US 2789935 A
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April 23, 1957 INVENTORS F0480 DRUMMOND MEL VIN J- H/LER ATTORNEYS F. E. DRUMMOND ET AL METHOD OF PRODUCING PAPER MADE WITH NYLON SCRAP AND APPARATUS Filed 001;. 7, 1954 United States Patent METHOD OF PRODUCING PAPER MADE WITH NYLON SCRAP AND APPARATUS Application October 7, 1954, Serial No. 460,952 Y 9 Claims (Cl. 154-100 This inv'ention relates to decorative material such asv wallpaper and a method of producing the same.
The invention has particular utility in the production of a continuous length sheet of self-supporting film hav-- ing a fibrilated film surface and which may be used directlytas a decorative paper for application to walls and surfaces, orunited with a backing sheet to form a laminated structure.
.It isan object of this invention to provide a decorative paper or the like product for application to articles, walls, or surfaces to be decorated, and which is relativelyinexpensive, durable and readily applied by the use of adhesive or the like in the conventional manner.-
, It is another object of this invention to provide a continuous film or paper-like sheet whichmay be felted to form a fibrous sheet having a film structure.
Another object of the invention is to provide thin flexible sheet which has a characteristic fibrilated, lacey pattern structure, and which film is substantially selfsupporting and capable of being transferred to a storage roll or backing, or to a felt surface to provide a laminated sheet.
. Another object of the invention is to 'providea decorative paper sheet having utility as a wallpaper; i Another object of the invention is to provide a pape having a fibrilated decorative surface, and which is formed in situ during manufacture of the paper by the addition of fibril-forming material to the paper.
and which is relatively tough and durable.
pleasing parchmentized ice , as by spraying or otherwise a thin liquid film of the solution onto a liquid surface such as water, to cause the solvent of the fibril-forming material to be leached out or extracted by leaving a thin skin-like film of the fibril-forming constituent which can be gathered up and drawn off from the liquid as a continuous sheet, or where the solution is applied in situ to a paper stock, is passed to the cushion roll, and from the forming wire and to the calender and press rolls to form a fibrilated paper.
' Referring to the drawing more in detail, Figure 1 .illustrates diagrammatically a suitable apparatus and I method for producing a fibrilated paper-like film. As
I illustrated, a tank 10 is provided which is'filled with liquid such as Water 12, the same being heated by electric heating; coils 14 arranged in the bottom of the tank.
Arranged adjacent one end of the tank 12 is an elongated spray nozZle 15 which is supplied with fibrilforming solution through the conduit 18. The fibrilforming solution is sprayed onto the surface of the liquid 12 through the nozzle openings 20, as illustrated in Figure l, and the film formed'during extraction of the solvent as at 2 1, spreads across the surface of the liquid and.
is gathered up by the roll 22 suitably journalled near the opposite end of the tank 12. The surface of the associated therewith which trims the edges as at 33, on the,
opposite sides of the sheet. The trimmed fibrilated sheet '35 having parchment-like fibrils 36is drawn over the supporting rolls 38 and between the attenuating rolls 40. The rolls 40 may be driven at the same speed or at a speed somewhat faster than the other to place the sheet under tension and stretch it to increase its tensile.
, strength. a
apparent from the following description taken inconjunction with the drawing,.wherein- Figure 1 illustrates diagrammatically a suitable apparatus and method of producing a self-supporting fibrilated film or sheet in accordance with this invention:
Figure 2 illustrates a modification thereof wherein a fibril-forming material is introduced into paper stock as the same is flowed onto the forming wire or screen in the production of the paper. V
Figure 3 illustrates diagrammatically an arrangement for making a laminated sheet structure utilizing the fibrilated film made in accordance with this invention.
' In the production of fibrilated films which are selfsupporting, in accordance with this invention, the same are produced as a thin film by providing a solution containing a film-forming constituent and thereafter removing the solvent or carrier forthe film-forming constituent with the resultant formation of a skin-like continuous film wherein the film-forming constituent is precipitated in the form of fibrils of various sizes and color, providing a'film having a pleasing decorative finish.
In accordance with the preferred method of making the decorative film, the same comprises providing a solution of a fibril-forming material and thereafter applying- After passing the fibrilated sheet 35 through attenuating rolls 40, it is drawn past the drier 42 which is arranged to deliver heated air through the elongated nozzle 44, the heated air being delivered across the drawn sheet, as illustrated by the arrows. Where desired, a similar blower may be arranged at the opposite side of the sheet to heat the sheet uniformly from both sides as the same is drawn along beneath the roll 45 and is then rolled up on the storage roll 46.
In the modification shown in Figure 2, a paper stock is modified by the addition of fibril-forming solution. As illustrated diagrammatically, paper stock passing from the header 49 onto the forming Wire 50 and to the cushof fibril-forming solution through the spray nozzle 55.
Fibril-forming solution is conducted to the nozzle 55 through the conduit 57, the spray nozzle being arranged immediately-adjacent the roll 58 so as to introduce the fi'bril-formingmaterial onto the surface of the aqueous pulp as delivered from the header 49 onto the forming wire 50. The spray 650 of the fibril-forming solution is adjusted and controlled to deliver a uniform amount of material onto the paper stock layer 62 as the same is passed along over the supporting rolls 64 and to the cushion roll 51. In this manner a paper having a parchmentized fibrilated structure is produced. The same may be calendered and processed similarly as paper sheet so I as to produce a finished fibrilated paper. 1
In Figure 3. a laminated structureis provided by passing a fibrilated film or web 79, produced for exampleas shown in Figure 1, over the roll 72 and between the rolls 75 where the same is'united to a backing of paper or felt 77. The finished laminated sheet 78 is then' rolled Patented Apr. 23, 1951 up on the storage roll 85). The fibrilated sheet or webbing 70 may be united with the backing sheet or felt 77 without the necessity of using adhesive or the like material, but when the fibrilated sheet does not properly adhere the use of adhesive or glue material applied to one side of the fibrilated sheet may 'be utilized to cause the same to firmly adhere to the backing of felting. Further, when making a laminated structure the fibrilated 'sheet may be passed directly from the attenuating rolls 40, for example to a laminating section as illustrated in Figure 3, and the drier or drying treatment conducted after forming the laminated sheet, such as shown at 78, the dried laminated sheet then being passed to the storage roll 80, as illustrated in Figure 3.
In forming the fibrilated paper web or sheet'70 having the parchment-like structure various fibril-forming solutions may he used.
A solution which may be used for this purpose consists of nylon scrap dissolved in a solvent which, for example, may be extracted readily by water, and particularly hot Water. Other solvents may be used but in each case the bath or surface on which the fibril-forming solution is delivered must necessarily contain a solvent which has a greater afiinity for the solvent in which the fibril-forming material is dissolved than the fibril-forming constituent itself. In this manner the solvent is readily extracted leaving the film-forming constituent for production of the skin-like film having the fibrilated structure desired.
Examples of appropriate solutions for use in carrying out the invention and the making of the fibrilated paper are given, the same being merely illustrative and not limitative of the invention.
Example I A solution consisting of nylon scrap dissolved in cresol (30-60 gms. nylon in 100 gms. of ortho-cresol or methyl or ethyl acetone). This solution can then be sprayed or-flowed onto the surface of the hot water bath and the fibrilated film formed drawn away from the surface of the Water and treated, for example as illustrated in the drawing.
The resultant fibrilated film is subjected to force air drying at temperatures of about 250375 F. for approximately one hour to drive oif the water and form a dry plastic film or webbing.
Example II .In this instance a solution of nylon dissolved in formic acid and ethyl acetone (1:1 by volume) in which approximately 10% by weight of the nylon is replaced by nitrocellulose (ll-12% nitrogen) as the fibril-forming constituent.
The fibril-forming solution may be utilized similarly as set forth in Example I to produce a fibrilated paper or the like webbing.
I Example III In this instance the fibril-forming solution comprises nylon solution similarly as in Example I, which is modi-' fied by the addition of -15% by weight of phenolformaldehyde resin.
The composition for forming the fibrilated film is utilized similarly as described above to produce a decorative paper or webbing as heretofore described.
Example IV in this instance a fibril-forming solution consisting of a 30% aqueous dispersion of superpolyamide '(e. g. made by polymerizing 60 parts by weight of hexamethyldiammonium adipate with 40 parts of capro'lactain) is sprayed onto the hot water bath surface, or applied to the aqueous paper stock, as illustrated in Figure 2, so as to produce a fibrilated film, the water and aqueous paper stock layer causing the .poly'amide to precipitate out as fine fibrils during production of the paper or formation of the film. The resultant paper or film may then be heated to drive off the water to produce a tough film.
Example V In this instance a pigmented composition is utilized in order to provide a colored fibril sheet or webbing.
A pigmented base, for example as prepared by milling a mixture by weight of zinc oxide 40-70%, blown castor oil 2 8%, and rosin-modified phenol-formaldehyde resin 10-25 the mixture being suitably milled together by running the same through a 3-roll paint mill.
Ten to fifteen percent of this pigmented mixture is then incorporated in the nylon solution prepared as in Example I, forming a pigmented fibril-forming composition.
This composition is then applied as by spraying or otherwise onto the surface of the water bath or solvent bath so as to form a fibrilated film.
Other pigments or dyes may be used to produce differently colored fibrilated films. For example, iron oxide may be utilized as a pigment for producing red, and chromium oxide for producing orange or yellow, etc., the same being incorporated in the form of a paste as described. Suitable dyes also may be used to produce the desired color or shade. Metallic powders, such as aluminum flakes, bronze powder and the like may be incorpo rated into the fibril-forming'liquid material to produce metalliz'ed films.
Other resins likewise may be employed, e. g., either natural or synthetic, which are compatible may be incorporated in the polyamide solutions. The fibril-form ing compositions containing polyamide also may be varied by the incorporation of suitable plasticizers such as castor oil, cotton seed oil, tricresyl phosphate, or the like to produce films having the desired characteristic physical properties.
Various synthetic polymers, other than nylon, also may be used in practicing the invention, for example fibrilforming constituents useful in producing the novel decorative films of this invention include synthetic linear polymers 'or interpolymers having recurring amide linkages. Linear superpolymers, and modified polyamides such as derived from diamines, diba'sic acids, glycols, and amino acids and hydroxy acids are suitable. Modifying agents which may be incorporated in varying amounts include vinyl polymers such as polyvinyl chloride, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polystyrene, and vinyl interpolymers such as are obtained by interpoly' merizing two or more of such synthetics as vinyl chloride, vinyl acetate, methyl methacrylate, methyl acrylate, acryloni-trile and styrene. Cellulose esters and ethers, e. g., cellulose acetate, cellulose acetate butyrate and ethyl cellulose also may be employed.
As solvents or liquid media which may be used as the extracting solvent 'or media for causing the film-forming solution to form fibrils, Water is preferably used for economical reason-s. Cold water, or such as commonly known as tap water is effective. However, the production of the decorative film is speeded up and in most instances the fibril pattern made more uniform when hot water is used, e, g., water heated to about to 210 .F. under normal atmospheric pressure conditions. In place or water, however, other liquids-or media may be used and which are volatile at the baking temperatures and do not readily dissolve the polymers or fibril-forming con-- cule. Polyesters formed by inter-molecular esterificati-on of hydroxy acids, dibasic acids, amino acids, and polyethers formed by inter-molecular esterification of glycol and polyanhy-dn'des derived from dibasic acid are also suitable for producing strong, tough and flexible films. For economic reasons, however, scrap nylon is used because it is more plentiful and less costly. Such materials may consist of discarded parachutes, shirts, stockings, etc. Other sources of Waste Nylon or polyamide type synthetics, of course,'may be utilized, the same being dissolved in an organic solvent, the solvent being readily soluble in Water, whereas film-forming nylon constituent is not.
A decorative paper suitable for use in decorating walls, andfor making wrapping paper, drapes, etc., may be made by forming :a self-supporting sheet or as modified with cellulose fiber, as in situ with paper stock, and for example as illustrated in Figure 1 or 2. The composition used in each instance comprises a solution or dispersion containing as a principal constituent a film-forming substance which is of fibrous character, the same being dissolved in a solvent. Such'a solution is then applied to the surface of a water bath or solvent-extraction liquid in the form of a thin film. Inasmuch as the film-forming constituent is regenerative upon extraction of the solvent therefrom as described, fibrils of the film-forming constituent are produced.
The solvent employed in the solutions described in the examples is readily miscible with water while the film-forming constituent which produces the fibrils is not. In this way the film-forming constituent is thrown outor precipitated in the form of fibrils when the solution is spread on the surface of the hot water bath,
Instead of spray application of the solution to the solvent-extracting media the same may be flowed, brushed. or otherwise applied onto the surface of the water bath.
It will be readily apparent that many different embodiments of this invention may be made without departing from the spirit and scope thereof, and such modifications, substitutions and variations of the proportionate amounts of constituents which will occur to those skilled in the art is intended to be encompassed in this application, except as indicated in the appended claims.
What is claimed is:
1. A method of producing a decorative paper sheet comprising the steps of applying a solution in the form of a thin sheet containing a fibrillous polyamide dissolved in a solvent onto the top of a liquid surface, said fibrillous polyamide being insoluble in said liquid while said solvent is soluble therein, extracting the solvent by leaching the same therefrom to produce a thin fibrilated self-supporting film, separating said film from the surface of the liquid and transferring said film to a supporting paper sheet, and drying the resultant laminated structure to produce a fibrilated paper sheet.
2. A method of producing a decorative paper sheet comprising the steps of applying a solution containing a fibril-forming constituent dissolved in a water-soluble solvent onto the surface of a water bath which extracts the said solvent therefrom to form a film containing fibrils dispersed throughout the film, separating the resultant.
fibrilated film from the surface of the liquid and transferring said film to a supporting paper sheet, and heating the resultant laminated structure to produce a dry flexible fibrilated paper sheet. 1
3. A method of producing a flexible sheet having a decorative fibrilated surface which comprises applying a solution of a fibrillous polyamide onto the surface of a body of water to cause said polyamide to precipitate as fibrils in a self-supporting film floating on the surface of said body of water, removing said film bodily from the surface of the water, attenuating the film to produce a tough film, transferring said film to a supporting paper sheet, and drying the resultant laminated structure to form a finished paper product having a fibrilated decorative sur' face.
4. A method'of producing a flexible sheet of paper having a decorative fibrilated surface which comprises applying a'solution of a fibrillous polyamide onto the surface of a body of water to cause said polyamide to precipitate, as; fibrils in the? self suppo'rting film floating on the surface of said body of water, removing said film bodily from the surface of the water, transferring said film to a supporting paper sheet, trimming the outer edges of the resultant laminated structure to provide a sheethaving the desired width, and heating the resultant trimmed sheet to form a finished paper sheet having a fibrilated decorative surface.
5. A method of producing a laminated sheet of paper having a fibrilated decorative surface which comprises applying a liquid solution containing a fibril-forming constituent dissolved in a water-soluble solvent onto the surface of a body of water, floating said liquid solution on the surface of the Water to extract said solvent and produces a self-supporting film having fine fibrils dispersed over the film surface, separating the resultant film from the surface of the liquid, and applying a backing paper sheet thereto to form a unitary laminated sheet structure one surface of which comprises a fibrilated decorative finish.
6. A method of producing a laminated sheet of paper having a fibrilated decorative surface which comprises applying a liquid solution containing a fibrillous constituent dissolved in solvent onto the surface of a body of liquid in which said solvent is soluble and said fibrillous constituent is insoluble whereby said solvent is extracted producing a self-supporting film having fine fibrfls dispersed over the film surface, separating the resultant film from the surface of the liquid, and applying a backing paper sheet thereto having an adhesive binder disposed therebetween to form a unitary laminated sheet structure one surface of which comprises a fibrilated decorative finish.
7. A method of making paper which comprises the steps of establishing an aqueous cellulose pulp mass, spreading the same onto a moving wire support, and simultaneously spraying onto the surface of the aqueous cellulose pulp mass a solution comprising a fibril-forming constituent which precipitates out as fibrils, conveying the resultant cellulose fibril-forming mass therealong while removing excess water to form a web of cellulose, passing the resultant cellulose web between press rolls to form a thin paper sheet, and drying the resultant sheet to form a paper having fibrilated decorated surface.
8. An apparatus for forming a decorative paper sheet, said apparatus comprising a tank for holding liquid, means disposed at one end of the tank for introducing a solution containing a fibril-forming constituent in the form of a thin liquid sheet onto the surfaceof said tank of liquid, said means extending laterally-of said tank for delivering the solution containing the fibril-forming constituent into the tank and on the-surface of the liquid therein to form the fibrillous film, and means for trans A ferring said film comprising a rotatable roll arranged in the opposite end of the tank for gathering up the fibrilforming film floating on the surface of the liquid during formation of the decorative paper sheet.
9. An apparatus for forming a decorative paper sheet, said apparatus comprising a tank for holding liquid, means disposed at one end of the tank for introducing a solution containing a fibril-forming constituent in the form of a thin liquid sheet onto the surface of said tank of liquid, said means extending laterally of said tank for delivering the solution containing the fibril-forming constituent into the tank and on the surface of the liquidtherein to form the fibrillous film, means for transferring said film comprising a rota-table roll arranged in the opposite end of the tank for gathering up the fibril-forming film floating on the surface of the liquid during formation of the.
'7 decorative rp'a'p er :tsheet, means ECOIIIIPfiSiHg zrolls for engaging and attenuating said sheet as delivered by said 1 011 arranged in :the i-tar'xk, rmeans for itrimming f'the e'dges of the :sheet, andr -meansifor dtying 'the'tfimmed attenuated sheet -to form afinished fibrilated decorative paper sheet.
References Cited-imthe. file of this patent UNITED STATES PATENTS Schmidt etal. -Mar. 5, 1929 Grofl June 25, 1933 8 tRicliter et-a1. o Tune 5, 1934 Taylor Apr. "30, 1946 -Osborne -Jan. 2 8,'1947 Osborne J'1 j1y"26, 194 9 "Photon Oct. 10, 1950 Arnold July 31, 1951 'Boese "Dec. 9, 1952 Bailey Mar. 17, 1953 Battista Aug. 4, 1953