CN1613635A - Production of multi-layer polyethylene terephthalate film - Google Patents

Production of multi-layer polyethylene terephthalate film Download PDF

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Publication number
CN1613635A
CN1613635A CNA2004100858803A CN200410085880A CN1613635A CN 1613635 A CN1613635 A CN 1613635A CN A2004100858803 A CNA2004100858803 A CN A2004100858803A CN 200410085880 A CN200410085880 A CN 200410085880A CN 1613635 A CN1613635 A CN 1613635A
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CN
China
Prior art keywords
film
cover layer
fused mass
effluent
additive
Prior art date
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Granted
Application number
CNA2004100858803A
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Chinese (zh)
Other versions
CN1613635B (en
Inventor
W·施蒂比
E·戈贝尔
K·纽康
魏文良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Uhde Inventa Fischer AG
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EMS Inventa AG
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Publication of CN1613635A publication Critical patent/CN1613635A/en
Application granted granted Critical
Publication of CN1613635B publication Critical patent/CN1613635B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • 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
    • 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
    • B29C48/695—Flow dividers, e.g. breaker plates
    • B29C48/70—Flow dividers, e.g. breaker plates comprising means for dividing, distributing and recombining melt flows
    • B29C48/705—Flow dividers, e.g. breaker plates comprising means for dividing, distributing and recombining melt flows in the die zone, e.g. to create flow homogeneity
    • 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
    • B29C48/74—Bypassing means, i.e. part of the molten material being diverted into downstream stages of the extruder
    • B29C48/745—Bypassing means, i.e. part of the molten material being diverted into downstream stages of the extruder for plasticising or homogenising devices
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B29C48/695—Flow dividers, e.g. breaker plates
    • 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
    • B29C48/74—Bypassing means, i.e. part of the molten material being diverted into downstream stages of the extruder
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/005—Oriented
    • B29K2995/0053—Oriented bi-axially

Abstract

To form a multi-layer film of polyethylene terephthalate (PET), the plastics is taken directly from the polycondensation stage (P) into the main flow without modification to be used as the base layer (B). A flow is diverted from the main flow, to be mixed with additives and passed to the film jet (3) as flanking flows (A) for the covering layers.

Description

The direct pouring of PET fused mass is become the method for plural layers
Technical field
The present invention relates to fused mass that a kind of utilization mainly is made up of PETG (PET) and make the method for plural layers.
Background of invention
In the known systems method, after granular materials is melted, in single-screw or double-screw extrusion machine, be made into film by so-called extruding or co-extrusion pressure mode.This type of extruder all is extremely advanced machine, and it purchases with cost of use all very expensive.
Except single thin film, also have two-layer or more multi-layered film for people are known in the prior art at present, for example, be applied to the film in packaging industry or the food industry.At this, for special-purpose, utilize specific additive to carry out modification and give the polymer of special nature, can be used in each individual layer.
Plural layers generally include a B of basic unit and one or more cover layer A, C etc., and their available identical or different modes are formed or made.
Concerning different compositions, adding necessary additive in polymer can finish in polycondensation process, perhaps, is more preferably by so-called master batch method and carries out separately finishing in the polymer beads fusion process in extruder.Two kinds of methods all have sizable shortcoming and need other equipment to make specific polymer composition.
Described in DE-A-1 604 368 because the influence of the thermal stress of the residual moisture of particle and polymer, any fusing, especially for the PET particle, can cause degraded and since under the viscosity general who has surrendered make polymer become inhomogeneous.This can influence the quality of casting output and film.Therefore, the PETG particle of manufacturing film must be through a meticulous multiple tracks and the very high baking operation of cost.
Summary of the invention
Therefore, the objective of the invention is to, avoid using particle to make PET film, particularly plural layers as the processing raw material.
This purpose is to realize by the method that directly the PET fused mass is cast into plural layers as claimed in claim 1.
Wherein a kind of scheme is a kind of like this method: the fused mass that will mainly be made up of PETG is delivered directly to the operation of casting film from polycondensation process.For this reason, be the so-called B of basic unit preferably with unmodified PET fused mass still.Concerning cover layer is made, before casting,, in identical fused mass, continue to add any additive by the equipment that cooperates in the effluent.
In this case, different naturally lateral-flow device and casting method separately thereof can be used to make identical or different product simultaneously, that is to say that for example those have the plural layers of different structure.On the other hand, a lateral-flow device also can provide several casting methods simultaneously.
Preferably, method of the present invention relates to the manufacturing of plural layers, and described plural layers are made up of a B of basic unit and at least one cover layer A.Basic unit and tectal quantity are than at 90-60: between the 10-40, concerning three-layer thin-film, at 85-75: preferable between the 15-25.
Plural layers made according to the method for the present invention, three-layer thin-film preferably can select to make the structure of symmetric or asymmetry.Like this, each individual layer just has different compositions because mixed different additives.
This method is suitable for making the flat film or the inflation film of multilayer.
In the preferred embodiment of a three-layer thin-film, basic unit B both sides are respectively in conjunction with a cover layer A, and wherein these two tectal fused mass compositions are preferably identical.
In the method, the PET fused mass of all layers use is made up of crystallizable PETG basically, according to the situation of prior art, can add a spot of polyester therein again.Example is that the polynaphthenic acid glycol ester that is used for esterification and ester exchange known in the state of the art and catalyst and additive are added.
The content of this polyester is that 0.1 to 5% (weight) is better.The intrinsic viscosity of polyester fused mass (IV) is better between 0.59 to 0.68.
Each individual layer, particularly cover layer A have also comprised the additive that for example helps thin film fabrication and so on, and these additives are modified to and are suitable for film, the perhaps use of granulated product again in the thin film fabrication.
For example, additive can be stabilizing agent, pigment, filler, fire retardant and conduction improver.Pigment preferably uses SiO 2
In further procedure of processing, preferably, film comes directed with a kind of well-known mode by biaxial extension.For example, preferable three-layer thin-film is under its elongation state, and thickness is between 0.5 μ m and 25 μ m, and the A layer thickness is preferably between 0.1 μ m and 5 μ m, and the B layer thickness is preferably between 0.3 μ m and 15 μ m.
The thickness of cover layer A at 1.0 μ m between the 1.5 μ m and the thickness of B is desirable especially at 10 μ m to the three-layer thin-film between the 15 μ m.
Preferably, according to known prior art, film is placed on the chilling roll that is in the electrostatic field after leaving the film mold.Behind the process chilling roll, film just can carry out the stretching of vertical and horizontal with 4: 12 total drawing ratio in Tg+10 ℃ to Tg+60 ℃ scope.Finally, with before for example 300 to 400m/min rotating speed is reeled, between 150 ℃ to 250 ℃, make the film thermosetting.
Description of drawings
Fig. 1 is a chart, its demonstration have two identical tectal three-layer thin-film ABA manufacture method circulation and by in a part of fused mass effluent of A, adding additive.
Fig. 2 is the another kind of conversion of the inventive method, with masterbatch fused mass form additive is joined in the fused mass effluent of A.
Reference numerals list
The P polycondensation process
The V allocation units
1 supply unit
2 supply units
3 film molds
4 effluent branches
5 conveying devices
The removal of 6 local flows
7 measuring units
8 measuring units
9 mixed cells
The adding of 10 additives
11 tie points
12 conveying devices
13 cover layer branches
14 blenders
The branch of 15 main flow B
The separation of 16 fused mass is used
The branch of 17 fused mass A
The recirculation of 18 fused mass A
19 deep processings
20 supply units
The specific embodiment
In Fig. 1, the PET fused mass behind the polycondensation P enters a conveying device 1, and described conveying device 1 is transported to film mold 3 to the smelt flow that is used to make the B layer by another conveying device 2.Can realize supply by an allocation units V to several different film lines.
At 4 places, from fused mass, tell an effluent and be used for making cover layer A, and be transported to film mold 3 via the branch 13 that makes two cover layer A by conveying device 5 and 12.
From effluent, tell a part of smelt flow at 6 places.This smelt flow is mixed with at least a additive 10 in mixed cell 9 then by measuring unit 7 and 8.Then, it converges at tie point 11 places again with the effluent that is used for making A, and mixes consumingly in blender 14.At branch 15 places, can from main flow B, distribute another part fused mass, do to use separately, for example be transmitted and make chip 16.
Be more preferably after passing through supply unit 20, the effluent A that comprises additive can flow out 10 to 20% by another branch 17, and flows back to by another tie point 18 again.This makes the circulation of mixed cell 9 keep constant, particularly runs into the situation that output changes or thin film fabrication is interfered at 3 places.It also can avoid the time of staying of smelt flow to change, and the polymer thermal degradation.
After leaving film mold 3, film is passed to deep processing 19 operations, particularly is delivered to biaxial tension.
In the another kind of conversion of the inventive method shown in Figure 2, be transferred among the effluent fused mass A through tie point 11 by supply unit 20 and measuring unit 8 at 18 place's masterbatch fused mass.
The characteristics of the inventive method are short especially to the distance the casting from polycondensation, so the quality of PET fused mass is highly stable.
A special advantage of this method is exactly, and cancelled fused mass extruding and meticulous drying unit with high costs, and these unit all are that the PET particle is needing process after the manufacturing and before being processed into film.
Therefore essence of the present invention is, the fused mass of all layers use in the methods of the invention is made up of the identical PETG or the PETG mixture that directly extract from polycondensation process, but if needs are arranged, fused mass can carry out modification by diverse ways.
Method of the present invention is got rid of clearly and is comprised the step of using particle.
The present invention also comprises the Biaxially stretched multilayered film that a kind of the present invention's of utilization method is made.

Claims (11)

1. method that the direct pouring of PETG (PET) fused mass is become plural layers, described plural layers are made up of a B of basic unit and at least one cover layer A with the additive modification, this method combines the smelt flow of A and B in a film mold, and the postorder deep processing is that described plural layers are carried out biaxial tension, it is characterized by
-PET directly extracts from polycondensation process with the form of smelt flow,
-by supply unit the PET fused mass is delivered to mold, wherein have a main flow that is used for making the non-modified of the B of basic unit at least,
-from main flow, tell at least one effluent, be used for making at least one cover layer A,
-wherein at least one effluent, distribute a part of smelt flow, toward wherein adding additive, this partial melting logistics is back to this effluent again and mixes with it, and perhaps additive adds in the effluent with masterbatch fused mass form,
-wherein can select to distribute another part fused mass to do to use separately.
2. the method for claim 1 is characterized by, and one of them cover layer A is different on ratio, quantity and/or the type of additive with other cover layer, and/or different on layer thickness.
3. method as claimed in claim 1 or 2 is characterized by, and makes a kind of plural layers, and it comprises a B of basic unit and on the two sides of B one cover layer A is arranged respectively.
4. method as claimed in claim 3 is characterized by, and in the three-layer thin-film of making, the quantity ratio of B of basic unit and cover layer A is 90: 10 to 60: 40.
5. method as claimed in claim 4 is characterized by, and in the three-layer thin-film of making, the quantity ratio of B of basic unit and cover layer A is 85: 15 to 75: 25.
6. the method according to any one of the preceding claims is characterized by, and the PET fused mass mainly is made up of PETG, has also added other polyester of 0.1 to 5% weight.
7. the method according to any one of the preceding claims is characterized by, and distributes the partial melting logistics from effluent A continuously, and it has at least a part to be back among the A continuously and mixing with it.
8. the method according to any one of the preceding claims is characterized by, and additive is selected from UV or heat stabilizer, pigment, fire retardant and conduction improver, and perhaps they are the granular again products of film.
9. method as claimed in claim 8 is characterized by, and pigment is SiO 2
10. the method for claim 1, it is characterized by, in deep-processing process, film is directed by biaxial tension, and as the three-layer thin-film that is in extended state, its thickness at 0.5 μ m between the 25 μ m, the thickness of A at 0.1 μ m between the 5 μ m, the thickness of B at 0.3 μ m between the 15 μ m, after leaving the film mold, film is sent to a chilling roll that is arranged in electrostatic field, and then, film carries out vertical and horizontal and stretches under Tg+10 ℃ to Tg+60 ℃ temperature, its total drawing ratio is 4: 12, at last, before reeling, under 150 ℃ to 250 ℃ temperature, make the film thermosetting with 300 to 400m/min speed.
11. plural layers of making according to each described method in the claim 1 to 10.
CN2004100858803A 2003-11-07 2004-11-04 Method for direct pouring polyethylene terephthalate smelt into film Expired - Fee Related CN1613635B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH01921/03A CH694291A5 (en) 2003-11-07 2003-11-07 Production of multi-layer polyethylene terephthalate film, for the packaging/foodstuff industries, takes a flow directly from polycondensation for the base and diverted flows to take additives for the covering layers
CH01921/03 2003-11-07
CH01921/2003 2003-11-07

Publications (2)

Publication Number Publication Date
CN1613635A true CN1613635A (en) 2005-05-11
CN1613635B CN1613635B (en) 2011-03-02

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CN102367571A (en) * 2011-09-20 2012-03-07 常州机电职业技术学院 Preparation method for improving surface hydrophilicity of nanometer polyethylene terephthalate (PET) films

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WO2016100060A1 (en) * 2014-12-18 2016-06-23 Dow Global Technologies Llc System and method for processing of low viscosity polymers

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Publication number Priority date Publication date Assignee Title
CN102367571A (en) * 2011-09-20 2012-03-07 常州机电职业技术学院 Preparation method for improving surface hydrophilicity of nanometer polyethylene terephthalate (PET) films

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Publication number Publication date
CN1613635B (en) 2011-03-02
CH694291A5 (en) 2004-11-15

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