TW200413151A - Polymer film production - Google Patents

Abstract

A process for the continuous production of polymer film in which a liquid polymer-forming composition at or in the region of room temperature is supplied to an inlet of slot die extrusion apparatus and after passing through said slot die extrusion apparatus is discharged from an outlet thereof onto a moving carrier, said polymer film forming on said carrier and being cured or allowed to cure.

Description

说明 Description of invention:

c Minghujin J This invention relates to a method for manufacturing a polymer film. More particularly (though not absolutely), the present invention relates to a method for manufacturing a hydrophilic polymer film that can be used in functional films, such as breathable film, and specifically used in The composite layer of clothing. H Ji currently has two commercial technologies available for continuous manufacturing of hydrophilic films. These two techniques are melt extrusion and solvent-based melt casting. However, both of these techniques suffer from disadvantages or limitations. The melt extrusion method is limited to hydrophilic polymers, which are generally less extruded than conventional extrusion. This low thermal stability limits the properties required for films. Because polymer stability is required at the melting temperature, the range of hydrophilic polymer materials that can be extruded is also limited. The melt extrusion method also requires experts to control and balance its operating parameters. The solvent-based dazzling scale method is commercially used for continuous production of films', for example, it can be widely used in functional clothing film layer = aminoacetic acid ethyl acetate film. This solvent-based feedstock method limits the cost and difficulty of making crosslinked polymer films. Solvents in the amount of $ 'will need to be recycled for reuse, so that the ring P can be reduced to a minimum. Solvent-based methods to produce hydrophilic amines-stilbenezine will be used. The amount of dimethylformamide ①) solvent. The reading solvent may be extracted into water or volatile. It is then recycled and then dried, which can increase the total manufacturing process cost and it limits the production speed. Therefore, it is desirable to develop an alternative continuous polymer film manufacturing technology that can avoid or minimize the disadvantages of known melt extrusion and solvent-based melt casting techniques. 5 Polyurethane is an example of a hydrophilic polymer, and it can be prepared by reacting a liquid component in a reaction vessel. Although the reagent is liquid when mixed at or slightly above room temperature, the polymer it produces is solid at room temperature. The reaction is therefore usually carried out in a solvent, which allows it to be removed from the container as a 10 liquid at the melting point of the polymer. A polymer having a very short chain can be produced by performing the above reaction, and the polymer is liquid at room temperature without using a solvent. The finished polymer is capped with an end-cap, so that the polymer no longer has any kind of reactive group that resides at its molecular end. In this way, a short-chain liquid polymer can be prepared, the polymer still has a terminal group 圑, 15 and the polymer can be further reacted. This polymer is called a prepolymer. The monoethylaminoacetate prepolymer has an isocyanate group which can react at its molecular end. These groups can be reacted with any kind of material containing -OH group (including water). The isocyanate group is bonded to the prepolymer 20 and is thereby used to make it nonvolatile. This prepolymer is less toxic than unreacted isocyanates when inhaled. This material will be very stable, but only if it is isolated from all sources of -OH groups. Therefore, this prepolymer can have a long or permanent "cabinet shelf life". 6 Suppose that a PU prepolymer is mixed with a molecule containing a material (for example, polyalcohol) containing more than 1 0H group in the correct proportion, the two reagents will react to form a polymer chain. A polymer can be formed only when both prepolymers have at least two active isocyanates and the polyol has at least two active OH groups. A monoisocyanate reacts with a -0H group to form an ethylamino group. Assuming that one molecule has two or more isocyanate groups (eg, diisocyanate, which has two isocyanate groups), the molecule can react with molecules containing more than one 0H group. This type of reactant is called a polyalcohol, and it forms a continuous long chain, the long 10-chain containing many amino ethyl acetate groups, and this material is called a polyamino ester. A prepolymer can be prepared by adding an excess of diisocyanate to a polyol and then heating the mixture in a reaction vessel. It is assumed that when the prepolymer is mixed with a polyol, the prepolymer reacts with it to form a polyurethane. 15 The present inventors now design a polymer film formation technology suitable for use in the manufacture of hydrophilic films by extrusion equipment, in which a polymer-forming composition that is substantially free of solvents is mixed and then successively formed by a continuous film formation technology in It is discharged from the extrusion device at or near room temperature. [Summary of the Invention] 20 According to one aspect of the present invention, the present invention provides a method for continuously manufacturing a polymer film, in which a liquid polymer-forming composition is at or near room temperature. , Is fed to the entrance of a slot die extrusion device, and then after passing through the slot die extrusion device, an outlet from the device is unloaded onto a mobile carrier. After being formed on the shaft U, it is hardened or hardened. The polymer-forming composition may be a #component system, for example, a polyurethane polymer, which may be unloaded onto a mobile device through the slit die extrusion device, and then borrowed successively. The film (and the support substrate) is used as a water material for a reactant to harden. The film and the substrate can be passed through one or several water tanks in a manner similar to the known water-dissolving water tank to harden the polymer film, and then heated in an oven or a heating drum to complete the reaction. The polymer-forming composition may be a "two-component ,, system, in which at least two reactive components are mixed and then fed into the slit as a positive reaction or a reactive mixture In a mold extrusion device, some polymer formation in the system occurs before unloading to a mobile support. In this two-component system, it is desirable to select the polymer to be included in the polymer forming composition. A reactant is formed, thereby giving the composition a gel time of about 5-10 minutes to avoid it from forming a polymer colloid before being ejected from the slot mold. Due to the use of this two-component system It involves mixing at least two kinds of reactions immediately before feeding to the entrance of the slot mold. Therefore, this two-component system is called reactive extrusion. The composite reaction can be used in extrusion. Afterwards, it is accelerated by heating. The present invention provides a method for eliminating or at least substantially reducing the environmentally undesirable solvent (eg, dimethylformamide (DMF)). In some specific examples of the present invention Middle One component in a two-component system is hardened at room temperature. In this case, a small amount of solvent is allowed to dissolve the component. These specific examples are formulated with a low solvent content (about 10 wt. Or less). %, But preferably not more than 7 wt% of the solvent). Compared with solvent-based fusion casting methods, such solvents (if used) still represent a reduction of about 70 times or less. Solvent content. Although the present invention provides a convenient method that can be used to continuously manufacture hydrophilic polymer films, the method for preparing hydrophobic polymer films is also encompassed by the present invention and is a feasible method. Water-based polymer film can be used as an intermediate bonding layer between a hydrophobic polymer surface and a porous substrate. This allows the deep-grained surface to be completely filled without substantial loss of water permeability Fortunately, the extruded thickness of the water-repellent film manufactured in accordance with the present invention falls within a range of 5 to 50 μm, preferably 5 to 30 μm, and more preferably 10 to 20 μm. The specific example of using a two-component reactive extrusion system to make a polyurethane polymer film may include the following steps: a. Under a kind of inert and moisture-free air, a polyfunctional isocyanate and a Multifunctional reactants containing hydroxyl, amine or imine groups are reacted to form a prepolymer with reactive isocyanate ends; b. With a chain containing hydroxyl, amine or imine groups Elongating agent to mix the prepolymer to form a polymer to form a composition; c. Optionally adding a polymerization catalyst to the composition; d to allow the polymer to form a composition at room temperature or near a chamber E. Pass the slitting mold at a warm temperature; e. Unload the polymer-forming composition from the slit tweezers onto / support the support substrate; and f. Harden the film. The prepolymer preferably contains 1- 5 repeating units. In a preferred embodiment, the prepolymer includes a selectable polyol unit and a polyfunctional isocyanate 5 ester unit. The molecular weight of the polyol is between 500 and 5000. The prepolymer may also contain a low molecular weight liquid diol, such as 1,4-butanediol. In a particularly preferred embodiment, the polyol preferably contains one or more polypropylene glycols, polyethylene glycols, or polytetramethylene alcohols, but more preferably contains polyethylene glycols or a polypropylene glycol / polyethylene glycol. An adduct or copolymer of alcohol. 10 In a preferred embodiment of the two-component reaction system, the chain extender contains a reactive meridian or imino group. In some preferred embodiments, the chain extender contains an amine ', although in other embodiments the chain extender contains an aromatic diol optionally conjugated to a fatty diol. The aromatic diol which the chain extender can conveniently contain is hydroquinone di (β-hydroxyethyl) ether [HQEE]. The 15 chain extender can be formulated in dimethylformamide (DMF) in any ratio required for the desired properties. The advantage of using a liquid chain extender (for example, a butanediol residue) is its balance-promoting properties. Liquid extenders can impart desired properties to a 100% solids (essentially solvent-free system), and can further impart a beneficially balanced substantial "pot-hfe", and a An acceptable short hardening time. In this "two-component," reaction system, it is desirable to achieve the longest operating time with the fastest hardening time. A polymerization catalyst, preferably a barrier polymerization catalyst, which has a catalyst function only when the temperature is significantly higher than room temperature (25 ° C, RT), and can be formulated into the polymer to form a composition Within the object, the hardening time is accelerated under the condition of no / 2. _ 物 FORMING COMPOSITION = Contains (provided that the desired species is used as a release agent to assist the release of the film from its casting surface .: The agent also provides anti-sticking properties, and thereby Improve the surface wetness of the support. W The present invention provides a secret polymer film, preferably a polyurethane film for the fabric layer, thereby making a kind of fabric On the urethane film, during the hardening of the film, the fibers of the material are combined with the film during the hardening process. For example: _reaction =: the material can be used with a film or a fabric or while it is still wet. Other thin, 'from being extruded and layered. Assuming that the layer material is water vapor permeable', this is also the case of the most layered layer material on «, then the pre-polymerization: 物 月 b is enough in water Or it is hardened in the presence of water vapor. Furthermore, a specific example of the present invention is a composite layer composed of a hydrophilic polymer film and a different plastic material (for example: microporous poly (tetrafluoroethylene)). This provides A breathable plastic film. The polymer is made into a film that can interact with the constituent fibers The -0H group of one of the vitamins reacts violently. Both the one-component and two-component systems allow a "single step" to make a layered fabric, which is roughly bound by chemical reactions. These A further important property of reaction films is that they do not shrink significantly when hardened because there is no loss of solvent. These reaction films are therefore ideally suited for making a reasonably flat single-step forming layer In the layering process, the film is hardened at the same time. Any layering product that condenses or volatilizes a film on a layerable layer will show severe curling. Therefore, all layers Incorporation is performed in two stages (ie, film manufacturing), followed by separate layering. The inventors have discovered that the hydrophilic polymer 5 film made by the method of the present invention can be very effectively borrowed The surrounding surface cellulose is combined with PTFE to make a flat PTFE layer. These layers are considered difficult to achieve, but the one-component and two-component systems are suitable. Manufactured using this seed layer material.

I: Embodiment I The present invention will now illustrate at least three specific examples of useful polymer-forming compositions of the present invention by using them as non-limiting examples only. A low molecular weight prepolymer is first produced. The prepolymer is then mixed with a chain extender in a static mixer, and the polymer-forming composition is passed through a slot mold as a film-forming liquid, which is applied to a moving support after 15 (Eg: a release paper web). The thin film thus formed is thereafter hardened, and then the support can be removed. The prepolymer is preferably composed of 1-5 repeating units, and is typically a soft (or liquid) material having a low molecular weight. The prepolymer typically contains a series of selectable polyfunctional alcohols (polyols) and polyfunctional 20 isocyanates, which are connected by a urethane bridge. Due to the aromatic nature of the isocyanate and the formation of crystalline regions within the material (commonly referred to as hard blocks, which are hard local agglomerations that reside in the soft polyol), the urethane bridge is very strong. This makes the polymer tough and imparts toughness. 12 The prepolymer can (if required) contain only 1-2 polyol molecules. At this length, the prepolymer will have a low melting point and easily enter into a liquid form. For example, during polyurethane formation, an excess of isocyanate 5 is typically used to ensure that the end residues of the prepolymer are isocyanate residues. The length of the prepolymer molecule can be controlled by adjusting the molar reaction ratio of the polyol to the isocyanate S. To allow the film hardness to be changed, additional low molecular weight glycols can be added to the polyol. The resulting diol / isocyanate linkage results in short-chain hard 10 blocks. Typically, the polyalcohol may comprise a polyester or a polyether. It is assumed that when used as a polyester, the composition of the polyester can be changed to change the hardness of the film. Several different polyethers are suitable for use as the preferred polyol. For example, propylene glycol (PPG), ethylene glycol (PEG), propylene glycol (PPG), and tetramethylene glycol (PTMEG) 15 can be used as the main polyether, and the finished product can be endowed with different properties. For example: PPG provides an economical flexible film, PEG produces the most hydrophilic film, and PTMEG produces the toughest polymer film. In general, the properties of the film in the form of a polyol include elasticity, abrasion resistance, elongation coefficient, air permeability, and solvent resistance. PEG or PPG / PEG complexes are the best polyfunctional alcohols for making thin films of wet vapor permeable polymers. The melting point of the prepolymer is typically dependent on the polyol used and its molecular weight: PPG produces a dense liquid, polyester produces a denser liquid, and PTMEG and PEG produce a solid that can be melted at about 50 ° C. The viscosity of the prepolymer will decrease rapidly under heating and solvent. Optionally, 13 additional isocyanates can be added to reduce the viscosity (various prepolymers). The low melting point of the prepolymer means that the polymer can be prepared, worked and mixed without using temperatures exceeding 100 ° C. This reduces, for example, the risk of cleavage of ether bridges in PEG-based polyols due to instability. 5 The terminal isocyanate group of the prepolymer can be further reacted with a chain extender. The chain extender is a type containing 2 or more groups that can react with isocyanates, such as hydroxyl groups and / or Imine group. The chain extender may include an amine. Suitable commercially available amine chain extenders include, for example: Ethacure 100, Ethacure 300, and Unilink 4200. 10 Alternatively, 'water can be used as a chain extender for a prepolymer containing methyl diisocyanate (MDI). Water reacts with the MDI group to produce the corresponding amine, whereby the amine reacts with more MDI to form a urea group. The urea group produces an unexpectedly tough block that will increase the final polymer. Film tearing strength, elasticity and Young's module. Suppose that if such a polyurethane polymer is extruded into water or a vapor air, the polymer will react to form an elastic, hydrophilic polymer having commercially desirable properties. The resulting polymer fin is a poly-urea-urethane which is highly breathable and suitable for use as a functional clothing film. The pre-κ complex is typically in liquid form, allowing easier handling of reactants. Because it must have an equal number of isocyanates and reactive groups, the two-component system (prepolymer and chain extender) must be thoroughly mixed without trapping air before extrusion through a slot mold. The chain extension reaction is complete. Optionally, the mixing of the prepolymer and the chain extender can be performed with metering pumps to ensure the selected reaction ratio. 14 Typically, the mixing of these two components will initiate a reaction, thereby producing the final polymer. Immediately mixing the reactants in the selected polymer-forming composition on the production line immediately before passing through the slot mold can allow rapid hardening and therefore accelerate the production line speed, thereby leading to lower manufacturing costs. The 5 $ compound structure can be changed in other ways. For example, the overall structure, chain length, and physicochemical properties of the polymer material produced can be further changed by changing the selected prepolymer or chain extender, or by using a mixture composed of the reactants. In particular, it is possible to use a material having more than 2 functional groups or an isocyanate (for example, a -0H polyol having 3 to 10 functional groups) to make a crosslinked material. Such crosslinked polymers may not be as soft or physically releasable as non-crosslinked polymers, but the crosslinked polymers are generally more chemically resistant, a property desired for use in certain applications of the invention. In particular, this cross-linked film is resistant to visceral N, N_diethyl_3_fluorenylbenzidine or 15 difluorenylbenzamine) And other organic solvents. The final polyurethane rigid film can include 50-500 repeating units depending on the size of the polyol and the content of the hard block. The reaction rate of the prepolymer with the bond elongating agent depends on the form of the isocyanate and the chemical properties of the OH or the Corps. The reaction of the 'aliphatic acid 20 ester' is slower than that of various aromatic isoacid acids. Therefore, the reaction rate of the 'bond extension' can be changed from an instantaneous reaction to a slow reaction at the ambient temperature, even at the temperature of Ascending sound ~ A Kaikai. It is also possible to combine a chain extender to produce one step hardening. In the case where the two-component reactive polymer forms a composition, a kind of extender can be used to quickly react to it's increasing melt strength, and then a second slower extender can allow the liquid to have The time it was applied to the release surface. The reaction between this prepolymer and the chain extender is a highly exothermic reaction. Excessive heat generation will cause side reactions. This side reaction will cause unwanted cross-linking or gelation. 5 Therefore, it is ideal to be able to fully mix and dissipate heat during the application of the prepolymer and after being mixed with the bond extender. This sufficient mixing and heat dissipation can also facilitate a slow reaction rate, thereby enabling the heat generation to be more easily controlled and the temperature of the reactants to be better controlled. Typically, in order to make a hydrophilic film by two-component extrusion, the 10 polymer-forming composition will be passed through a slit mold and then discharged to a moving support (for example, a release paper roll). Or other suitable low energy to grab the surface. In order for the final film to have some resistance, thereby masking the final thin surface, the surface of the casting substrate must have a fine but rough cross section. The polymer-forming composition is formed by slit die-casting and molding. The slit 15 die-casting and extruding device is constructed and designed to allow a single film coating to be applied to a moving support and has a controllable thickness. To apply. The slit die-casting and extruding device preferably includes a die-casting block having an internal phase groove located in the hair. The internal groove is narrowed by a width and gradually narrows into two or two slits. The polymer is extruded to form a composition; the difference between ㈣20 and a die-casting extrusion device is that the device further includes two dry die lips that can be placed in contact with the substrate and a The polymer forms a moisturizing lip for the composition. The closed-loop control of the die casting thickness can optionally be assisted by an automatically expanding gap, or it can be incorporated into the slot die. And 鏠 16 is best that the reaction rate and temperature are carefully controlled. The rate should be slow enough to allow complete mixing and applied to the support before the gel, but still fast enough to allow the reaction to complete in a continuous process. The reaction rate can be changed by changing the form of the polyol, isocyanate and chain extender used, and it can be changed by the form and level of the catalyst. The film made by reacting a prepolymer with a chain extender is hardened after being applied to the surface of a support. A commercially available aromatic amine chain extender, for example: Ethacure 100 has a gel time of 2-5 minutes at ambient temperature, or 5-20 seconds at 50-60 ° C. For alcohol extrusion 10, the hardening time of Ethacure 100 is a relatively short. By using optional materials (such as Ethacure 300 and Unilink 4200), the hardening time can be slowed down to a difference of between 3 and 10 times. Since it is an optional amine chain extender, a diol can be used as a catalyst. This results in a better operating time without affecting the desired hardening time of about 15 minutes. The method of the present invention allows a hydrophilic film to be molded at a high speed, for example, at a molding speed of more than 10 meters per minute. In a conventional solvent casting method, the rate limiting step is to remove the solvent. In the specific examples of the present invention, substantially or completely free of solvents can help increase the speed of the production line. 2〇 Example 1-Basic linear prepolymer resin capable of continuous chain extension One example of such a product is:-a kind of (4,4, _ fluorenylene diphenyl isocyanate S | ) Prepolymer made by reacting with polyethylene glycol with a molecular weight of 2_, and 4-butanediol as a chain extender. 17 grams Molar Polyol PEG 976.4 0.4882 PEG 2000 Pugrade Chain extender BD 16.86 0.1873 1, Phenylene glycol such as: BASF Isocyanate ----------- MDI 506.8 2.072 For example: Desmodur44 of Bayer These materials are dried The reaction is performed at 45-70 ° C under nitrogen until all the hydroxy-functional groups have reacted with the isocyanate. Formulating this formula in a slight increment of DMF (79 grams) will ensure that this 5 formula is liquid at 25 ° C, thereby allowing (if desired) easier handling.俟 After the reaction is completed, the isocyanate content is measured immediately, usually by DNB (di-η-butylamine). The material is then rapidly mixed with the required amount of chain extender and then molded into a release paper 10 as a film. In the case of using Ethacure 100 as a chain extender, the mixture has a gel time at ambient temperature of about 20 seconds. To complete the reaction, the film / support is heated before the film is removed. Example 2-Extruded Prepolymer Material with High Solid Reactivity 15 1. Polyethylene glycol (PU grade 'e.g. Uniqenii) with a molecular weight of 2000, this South Molecular Weight Polyol can increase air permeability. 2. HQEE [di- (di- light ethyl & |)] per base (for example, can be bet from Arch Chemical), this kind of aromatic diol can form hard agglomeration in the film, to improve anti-mutual adhesion ( blocking). 20 3. Isocyanate is intended to be Desmodur 44M chips (stored in a sealed metal container at 15 to 20QC) available from Bayer. 18 4. The solvent is dimethylamidamine (for example, commercially available from Whyte Chemical). 5. P-toluenesulfonic acid (pTSA) (e.g., commercially available from BDH) is a neutralizing reagent for neutralizing amines formulated with DMF. 6. Additive: Trganox 245 (for example, commercially available from Ciba), a heat stabilizer for anti-oxidation. 7. Additive: Tinuvin 326 (for example, commercially available from Ciba) is a UV absorber. 8-phosphonium chloride (e.g., commercially available from Albion Chemicals (formerely

Hays)) is the solvent for materials (6) and (7). 9. Vinyzene (available, for example, from Rohm Haas), is a sterilant. 10. Polycat SA1 / 10 (available, for example, from Air Products), is a cohesive catalyst that provides extended operating time but reduced hardening time. 11. · 0.1N Hydrogen acid (commercially available from BDH) (for determination of isocyanate concentration). 12. Tetrafluoroethylene (for example, commercially available from BDH) (for determination of isocyanate concentration). 13. 0.1N dibutylamine solution in tetrafluoroethylene (for measuring isocyanate concentration). 14. Supply dry nitrogen (for dehumidification). 15. Felix Scholler 051 Die Casting Paper. 16 · Industrial spirits (solvent for indicator) 17. Distilled water (solvent for indicator) 18 · Bromophenol blue indicator solution 0.2 / 50/50 IMS / distilled water (for indicator) Solvent) Apparatus 1. Colette model MP20's flat stirring cry 2. 25 ml burette 3. 10 ml straw 4. 2L stainless steel pot with lid 5. Oven for experiment, ambient temperature to 200 ° C. 6. Pressure control valve for nitrogen supply 5 7. Temperature control circulator for experiment (Tachne C-85A) 8. Experimental balance, 200 g X 0.0001 g, and 16 〇g X 0 · 1 g 9. Werner- Mathis Squeegee Coating Apparatus, or a suitable manual squeegee (for example, available from: Sheen Instrumnets) 10 10. 2L reaction tank, equipped with a powered stirring paddle and nitrogen purge 11. 1 liter measuring cup 12. 50ml Quickfit conical flask And stopper 13. Water bath with flow device and adjustable to 0. rc 14. Brookfield LVT viscometer with 4 gauge needle and squeeze device 15 Method to determine the concentration of free isohelium ester 1. Accurate weighing Erlenmeyer flasks and stoppers 2. Add 1 gram of prepolymer to the Erlenmeyer flask, then weigh again 3. Use a pipette to add 10 ml of tetrafluoroethylene (THF) & 10 ml of 20 0.1NDNB solution 4. Cap the Erlenmeyer flask and shake to dissolve it. 5. Add a few drops of bromophenol blue solution. 6. Titrate to a green / yellow end point with 0.1N hydrochloric acid. Pay attention to the volume of HC1 solution used. Contain prepolymer as a control test, repeat the above step 8. Calculate the difference Ester content Isocyanate concentration (mL / g) = Sample reset Preparation of prepolymer 5 3.0% nitrogen 100% solids Prepolymer formulation: Formulation: Polyethylene glycol 2000PU 1344 g HQEE 32 g MDI 624 g 1. On In a covered stainless steel pot, dissolve HQEE in polyethylene glycol at 130 ° C for 45 minutes. Shake the container from time to time to dissolve it. 2. Once completely dissolved, allow mixing to cool to 60 ° C.

3. Set the Collete water bath temperature to 50 ° C 10 4. Transfer the PEG / HQEE to the mixing bowl of the Collete mixer, and then clean the container with nitrogen. 5. When the temperature is stable at 50 ° C, add MDI chips. Mix at high speed for 10 minutes until all MDI is dissolved. 6. Reduce the stirring speed and set the temperature to 60 ° C. Let it react for an additional 3 hours and 15 hours, or until a constant isocyanate concentration is reached. 7. Measure the free isocyanate concentration of the prepolymer. 8. Move the prepolymer into an air-tight container or applicator and mark it with the measured NC0 value. The prepolymer has reactive isocyanate end groups, and must be shielded from air and moisture. 20 Chain extender 1. The required amount of HQEE is calculated as follows: 21 HOEE heavy denier = 0.95 x (NCo concentration expressed in ml equivalent / gram) x batch weight in grams x 99 ^ 1000 2. Let HQEE Dissolve in DMF to prepare a 60% solid solution. 3. Store at 40 ° C to prevent precipitation of HQEE. Stabilizer 5 1. Prepare a stock solution 1 by mixing the following compounds:

Tinuvin 326 8.0 g

Irganox 245 32.0 g methylene chloride 40 g 2. Prepare stock solution 2 by mixing:

Vinyzene 20.0 grams of dimethyl ammonium amine (DMF) 80.0 grams to prepare the coating mixture 1. Weigh 100 grams of 3.0% nitrogen prepolymer 2. For each 100 grams of 3.0% nitrogen prepolymer, add 5.625 grams of stabilizer 10 Solution 1 and 5.0% stabilizer solution 2

3. For each 100 grams of 3.0% nitrogen prepolymer, add the required weight of HQEE / DMF 4. For each 100 grams of 3.0% nitrogen prepolymer, add 0.25 grams of Polycat ^ SA1 / 10 15 5. Mix thoroughly, Then degassing under suction for 2 minutes to make a film 1. Apply a mixed prepolymer of appropriate thickness to the release paper with a doctor blade 2. In a drying oven, harden the film at 150 ° C for 1 minute . 3. Allow to cool and then remove from the paper20 By using individual reactants that can be stabilized without the need for a large amount of solvent, 22 and can significantly reduce or substantially eliminate the use of all the involved secondary processes, thus having environmental and economic benefits And the advantages of implementation. A hydrophilic film made by a solvent-free or substantially solvent-free method (which does not require a melting process) allows a degree of cross-linking that resides in the film 5, thereby making the film solvent resistant (A melting process or a solution-based process does not produce such cross-linking), and a solvent-free method is economically and environmentally beneficial. Example 3-Solution-based highly hydrophilic thin film material 10 Same as Example 2 Apparatus Same as Example 2 Preparation of polymer 3.0% nitrogen polymer 178.56 g 38.58 g 82.9 g 700.03 g 0.045 g

Formula: PEG 2000PU HQEE MDI DMF PTSA 15 1. Load PEG2000, HQEE, and DMF into the reaction vessel 2. Set the water bath temperature to 50 ° C, and then set a slow nitrogen purge 3. Keep it under constant stirring Until the temperature is constant. 4. Add DMF to increase stirring speed 5. 5. DMF dissolves and decrease stirring speed

20 6. Let stand for 15 minutes, then increase the temperature to 6CTC 7. Allow the reaction for 2 hours, and then measure the isocyanate concentration 23 8. Let stand for 15 minutes, and then measure the isocyanate concentration again. 9. If the NOC If the concentration drops, stop for another 15 minutes and measure again. Continue this step until the value stabilizes. Or take the average of the two values] and 2. 5 Calibration stage: 1. Using the measured isocyanate concentration, add the butanediol bond elongation agent calculated by the following formula 2. Glycol will be reduced to ~ ^ 1 ^ 1_ melester concentration) > < Check ^ Gram weight 45 1000 ^^ 3. Dilute the diol with the same amount of DMF, add to the reaction, and then stir at 6010 ° C 4. Measure the viscosity every 30 minutes 5. When the viscosity reaches 300P oisc The reaction was covered by adding an equal amount of succinyl alcohol. _ Ride to disperse the triol and dump it into a sealed metal can. 15 Brief description of the drawings Now referring to the attached drawings, among them: Figure VII is a cross-section view of a narrow die that fits the form. Figure 2 is a diagram of a form suitable for being attached to a slot mold to a 20-piece reactive coupling system. Figure 3a shows a suitable single-component film mold scale unit. Fig. 3b shows the rest of the device of Fig. 3a; and Fig. 4 shows a condensed character film manufacturing device suitable for Putianyu for the above two-component system. Mouthpiece 24 _ Baixian tea according to the first picture, _ scheme _ shown-a form suitable for each of the 4 branches 4 cast pull body 丨 has a silk asset that can be connected to and removed from the mobile carrier net 6 2, and-the moist lip 4 of "Jian_Si_" The moist lip 4 can help to disperse the applied composition, which forms a polymer film 9 of the coating on the material. The path of the net will be affected by ice and miscellaneous rights. The support net is shown in a form supported by a pair of moving rollers 7, 8 which are part of a manufacturing tool described below.

The predetermined polymer-forming composition is fed into a slotted mold into the feed inlet 3. This is particularly suitable for " single component " systems, where the polymer composition (for example) mainly contains a polyurethane polymer (with a long or unlimited operating time), which can It is fed to the entrance of the slit mold without using a related hybrid or mash. H The composition is pressed before passing through a slit defined as a narrow channel, 15 advanced, a mold groove 10, after which the composition is applied to the carrier

厚度 The thickness of the applied coating is adjusted by the bolt 5 member connected to the wet mold lip *. Seen from Figure 2, it shows a static mixer H in which the two-component system consisting of a metering prepolymer 12 and a metering key extender 13 is fed (compared to It is better to measure accurately), then immediately before feeding to the slit mold, it is completely waved and mixed through the feeding line 15. A cleaning device 14 is provided for cleaning the polymer in the event of a process shutdown. The static mixer can be attached to the slit mold, thereby allowing the reactive mixture to be fed into the mold inlet from the feed 25 line 15 without being trapped or full of air. Figure 3a shows a part of a polymer film molding unit that can be used in the "one-component, polymer-forming composition. A support net 16 continuously supports a support substrate (eg, polyester film 5). ) 6 is fed to the support rollers 7, 8 and the slot mold 丨 is located between the support rollers 7, 8 in a way to apply the polymer composition to the support, thereby polymer A film 9 is formed on the support. Optionally, a layerable net 17 is used on the production line to feed the material directly to the film or composition. 10 Via a roller for the son-in-law, the The substrate / film will be transported to a water bath 19 with a immersion drum 20. A section 21 of the molding unit will control the humidity to start the polymer hardening process. It is estimated that the stagnation is in the humidity control section One time is about 2 minutes. Figure 3b shows the rest of the single-component forming unit of Figure 3a. After 15 water bath treatment, the substrate / film is guided to a heating drum with a temperature of about 丨 ⑺ ^; 21, followed by final rollers 22, 23 Membrane / substrate separation. The separation film is stored in the product reel 24, and the carrier substrate is stored in the substrate web reel 25. It is estimated that a dead time from the slit mold applicator to the heating drum is about 7 20 Finally, FIG. 4 shows a production apparatus suitable for producing a polymer film from a two-component reactive polymer composition. It is suitably the same as those cited in FIGS. 3a and 3b. Reference numerals are used to indicate parts. Therefore, a substrate web 16 continuously feeds a carrier substrate 6 to the support rollers 7 and 8, and the slot mold is in the same manner as described in FIG. The installation is located between the support rollers 7 and 8. If necessary, a net 17 composed of a layerable material 18 is used on the production line, and is used for layering the film into a clip type. Between the rollers. The film / substrate is conveyed to an oven 26 having a primary heating zone 27 of about 100 ° C and a secondary heating zone 5 28 of about 150 ° C. The stagnation is estimated to be within One time is about 1 minute. It is used similarly to Figure 3b By means of the object reel 24 and the substrate mesh reel 25, the film is separated from the substrate at the rollers 22 and 23. The installation can provide a fast production line speed and avoid the preparation of a significant amount of solvent in the polymer forming composition Requirements, and a disadvantage of hardening in 10 layers of water. It can be understood that because these polymer systems can be heated by RF energy, other installations (such as a microwave oven) can be used, so it should be displayed The installation in Figure 丨 -4 is only used to explain the non-limiting embodiment. [Simplified description of the drawing] 15 Figure is a cross-section view of a slit-mold of a pass-fit form. Figure 20a of a static mixer for a reactive two-component system that can be attached to a slot mold for supply And FIG. 4 shows that one is suitable for use in the above-mentioned two-component film manufacturing apparatus. ^ Traditional polymers

27 [Representative symbols for the main components of the figure] 1 ... Prayer mold body 15 ... Feeding line 2 ... Drying mold lip 16 ... Support net 3 ... Slot mold feed inlet 17 ... Can be laminated Mesh 4 ··· Wet mold lip 18 ... Laminateable material 5 ... Bolt 19 ... Water bath 6 ... Moving the support net 20 ... Immersion drum 7, 8 ... Roller 21 ... Heating drum 9 ... Films 22, 23 ... Final roller 10 ... Mould groove 24 ... Product roll 11 ... Static mixer 25 ... Substrate web roll 12 ... Prepolymer 26 ... Oven 13 ... Key elongator 27 ... Zone 14 ... sweeping device 28 ... secondary heating zone 28

Claims (1)

Scope of patent application: 1. A method for the continuous production of polymer films, in which a liquid polymer forming composition that resides or falls within the range of room temperature is applied to a slot mold and extruded. The population is then unloaded from a port on a mobile support after passing through the slit scale extrusion device. The polymer film is formed on the support and is hardened or allowed to harden. 2. As the oldest method in the scope of patent application, wherein the polymer-forming composition is solvent-free, substantially solvent-free, or mainly solvent-free. 3. The method according to item 2 of the patent application range, wherein the polymer-forming composition = capacitor content is less than 10 ca. based on the total weight of the composition. 4. The method according to any one of the foregoing patent claims, wherein the formed film is a polymer having a thickness in the range of ㈣_ 之 _ 15 The method of claim 4 in the patent scope, wherein the film is provided with ^ The thickness is in the range of 10-20 μπι. 6. The method according to any one of item (1) of the application, wherein the polymer-forming film can be used to prepare a hydrophilic polymer film. 17. The method according to item 6 of the application for a patent, wherein the polymer film comprises a polyaminotanoate or a polyurea-urethane. 20 8. As for the scope of patent application! The method according to any one of items 7 to 7, wherein the liquid polymer-forming composition comprises a one-component system mainly composed of a prepolymer, for example, a polyaminomethylamine prepolymer. 9. The method according to claim 1, wherein the liquid polymer-forming composition comprises a two-component system having at least two reactive components as the main component. 10. The method of claim 9 in which the reactive component comprises a prepolymer and a bond extender. 11. The method of claim 10, wherein the prepolymer comprises a reactive polyaminophosphonate prepolymer terminated with 5 isocyanate, and the chain extender comprises a reactive hydroxyl, amine or Amino hydrazone. 12. The method according to any one of claims 1 to 11, wherein the entrance of the slot mold device is equipped with a static mixing device which can be used for receiving and mixing by its mixer. When several reactive components are mixed by Lu 10, the liquid polymer-forming composition is produced. 13. The method according to any one of claims 1 to 12, in which an additional material layer is applied to the polymer film, thereby becoming a layer of the film. 14. The method of claim 13 in which the additional layer is fed 15 to the production line to contact the polymer film or film-forming composition. 15. The method of claim 13 or 14, wherein the additional layer comprises a textile material or polytetrafluoroethylene (PTFE). Lu 16. A method that can be used to continuously manufacture a polymer film according to any one of the foregoing patent applications, as actually described, exemplified or explained in this case. 20 17. A method of constructing and installing a device for continuous manufacturing with reference to any one of claims 1 to 16 of the scope of the patent application, the device comprising a device for forming a composition from the liquid polymer Slot cast-grinding and extruding device supplied to the moving support. 18. The device according to item 17 of the scope of patent application, which is a combination of a net made of 30 layers of material, which is arranged to supply the production line material to the polymer film or polymer film.组合 物。 Composition. 19. If the device of claim 17 or 18 is applied for, the device is actually explained in any one of the drawings in this case. 31