JPS61500289A - Protection of sensitive materials - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Protection of sensitive materials The present invention is designed to prevent physical damage and/or contamination and/or undesirable chemical reactions. Concerning the protection of sensitive materials from

Removable coatings, e.g. dissolvable coatings, e.g. , or used to protect sensitive drugs against permeation reactions or contamination. liquid Body-permeable coatings are used, for example, to control the release of drugs in the human body.

The present invention provides an object in which at least a portion of the object is protected by a fluid-permeable protective material. 1. A method of manufacturing an article comprising: (a) at least an object of a sensitive material; an object of sensitive material protected in part by a relatively fluid-permeable protective material and (b) relatively flow the protective material without significantly changing its composition. involves changing the physical structure of the protective material in situ to make it permeable to the body. provide a way to

The protective material must at least perform the desired end-use function of the sensitive material prior to any change in its structure. Preferably, it is sufficiently opaque so as not to significantly impede it.

The protective material is designed to substantially prevent the sensitive material from performing its desired end-use function. sufficiently opaque to allow it to perform its function, and sufficiently transparent to allow it to perform its function. It is further preferred that the structural change is required. However, this structural change can be The material encases the protective material already in place for the sensitive material to perform its end-use function. Contains. Structural changes may improve its function or obtain more useful effects. enable.

The method of the invention has the advantage that the protective material serves two purposes. First, relative In a fluid-impermeable state, the protective material is resistant to physical or chemical damage. Gives you the best protection. Second, after changing to a fluid-permeable state, the protective material A source of physical support of a certain degree1, which provides protection while providing responsiveness for various desirable purposes. allows greater access of the fluid to the material. Therefore, the final use purpose Fairly thick films can be used while still allowing adequate access of fluids.

This retention of a relatively fluid-permeable protective film is unique in that porous physical shields are not. Useful in end-use applications in which a large number of separately supplied materials are used. For example, if a sensitive material In the case of electrodes for air instruments, the protective material can be used as a pre-assembled electrode separator. function and thus eliminates some of the problems of handling electrodes and separators during appliance assembly. Eliminate the problem. Problems with such handling include devices with highly reactive electrode materials (e.g. For example, lithium cells).

Sensitive materials include a wide range of materials that are "sensitive" in many different ways, e.g. Materials subjected to the action of the atmosphere or moisture during storage; premature contact with liquids during use materials that are sensitive to contamination during storage; and materials that are sensitive to physical strength or may be selected from materials that lack integrity and therefore require protection from physical damage. . The present invention allows fluid access to the material during use rather than storage, but reduces physical brittleness. or other physical weaknesses that require intensive physical protection. . Two functions of the transformable protective material of the present invention are very advantageous. After the change The remaining permeable material provides this physical protection. The protective material is By appropriate selection of its components, other secondary functions (e.g. sensitive materials supplying chemical reactants or catalysts in a porous layer on the surface of Can also be done.

A change in the structure of the protective material means that the protective material protects the sensitive material from the door, i.e., the sensitive material It means that changes are made without removing the protective combination with the material. So The fact that its structure changes without changing its composition is called a structural change process. Thus, the possibility of small or localized compositional changes occurring is not excluded. for example , when drilling holes in a protective material with laser light, a certain compositional change will cause all of the individual holes to It may occur near the area.

The sensitive material may be coated with a protective material, providing a non-stick, preferably self-supporting It may be sealed by a layer of protective material.

The protective material is preferably flexible, is selected according to the required properties, and is organic The material is a polymeric material, preferably an organic polymer (e.g. a polymerizable polymer). polymers of compounds having bonds, and condensation polymers of condensable compounds). That's fine.

Useful polymers of compounds having polymerizable double bonds include ethylene oxides having 2 to 12 carbon atoms. Lenically unsaturated hydrocarbons (e.g. ethylene, propylene, n-hexylene, n- Polymer of dodecene (4-t-butylstyrene), and vinyl ether (eg methyl or ethyl vinyl ether). child Preferred among these compounds are polyethylene and polyethylene because of their low cost. It is ripropylene.

Copolymers of the above monomer compounds are also suitable for use in offspring.

Useful condensation polymers include self-condensates of ω-amino fatty acids and their lactams (e.g. For example, condensation polymers of caprolactam and condensation of +1-aminoundecanoic acid polymer).

The condensation polymer is a polymer of diamine having 6 to 9 carbon atoms and dicarboxylic acid having 6 to 10 carbon atoms. It may be lyamide. Typical and useful diamines include hexamethylene diamine amines, nonamethylene diamines and aryl diamines (e.g. m- and p-phthalenes). phenylenediamine). Typical and useful dicarboxylic acids include adipi These include phosphoric acid, superic acid, azelaic acid, terephthalic acid and isophthalic acid. Ru. A preferred polyamide is hexamethylene diamide due to its general availability. It is a condensate of amine and adipic acid.

Condensation polymers can contain aryl dicarboxylic acids (e.g. phthalic acid, terephthalic acid and isophthalic acid) and glycols having 2 to 6 carbon atoms (e.g. ethylene glycol, You can also choose from polyesters of butylene glycol and hexylene glycol. Wear.

The polymer used is Ethylene/chlorotrifluoroethylene copolymer, poly(2-methylpropene) ), polypropylene, poly(4-t-butylstyrene), polystyrene poly(vinyl methyl ether), poly(6-aminocaproic acid), poly(II-aminoundecanoic acid), polyethylene terephthalate), poly(decamethylene sebacamide), poly(heptamethylenepimeramide), poly(octamethylene veramide), poly(nonamethylene azelamide), Poly(hexamethylene adipamide) is included.

The protective material may be damaged by contact with the fluid, or regardless of contact with the fluid, e.g. It is formed so that its structure changes when heated, drilled or stretched. Canada When heat is used, the protective material shrinks due to heating, for example, and the structure, preferably its may include a heat-shrinkable material that alters the apertures within the pores. The formation of pores stretches the protective material. This may be done by diaphragm, but if the material is suitably made permeable, There is no need to specifically form holes due to changes due to stretching. Changes due to drilling are Protective material against penetration by electric fields, particle bombardment or irradiation (preferably laser light) This may be done by exposing the material or by mechanical punching. irradiation, particles Bombardment or other non-permeable methods of effecting structural changes in suitable materials applicable in law. Changes due to fluid contact may cause the protective material to touch includes. This includes, for example, integrating cell electrodes into the cell and applying protective materials to the cell. The cell electrode becomes a protective coating until it comes into contact with the electrolyte element and transforms into an electrode separator. This has the advantage of being protected. The protective composition substantially reacts with the sensitive material. Although it is preferred that there is no reaction, in the present invention there is a useful reaction between the sensitive material and the protective composition. There may be.

Changes from a substantially non-porous state to a porous state occur frequently in practice and are often (e.g., the composition can transform into a liquid swell without becoming porous). and) is preferred over other methods of achieving fluid permeability.

The sensitive material may be modified such that its thickness is reduced or otherwise (e.g. the surface shape shaped by protective materials to suit a specific end use. May be deformed while being protected. This is because sensitive materials are highly reactive and Materials that are of practical value and/or physically fragile and highly reactive Manufacture electrodes for electrical appliances from materials (e.g. alkali metals or alkaline earth metals) It is particularly useful for

Due to such deformation, the sensitive material may cause unacceptable damage to the protective layer. It is advantageous for the metal to be malleable at temperatures and pressures that do not .

Such devices (e.g. lithium cells) have thin strips of reactive metal as electrodes. Lip or sheet can be used. The price and difficulty of working with such metals is , tends to increase rapidly as the thickness decreases. lithium strip thickness In order to reduce the thickness of the machining material, it is necessary to change its form or surface shape in other ways. The rolling of the lithium strip for lithium is carried out by the protective material according to the present invention. Easy to use while protecting. Reinforces protective material or metal and is easily handled While giving processed products. In this way, a thin layer of lithium (for example, a thickness of approx. 0.075 mm) sheets, which would otherwise be difficult and expensive to manufacture and handle. However, it can be manufactured from readily available 0.25 mm strips. Protective material relative The non-permeability reduces the need for dry room handling. However, long-term storage in dry airtight cans Kura is preferable. The most important protective materials (especially those based on organic polymers) are This is because it transmits water vapor over a long period of time.

The protective material is deformed regardless of the deformation of the sensitive material. Often, the structure is altered as described above to become relatively transparent, or its eyes Later structural changes are promoted because of the target.

In addition to the sensitive and protective materials, the articles produced according to the invention contain It may include at least one additional material that can function in the end use. for example, A current collector may be on both sides or one side of the lithium electrode. Protective material is sensitive material Protecting or adhering to sensitive materials is the This does not exclude such a possibility that more materials are involved.

The present invention provides a method by which a protective material is changed to a fluid permeable state in situ in a device. includes. Of particular importance is the use of sensitive materials as anodes or cathodes for electrical appliances. The method is such that the permeable protective material can function as an electrode separator.

The present invention provides: (X) manufacturing an article by the method of the present invention; and (y) electrically disposing the article. A method of manufacturing an electrical appliance is also provided, comprising incorporating it into an appliance.

The changes may be made before or after incorporation of the article into the device using any of the suitable techniques described above. That's fine. The method includes, as described above, such that the surface shape of the sensitive material changes; and/or should not be protected by a protective material so that the thickness of the sensitive material is reduced. The method may include the step of deforming the sensitive material.

The present invention provides that an article is manufactured by the method of the present invention and that a plurality of electrical appliances (or other (particularly when the equipment is used to incorporate a portion of the article into a final product) Automatically feed successive parts of an article into a series of appliances or other products Provides an effective assembly method (when assembling). In this specification, the Manufacturing equipment that can perform this type of automatic method is easily available once the product and other materials are in place. I can figure it out. The device stretches the article such that the protective material is fluid permeable It is advantageous to have means to make the protective material fluid permeable and/or to make the protective material fluid permeable. may have other means of doing so.

When applied to the manufacture of electrical appliances using sensitive materials as electrodes, (preferably automatically and continuously) can cut a part of an article into a series of continuous parts. The electrode articles are used in long continuous (preferably It is another advantage of the invention that it is supplied in strip form (preferably coiled). be. Such an automatic assembly method can be used in the absence of an article manufactured according to the invention. (particularly for alkali metals or or alkaline earth metal electrode materials). In this gist of the invention In this case, the protective material may be in the form of a long, continuous strip of electrode material. For example, a tube surrounding a strip of sensitive material may It may be in the shape of a square. However, adhesive protective materials are preferred.

Such an electrode article produced by the method of the invention comprises a mating electrode material and Can be assembled together with other elements of the appliance. In this case, it is not protected. Electrode materials, especially reactive metals (e.g. alkali metals or alkaline earth metals) Much easier to handle and match. Appropriate electrical equipment (e.g. The anode or cathode, or both, of a gas cell) can be supplied by an article of the invention. . Reactive metal anodes, especially lithium anodes, in electrical cells (especially non-aqueous cells) It has important practical applications. The article consists of a portion of electrode material (e.g. a flat strip). (one major surface of the electrode) with other conventionally known elements (e.g., the current collecting layer described above). You may do so. Such current collecting layers are electrically conductive and typically include protective materials such as those of the present invention. May be under insulating material. However, manufacturing articles for these or other purposes If so, other arrangements may be used to accommodate other additional elements.

The protective material can be formed by any convenient method, e.g. by a suitable organic polymer. materials alone or with other preferred ingredients (e.g. fillers, antioxidants, crosslinkers) or by melt-mixing such components in a suitable solvent. It can be prepared by mixing liquids. Unacceptably detrimental to sensitive materials The application to sensitive materials is carried out by a method that does not involve The protective material itself Preferably no interaction with sensitive materials, but beneficial interactions may occur . Examples of methods for preparing and applying protective materials include compression lamination, solution casting and and preferably extrusion coatings, which are novel and advantageous for cell electrodes. It will be done. The protective material is designed to meet the requirements for void volume, pore size, uniformity, and other requirements for the intended end use. properties (e.g. by choosing appropriate particle sizes and/or Filling and/or machining of the particulate components as described above is necessary in the protective material. by controlling the dispersion). Advantages of the invention include (e.g. known handling and preserving sensitive materials (as known in lithium cell assembly methods) Possible in self-supporting porous films that must have sufficient strength to This means that it can withstand a larger pore volume than the

Crosslinked protective materials (particularly polymers crosslinked by ionizing radiation) are particularly suitable for ANS Cross-linked to a gel content of at least 60% as measured by I/ASTM D2765 68 If so, it has beneficial temperature or solvent resistance or other desirable properties.

An example of the production of a protective material and its properties when applied to lithium illustrates the invention. Explain by doing.

Example 1 Medium density polyethylene (Sclair® 840, commercially available from DuPont) 5) into a 32m barn + n-axis screw extruder (L/D ratio -25/1) Therefore, I made it into a thin film. The film is 0.25mm thick. stomach The film was stretched by 25% at 23°C using a Nstron tensile tester. An initial extension of 150% was carried out at 100°C.

Stretched and unstretched films are laminated onto lithium strips. Lithium bromide setonitrile (0,5 M) Evaluate whether the permeability of the film to the conductive solution changes due to stretching. Ta.

The specific conductivity of the unstretched film in the thickness direction is 3xlO'Ω-cm-'. The value of the stretched film was 3.5 x 10-5 Ω-1 cm-'. Okay As such, the stretched film is significantly more fluid accessible.

Example 2 Sflare 8405 was again used to produce lithium fills. Barn 32mm- Using a screw extruder (L/D ratio -25:I), lithium foil (Foute Mineral Can Panny (commercially available product) is supplied to the cloth through a rad die, and the polymer is stretched into a stretched tube. Enclosed. Lamination involves stretching the composition between nip rolls immediately after extrusion. So it's completed.

The lithium was stretched by a total of about 300% in two steps. Approximately 15% growth is -40 C. and then the remainder of the approximately 300% elongation at 60.degree. The elongation is la constant so that thickness decreases and elongation occurs as the laminate passes through the nip under tension This was done by rolling the laminate between the nib rolls of the nib.

Stretched and unstretched laminates have a melt a of 0.5 within the cell. M's L　CF　s　S　O3's dimethoxyethane/propylene carbonate The conductivity cell of FIG. 1 of the accompanying drawings, which is a 50/50 solution, was used for evaluation.

The specific conductivity through the thickness of the unstretched polyethylene filler is approximately 9XIO-'Ω- 1 cm-' and the value of the expanded polyethylene inclusion is 5X10-6-1 x l　O-'Ω-1, cm-1.

In these Examples, the conductivity test was conducted as follows. Figure 1 of the attached drawings See the conductivity cell outlined in .

The sample of laminate of lithium 2 and polymer 1 connected to nickel mesh piece 3 is The O-ring 4 encapsulates the conductivity cell. Add specific electrolyte and connect electrode 6 The conductivity of the polymer was measured on both sides of the lithium using a conductive bridge 7.8. .

Example 3 FIG. 2 of the accompanying drawings shows an electric cell manufacturing apparatus capable of carrying out the method of manufacturing an electric appliance of the present invention. FIG.

In Figure 2, the invention makes the lithium porous (as well as thinning it). Through the roll 3 it is protected by a protective polymer material which is stretched so that It is supplied to the layup roll 4. In layup roll 4, feed low The strip 5 of cathode material from the cell 6 is closely aligned with the protected anode and the lithium anode A non-porous protective material held at the pole is sandwiched between the anode and the cathode. Then match The anode/cathode assembly includes a spool threading unit 7, further comprising: It passes through the spool winding unit 8. Here, the assembly is a coil The coils are spooled into a shaped electrode assembly.

The coiled assembly is then combined with a suitable electrolyte. It passes through a spool casing unit 9 enclosed in a cell case. like this Suitable practical embodiments of the manufacturing apparatus outlined in can be easily devised.

Stretching or other processing of the protective material that renders it fluid permeable should be done with appropriate equipment. may be included in the location. An example of such a suitable device is shown schematically in FIG. 3 of the accompanying drawings.

A lithium/polymer article 31 advances along feed roll 3o.

However, if desired, it is possible to proceed directly from the extrusion or lamination equipment that forms the article. It's okay. Article 31 passes through feed rolls 32 and reaches cold stretching unit A. Ru. In unit A, the article is cooled by a cooling roll 33 and is cooled by a guide roller. 34 to give an initial "cold" stretch to the protective polymer. It passes through an elongated two-tube roll 35 that is driven rapidly.

The cold-stretched article then passes through a feed roll 36 and is transferred to a high-temperature stretching unit. reach In unit B, the polymer is heated by heating rolls 37 and Stretch nip rolls 39 which give a 7" stretch to the polymer pass through.

It is then stretched to a fluid permeable state suitable for its intended function as an electrode separator. The article with the protected polymer passed through the feed roll 4o to the annealing unit. reaches cut C. In unit C, the temperature control annealing roll 41 The excess stress on article 31 is removed and article 31 is removed from feed roll 42 and take-up roll. 43. If necessary, the automatic cell assembly of the present invention can be carried out without using the take-up roll 43. It may be fed directly to the vertical equipment.

International 1A inspection report -1--^-”””” PCT/GB 84100374-2-r:::;Mini XTot::;Li ni r'MTE2RN;, τ 工C: く入LSE;-RC)iR X2≧0RTOdFR-A-605147hane D=-person-245900916106/76 NoneGB-to-532581 None US-A-1402070Nor, e US-A-1376034None FR-A-1100088None FR-A-7m3877 None FR-ni-1512606:1+cneGE-A-96ε285 None

Claims (1)

[Claims] 1. a sensitive material at least a portion of which is protected by a fluid-permeable protective material 1. A method of manufacturing an article comprising an object of a synthetic material, the method comprising: (a) at least a portion thereof; Minutes supply objects of sensitive material protected by a relatively fluid-permeable protective material and (b) relatively fluid permeable through the protective material without significantly changing its composition. a process that involves changing the physical structure of the protective material in situ so as to make it Law. 2. The protective material diminishes the desired end-use function of the sensitive material prior to any change in its structure. 2. The method of claim 1, wherein the method is sufficiently non-transparent to significantly impede both. 3. The protective material is filled to prevent the sensitive material from performing its desired end-use function. be sufficiently opaque and transparent enough to perform its function. 2. The method according to paragraph 2, which requires a structural change. 4. The protective material is substantially non-porous in a relatively fluid-impermeable state. , whose structure changes to make the protective material porous and therefore relatively fluid permeable 4. The method according to any one of items 1 to 3. 5. The object of sensitive material is at least partially covered with a protective material. The method described in any of the paragraphs. 6. The object of sensitive material is at least partially covered by a non-adhesive self-supporting layer of protective material. 6. A method according to any one of clauses 1 to 5, wherein the method is partially encapsulated. 7. 7. A method according to any of the preceding clauses, wherein the protective material comprises a polymeric material. 8. 8. The method of claim 7, wherein the protective material comprises a crosslinked polymeric material. 9. 9. The method of claim 8, comprising the step of crosslinking the polymeric material. 10. 10. The method according to item 9, wherein the crosslinking is carried out before the structure of the protective material changes. 11. The method according to any one of items 1 to 10, wherein the protective material comprises an organic material. . 12. The protective material structure changes independently of any fluid contact. The method described in any of the following. 13. 13. The method according to any one of items 1 to 12, wherein the structure is changed by heating. 14. Protective materials include heat-shrinkable materials that contract and change structure when heated. The method according to item 13. 15. Any of items 1 to 14, wherein the structure is changed by stretching the protective material. Method described in Crab. 16. The structure is constructed by exposing the protective material to irradiation, particle bombardment or electric fields. 16. The method according to any one of items 1 to 15, wherein the method is changed by: 17. 17. The method according to any one of items 1 to 16, wherein the structure is changed by drilling. 18. Drilling exposes the protective material to penetration by radiation or particle bombardment. The method according to item 17, which is carried out by. 19. 18. The method according to item 17, wherein the hole is made by a mechanical punch. 20. The protective material structure is modified by contacting the protective material with a fluid. The method according to item 12. 21. The protective material comprises a material that contracts and changes structure upon fluid contact. The method according to paragraph 20. 22. The protective material structure prevents the article from coming into contact with fluid elements of the appliance in which it is incorporated. 22. The method according to claim 20 or 21, wherein the method is changed accordingly. 23. The article contains sensitive materials and protective materials as well as functional materials for the desired end use of the article. 23. The person according to any of paragraphs 1 to 22, comprising at least one additional material capable of Law. 24. a step of deforming the object of sensitive material while being protected by a protective material; 24. The method according to any one of items 1 to 23. 25. The object is protected by a protective material while reducing the thickness of the sensitive material. 25. The method according to claim 24, wherein the method is modified to: 26. The object changes the surface shape of the sensitive material while being protected by the protective material. 26. The method according to claim 24 or 25, wherein the method is modified to 27. The protective material is protected against subsequent structural changes to make the protective material relatively fluid permeable. 27. The method according to any one of paragraphs 1 to 26, wherein the method is modified to promote oxidation. 28. The sensitive material is any one of paragraphs 1 to 27 capable of functioning as an element of an electrical appliance. Method described. 29. 28. The method of claim 27, wherein the sensitive material can function as an electrode in an electrical appliance. . 30. The guarantee material can be made relatively fluid permeable to separate the electrodes in the instrument. The method of paragraph 28 or paragraph 29, which is capable of functioning as a controller. 31. The article functions as a sensitive material and a protective material as well as other elements of the electrical appliance Paragraph 28, 29 or 30 containing at least one additional material that can Method described. 32. 32. The method of claim 31, wherein the additional material can function as a current collector. 33. Any of paragraphs 1 to 32, wherein the sensitive material comprises a metal or a metal alloy. Method described. 34. Clause 33: The sensitive material comprises an alkali metal or an alkaline earth metal. Method described. 35. Any of clauses 1 to 32, wherein the sensitive material comprises a conductive polymer composition. The method described in. 36. The sensitive material is in the form of a thin strip or sheet. The method described in any of the following. 37, (x) Manufacture an article by the method described in any of paragraphs 1 to 36, and and (y) assembling the article into an electrical appliance. 38. 38. The method of claim 37, wherein the sensitive material is electrically conductive. 39. 39. The method of claim 38, comprising forming the article into an instrument electrode. 40. Sheet or strip shape to supply coiled electrical cell electrodes 40. The method of claim 39, comprising forming the article into a coil. 41. The structural change of the protective material is carried out in any of paragraphs 37 to 40 before the article is incorporated into the device. The method described in 42. The structural change of the protective material may be carried out in any of paragraphs 37 to 40 after the article is incorporated into the device. The method described in 43. 37th supplying the article to an apparatus for incorporating portions of the article into a plurality of appliances; 41. The method according to any one of items 40 to 40. 44. The apparatus receives a substantially continuous supply of articles and delivers successive portions of the articles in a series. 44. The method of claim 43, wherein the method is automatically integrated into an electrical appliance. 45. Changes that make the protective material relatively fluid-permeable may result in the addition of articles to or within the device. 45. The method according to claim 43 or 44, which is carried out while supplying. 46. 2. A method according to paragraph 1 substantially as described in Example 2 or 3. 47. 38. The method of clause 37 substantially as described in Example 2 or 3. 48. Producing an electric cell by the method described in paragraph 44, paragraph 44 or paragraph 45 Electric cell manufacturing equipment. 49. 48 substantially as hereinafter described with reference to FIGS. 2 and 3 of the accompanying drawings. Apparatus described in section. 50. Article manufactured by the method according to any one of items 1 to 36 and 46 . 51. An electric battery manufactured by the method according to any one of paragraphs 37 to 45 and 47. Qi equipment.