid to be separated). This means that no heat of vaporization is extracted from the system; the pigment / polymer melt remains in the plastic phase.
• a differential pressure control preferably a fully automatic differential pressure control with the aid of a control valve, prevents the liquid to be separated from evaporating in the extruder, which would have the consequence that, due to the relatively large volume of the gas, the kinetic energy on leaving the system would be so large that parts of the pigment / Polymer melt would be entrained in the gas stream.
• the water and / or solvent is preferably separated off liquid via a constant differential pressure via one or more twin screw locks which are sealed for a pressure of up to 30 bar, then cooled and let down.
• the thermal energy of the separated water and / or solvent can be recycled and used, for example, to warm the press cake before it is injected into the extruder.
• Remaining amounts of water and / or solvent can be drawn off from the pigmented polymer melt using a subsequent degassing device (atmospheric or vacuum) on the extruder.
• the pigmented polymer melt is then discharged from the extruder, the resulting pigmented polymer strands are cooled, for example in a water bath, and granulated.
• the process according to the invention offers compared to conventional manufacturing processes for master batches, e.g. the hot-cold mixing process, comparable space-time yields of the overall process, lower overall energy consumption and surprisingly also better ones
• the filter value and film grade describe the dispersion quality of a pigment in a masterbatch.
• a defined amount of masterbatch is melted in a single-screw extruder with a downstream gear pump and pumped through a mesh screen with a defined mesh size. If incompletely dispersed pigment particles (pigment agglomerates) are contained in the masterbatch, they get caught in the mesh of the sieve. This reduces the flow cross-section of the sieve, which leads to an increase in pressure upstream of the sieve.
• the specific pressure difference from the start to the end of the test is the so-called filter value.
• a blown film is produced which is colored using the masterbatch to be tested. Pigment agglomerates are then visible in the film as specks. The number of specks (error index) and size are evaluated against reference samples. Correlation between error index and foil grade:
• % means percent by weight.
• FIG. 1 shows the basic structure of the extruder and the temperature distribution in the extruder.
• a polyethylene granulate ( ⁇ Riblene MR 10) was continuously metered into the first cylinder of the extruder by gravimetric metering at a constant feed rate (12 kg / h).
• the polymer was melted in the following two cylinders.
• the aqueous press cake (pigment content: 25% by weight of PV real yellow HG / PY 180) was metered into the 4th cylinder via an eccentric screw pump (likewise continuously and at a constant feed rate of 32 kg / h).
• the pressure here was 7 bar.
• the temperature at the inlet opening of the extruder was 140 ° C. In cylinders 5 and 6, the pigment was introduced into the polymer and dispersed.
• the water was then over two Twin screw locks, each with 200 revolutions / minute, separated from cylinders 7 and 10 at temperatures> 100 ° C.
• the cylinders 8, 9 and 11 are used for intensive dispersion of the pigment in the polymer.
• the polymer strands were then conveyed out of the extruder via a perforated plate, cooled in a water bath, dried with the aid of suction and strand pelletized.
• Figure 1 Structure of the extruder and axial temperature distribution in the extruder
• the product was a dry masterbatch granulate with a pigment content of 40% and a polyethylene content of 60%. Although no wax or a similar additive was added, this masterbatch has a better dispersion of the pigment in the plastic than a comparable product standard of conventional production (40% pigment, 40% wax, 20% polyethylene, hot mixed in a high-speed mixer and then cooled and extruded in a cooling mixer ).
• Table 1 compares the film grade and filter value.
• Table 1 Foil grade and filter value of a masterbatch using the method according to the invention and a masterbatch standard
• Example 2 A co-rotating twin-screw extruder with a screw diameter of 40 mm and an L / D ratio of 52 was used to prepare the masterbatch (13 cylinders; 1 cylinder corresponds to 4D). The speed of rotation of the screws was 500 revolutions / minute.
• Figure 2 shows the basic structure of the extruder.
• FIG. 2 Structure of the extruder and axial temperature distribution in the extruder.
• the polypropylene granules (MFI 36) were metered continuously into the first cylinder of the extruder by gravimetric metering at a constant feed rate of 17.5 kg / hr.
• the polymer was melted in the following two cylinders.
• the aqueous press cake (pigment content: 20% by weight PV real pink E / PR 122) was metered into the 4th cylinder via a Eccentric screw pump (also continuous and with a constant feed rate of 37.6 kg / hr).
• the pressure here was 8 bar.
• the temperature at the inlet opening of the extruder was 160 ° C.
• an additive was added to the press cake to improve the flow behavior (acrylic polymer base; 1% based on the pigment content).
• the pigment was introduced into the polymer and dispersed.
• the water was separated from cylinders 7 and 10 at temperatures> 100 ° C. via two twin screw locks (1: 300 revolutions / minute; 2: 200 revolutions / minute).
• the cylinders 8, 9 and 11 serve to further disperse the pigment in the polymer.
• Cylinder 12 has a vacuum connection for residual dehumidification of the pigment / polymer melt.
• the polymer strands were conveyed out of the extruder via a perforated plate, cooled in a water bath, dried with the aid of suction and strand pelletized.
• the product was a dry masterbatch granulate with a pigment content of 29.9%, an additive content of 0.3% and a polypropylene content of 69.8%. Compared to a conventional product standard, this masterbatch has a better film grade and a better filter value (see Table 2).
• Conventional product standard 30% pigment, 30% wax, 40% polypropylene, hot mixed in a high-speed mixer and then cooled and extruded in a cooling mixer).
• Table 2 Foil grade and filter value of a masterbatch according to the inventive method and a masterbatch standard

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

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• 2003
  • 2003-08-06 DE DE10335863A patent/DE10335863A1/de not_active Withdrawn
• 2004
  • 2004-07-28 KR KR1020067002440A patent/KR20060087502A/ko not_active Application Discontinuation
  • 2004-07-28 WO PCT/EP2004/008420 patent/WO2005017003A1/de active Application Filing
  • 2004-07-28 EP EP04741294A patent/EP1654308A1/de not_active Withdrawn
  • 2004-07-28 CN CNB2004800246881A patent/CN100366664C/zh not_active Expired - Fee Related
  • 2004-07-28 JP JP2006522287A patent/JP2007501299A/ja not_active Withdrawn
  • 2004-07-28 US US10/567,308 patent/US20070182053A1/en not_active Abandoned

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