Method of making a multi-layered article

• US 5,032,461 A
• Filed: 10/12/1990
• Issued: 07/16/1991
• Est. Priority Date: 12/19/1983
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: Spectrum Control Incorporated (API Technologies Corporation)
• Inventors: Strycker, Donald S., Ham, Mooyoung, Yializis, Angelo, Shaw, David G.
• Primary Examiner(s): Morgenstern, Norman
• Assistant Examiner(s): Owens, Terry J.
• Application Number:
  US07/597,112
• Time in Patent Office: 277 Days
• Field of Search: 118/50.1, 118/718, 118/719, 118/720, 118/730, 427/35, 427/36, 427/44, 427/79, 427/80, 427/81, 427/251, 427/299, 427/327, 427/255.6, 264/81, 29/25.42, 361/313, 428/461, 428/462, 428/515, 428/519, 428/521, 428/463
• US Class Current: 428/461
• CPC Class Codes: B05D 1/60 Deposition of organic layers from vapour phase vapour phase deposition in general C23C14/00, C23C16/00
• CPC Class Codes: B05D 3/068 using ionising radiations (gamma, X, electrons)
• CPC Class Codes: B05D 3/148 affecting the surface properties of the coating
• CPC Class Codes: B05D 7/24 for applying particular liquids or other fluent materials
• CPC Class Codes: B05D 7/56 Three layers or more
• CPC Class Codes: H01G 13/00 Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
• CPC Class Codes: H01G 4/145 vapour deposited
• CPC Class Codes: H01G 4/306 made by thin film techniques
• CPC Class Codes: Y10T 428/31692 Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31909 Next to second addition polymer from unsaturated monomers

Abstract

A high speed process for forming a multi layered thin film structure in a vacuum wherein each film is less than about four microns thick and the total layers can reach upwards to 4,000 or more. The polymeric layers are formed of a cross linked component selected from the group consisting of polyfunctional acrylates and mixtures of polyfunctional acrylates and monocrylates with the component having a preferable molecular weight of between 200 and 300 and a vapor pressure preferably in excess of 1×10^-2 Torr. The polymeric layers may be interleaved with metal layers.

Claims

1. A high-speed process for forming a multi layered article having a plurality of substantially delamination free, pin hole free and void free layers, comprising the following steps:

(a) providing a vacuum chamber containing;

i) a movable support, ii) at least one vapor outlet of a dielectric flash vaporizer mounted adjacent to an upstream portion of said support, iii) at least one curing means mounted adjacent to a downstream portion of said support, and, iv) means for maintaining said support at a temperature below that of said vaporizer;

(b) evacuating gas from said chamber until the pressure within said chamber is less than about 1×

10^-4 Torr;

(c) selecting a curable component comprising;

i) polyfunctional acrylates, or ii) mixtures of monoacrylates and polyfunctional acrylates, said mixtures having an average of about two or more olefinic groups per molecule, said curable component having;

i) an average molecular weight between 150 and 1,000, and ii) a vapor pressure in the range of 1×

10^-6 to 1×

10^-1 Torr at standard temperature and pressure;

(d) metering a quantity of said curable component into an inlet portion of said vaporizer;

(e) flash vaporizing said component within said vaporizer;

(f) moving said support relative to said vapor outlet and said curing means at a rate of between about 1 cm/sec and 1,000 cm/sec;

(g) condensing a film of vaporized component dispensed from said vapor outlet onto the surface of said support, said film having a thickness of 4 microns or less;

(h) activating said curing means whereby a substantially cross linked polymer film is formed on said support; and

,

(i) repeating steps (c) through (h) whereby a multi layer article is formed.

5. A process in accordance with claims 1, 2 or 3 and further including the placing of a removable substrate on said movable support prior to said vaporizing and curing whereby a plurality of polymer layers are deposited on said substrate.

6. A process in accordance with claim 5 and including the depositing of a release means on said substrate for releasing said article, said release means being deposited prior to said vaporizing step.

7. A process in accordance with claims 1, 2 or 3 and including the depositing of a release means on said movable support prior to said flash vaporizing step for releasing said multi layered article.

8. A process in accordance with claims 1, 2 or 3 and further including providing a plurality of said vapor outlets in said vacuum chamber;

selecting curable components from the group consisting of polyfunctional acrylates and mixtures of monoacrylates and polyfunctional acrylates, said components having an average molecular weight between 150 and 1,000, and a vapor pressure in the range of 1×

10^-6 to 1×

10^-1 Torr at standard temperature and pressure;

metering a quantity of said curable components into at least two of said vapor outlets;

vaporizing the components;

moving said support relative to said vapor outlets and said curing means at a speed of between about 1 cm/sec. and 1,000 cm/sec.

condensing one or more films of vaporized curable components dispensed from said vapor outlets on to the surface of said support, each film having a thickness of 4 microns or less;

activating said curing means whereby substantially cross linked films are formed on said support.

9. A process in accordance with claim 8 and further including the steps of repeating of said metering, vaporizing, moving said support, condensing and operating said curing means to provide the desired number of films to form said multi layered article.

10. A process in accordance with claim 9 wherein said curable components metered into each of said vapor outlets are the same.

11. A process in accordance with claim 10 wherein said curable components selected from said group are different.

12. A process in accordance with claim 8 and further including the steps of

placing a plurality of said curing means within said chamber, each curing means being located downstream of a vaporizer outlet;

and,

activating at least one curing means following the condensing of a film of vaporized component on said support.

13. A process in accordance with claim 12 including the step of sequentially condensing a film of curable component and activating one of said curing means to cross link said condensed component.

14. A process in accordance with claim 1, 2 or 3 and further including the step of removing gases from said curable component prior to said metering.

15. A process in accordance with claim 1, 2 or 3 wherein said support moves continuously.

16. A process in accordance with claim 1, 2 or 3 wherein said support is indexed.

17. A process in accordance with claim 1, 2 or 3 wherein said curable component is a diacrylate.

18. A process in accordance with claim 5 wherein said substrate is flexible.

19. A process in accordance with claims 1, 2 or 3 in which said movable support comprises a rotatable drum.

20. A process in accordance with claims 1, 2 or 3 in which said movable support comprises a disk.

21. A process in accordance with claims 1, 2 or 3 in which said movable support comprises a continuous belt.

22. A process in accordance with claims 1, 2 or 3 in which said curing is by means of electron beam.

23. A process in accordance with claims 1, 2 or 3 and further including the forming of a continuous multi layered strip on said movable support;

and,

removing said continuous strip from said movable support.

24. A process in accordance with claim 23 in which said movable support is a rotatable drum.

25. A multi layered article made in accordance with the process of claims 1, 2 or 3.

26. A multi layered article made in accordance with the process of claims 1 or 2 wherein said product comprises at least 1,000 layers.

29. A process in accordance with claims 1, 2 or 3 wherein said polyfunctional acrylate has the formula:

##STR6## wherein;

R¹ is an aliphatic, alicyclic or mixed aliphatic-alicyclic radical derived from a compound of the formula R¹ (OH)_m ;

R² is a hydrogen, methyl, ethyl, propyl, butyl or pentyl;

n is from 2 to 4;

m is 2 or more.

30. A process in accordance with claims 1, 2 or 3 in which said monoacrylate has the formula:

##STR7## wherein;

R², r and 2 are defined above;

x¹ is H or;

##STR8## X³ is CN or COOR³ wherein R³ is an alkyl radical containing 1-4 carbon atoms.

31. A process in accordance with claims 1, 2 or 3 wherein said polyfunctional acrylate comprises a diacrylate of the formula:

##STR9## wherein;

r and s are each 7 or 8 and the sum of r and s is 15.

32. A process in accordance with claims 1, 2 or 3 wherein said polyfunctional acrylate is selected from the group consisting of:

(i) 1,6-hexane diol diacrylate;

(ii) alkoxylated cyclohexane dimethanol diacrylates;

wherein the alkoxy group contains 1 to 4 carbon atoms and

(iii) ##STR10##

33. A process in accordance with claims 1, 2 or 3 wherein said movable support is maintained at a temperature in the range of about -7°

C. to about 80°

C.

34. A process in accordance with claims 1, 2 or 3 wherein said movable support comprises a rotating drum and said drum passes said vapor outlet and said curing means at a speed of about 100 cm/sec.

35. A process in accordance with claims 1, 2 or 3 in which said curing means comprises a gas discharge electron beam.

36. A process in accordance with claim 8 in which said vaporizers are flash vaporizers and said components are flash vaporized.

2. A high-speed process for forming a multi layered article having a plurality of substantially delamination free, pin hole free and void free layers, comprising the following steps:

(a) providing a vacuum chamber containing;

i) a movable support, ii) at least one vapor outlet of a flash vaporizer mounted adjacent to an upstream portion of said support, iii) at least one curing means mounted adjacent to a downstream portion of said support, and iv) means for maintaining said support at a temperature below that of said vaporizer;

(b) evacuating gas from said chamber until the pressure within said chamber is less than about 1×

10^-4 Torr;

(c) selecting a curable component comprising;

i) polyfunctional acrylates, or ii) mixtures of monoacrylates and polyfunctional acrylates, said mixtures having an average of about two or more olefinic groups per molecule, said curable component having;

i) an average molecular weight between 150 and 1,000, and ii) a vapor pressure in the range of 1×

10^-6 to 1×

10^-1 Torr at standard temperature and pressure;

(d) metering a quantity of said curable component into an inlet portion of said vaporizer;

(e) flash vaporizing said component within said vaporizer;

(f) moving said support relative to said vapor outlet and said curing means at a rate of between about 1 cm/sec and 1,000 cm/sec;

(g) condensing a film of vaporized component dispensed from said vapor outlet onto the surface of said support, said film having a thickness of 4 microns or less;

(h) repeating steps (c) through (g) whereby a plurality of films of said component are deposited; and

,

(i) activating said curing means whereby said films are cured to form a substantially cross linked polymer film on said support.

3. A high-speed process for forming a multi layered article having a plurality of substantially delamination free, pin hole free and void free layers, comprising the following steps:

(a) providing a vacuum chamber containing;

i) a movable support, ii) at least one vapor outlet of a flash vaporizer mounted adjacent to an upstream portion of said support, iii) at least one curing means mounted adjacent to a downstream portion of said support, iv) means for maintaining said support at a temperature below that of said vaporizer; and

v) means for depositing an inorganic material;

(b) evacuating gas from said chamber until the pressure within said chamber is less than about 1×

10^-4 Torr;

(c) selecting a curable component comprising;

i) polyfunctional acrylates, or ii) mixtures of monoacrylates and polyfunctional acrylates, said mixtures having an average of about two or more olefinic groups per molecule, said curable component having;

i) an average molecular weight between 150 and 1,000, and ii) a vapor pressure in the range of 1×

10^-6 to 1×

10^-1 Torr at standard temperature and pressure;

(d) metering a quantity of said curable component into an inlet portion of said vaporizer;

(e) flash vaporizing said component within said vaporizer;

(f) moving said support relative to said vapor outlet and said curing means at a rate of between about 1 cm/sec and 1,000 cm/sec;

(g) condensing a film of vaporized component dispensed from said vapor outlet onto the surface of said support, said film having a thickness of 4 microns or less;

(h) activating said curing means whereby a substantially cross linked polymer film is formed on said support;

(i) repeating steps (c) through (h) and,

(j) depositing a layer of inorganic material on one or more substantially cured polymer films whereby a multi layered article comprising a plurality of polymer layers and at least one inorganic material layer is formed.

4. A process in accordance with claim 3 wherein a plurality of inorganic material layers are interleaved between said polymer layers.

27. A multi layered article made in accordance with the process of claim 3 wherein said product comprises at least 1,000 layers of cured component.

28. A multi layered article made in accordance with the process of claims 3 or 4 wherein said inorganic material is a metal.