US2760884A - Composition and method for impregnation of sheet materials with synthetic resin latices - Google Patents

Composition and method for impregnation of sheet materials with synthetic resin latices Download PDF

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US2760884A
US2760884A US445183A US44518354A US2760884A US 2760884 A US2760884 A US 2760884A US 445183 A US445183 A US 445183A US 44518354 A US44518354 A US 44518354A US 2760884 A US2760884 A US 2760884A
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latex
weight
sheet material
resin
impregnated
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Jr George Leonard Graf
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Celastic Corp
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Celastic Corp
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Priority to US445184A priority patent/US2805962A/en
Priority to GB8871/55A priority patent/GB766866A/en
Priority to GB8872/55A priority patent/GB785058A/en
Priority to FR1139582D priority patent/FR1139582A/en
Priority to FR1139583D priority patent/FR1139583A/en
Priority to DEC11589A priority patent/DE1024481B/en
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D06M11/71—Salts of phosphoric acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/31—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles

Definitions

  • This invention relates to a method for stiiiening a fibrous sheet material,v and more particularly, it relates to a method of preparing shoe stiffeners by treating a sheet material with a synthetic resin'latex.
  • High quality shoe stiffeners in the past have been made by impregnating a flannel sheet material with finely (livided particles of cellulose nitrate. After product was stored until ready for use, at which time the impregnated flannel was dipped into a solvent for the cellulose nitrate, applied to the appropriate shoe part and allowed to dry to a stifiened condition.
  • sheet materials such as flannel may be impregnated by dipping the flannel into an aqueous dispersion of synthetic resin, such as a synthetic rubber latex.
  • synthetic resin such as a synthetic rubber latex.
  • the porosity of the impregnated material is low and the ability of the material to absorb solvents is poor.
  • the low porosity and poor solvent absorption prevents the achievement of the greatest stifiness for a given composition of impregnated fabric.
  • heavier flannels or'other supporting materials must be impregnated with a greater amount of resin, and such procedures are commercially unattractive.
  • the sheet material utilized in this ingenr tion may be of the lightest grade and yet be impregr nated with a sufiicient amount of resin to bestifiened j a very high degree, because'the present process produces a highly porous impregnated fabric having the ability to e s bl s r Perc nta e o olven tha h e eribs chiev d y t e u of syn t e n la ex imprs aat ea-
  • the attached drawing illustrates,,by means of a self.-
  • the sheet mate After stripping the impregnated sheet material of excess liquid, the sheet mateis heated to a temperature above from about 40 C tofabout 100 C., causing the dispersing agent to insolubilize and allowing the coagulant to cause the resin particles toforrn small agglomerates dispersed through.- .out the sheet material, which as a result of this treatment has a non-tacky, but somewhat moist surface. The renaming moisture is then removed by drying the sheet material by any known means.
  • the dry impregnated sheet material may be treated with a volatile solvent for the resin agglomerates, the sheet may then be formed into the desired shape, and dried by e apora n e s P a or on of he salien the sheet material stifiens.
  • a yolatile solvent for the resin such as methyl ethyl ketone, toluene, mixtures of these materials wi-t-h diluents, 9. th k wn Solvents, ap d o hease hih s 19 be stitfened, and the solvent is allowed to evap0rate, tl 1 us producing. a stifiened sheet material.
  • Example 1 A latex blend was prepared by mixing 3 Parts I a Pol styrene qus uslat x containing 5.0% resin solids and 1 part of aqueous latex of a copolymer of styrene and butadiene in the proportions of /20, this latex contained 45% resin solids. Into 600 grams of this latex blend there were added'the following water at temperatures from about 40 C. to about '65; s
  • This latex mixture was used to impregnate pieces of cotton flannel having a twill weave and a thickness caliper of 0.033 inch to 0.039 inch and a weight per square yard of 0.35 to 0.38 pound.
  • a piece of this flannel measuring 10 x 15 inches was impregnated by dipping the flannel into the above latex mixture followed by stripping the wet material between rolls placed 0.049 inch apart.
  • the impregnated fabric was then placed in a chamber filled with steam at 95 C. to 100 C. in such a manner that both sides of the fabric were exposed to the steam. After the fabric had been in the steam chamber for 1 minute it was removed and placed in a circulating air oven at 110 C. for 1% hours.
  • 72.8% by weight was resin. This figure is called the percent resin loading hereinafter.
  • the value of stifiness by the above ASTM testing method was subject to wide variations which were believed to be due principally to the leather thickness. Accordingly, from the data obtained from the ASTM test there was calculated a value called rigidity which was independent of the leather thickness. This value is the inch-pounds of work required to deflect a one inch wide specimen with a lever arm of two inches through a deflection angle of 30. The total distance through which the free end of the specimen moved was one inch. Thus the value of rigidity is reported in terms of inch-pounds of work per inch of deflection. The rigidity of these specimens is compared with the ASTM stiflness for each specimen in the following table.
  • Laminate A 9. 5 145,000 Specimen 2
  • Laminate A 11.0 165, 000
  • Laminate B 9. 7 173,000 Specimen 2
  • Laminate B 9. 5 137,000
  • Example 2 A latex blend was prepared in all reaspects similar to Example 1 except the calcium carbonate was omitted and replaced with additional water to prepare a 40% resin solids latex. Identical pieces of flannel were impregnated and were subjected to steam treatment and were dried in an air oven in the same manner as described in Example 1 with the single exception that in this case the temperature of the air oven was 120 C. The percent resin loading in the impregnated fabric was 71.8%. Two small pieces A and B were treated with solvent as described in Example 1 and were found to have a percent solvent absorption of 130% and 129% respectively.
  • Laminates were prepared from leather, doubler cloth, stiifener, and liner cloth as described in Example 1 and were found to exhibit good adhesion between all adjacent layers of the laminate and the resin migration was found to be good. From each of the two pieces A and B specimens were cut and subjected to tests to determine the ASTM stiffness and the rigidity as defined in Example 1. The following results were obtained:
  • Specimen 2, Laminate B Example 3.A latex mixture was prepared in the same manner as described in Example 1 with the exception that 1.25% by weight of resin solids of methyl cellulose was added as a thickening agent and various amounts of calcium carbonate were added as a filler to determine the effect upon solvent absorption of the impregnated fabric and thereby the effect upon its rigidity.
  • the addition of methyl cellulose is advantageous in maintaining the large amounts of filler in a dispersed condition. By increasing the filler concentration the amount of resin picked up by the fabric was decreased although the total solids (resin plus filler) remained relatively constant.
  • the following table shows the results obtained from the impregnation of flannel and the preparation and testing of laminates in the same manner as described in Example 1.
  • Example 4 An impregnating mixture was prepared by mixing 600 grams of an aqueous latex, the solid material comprising essentially a copolymer of vinyl chloride and vinylidene chloride (the latex containing approximately 56% resin solids and being sold commercially by the B. F. Goodrich Company under the name Geon 351) with 9.7 grams of dodecylphenyl polyglycol ether, 124.5 grams of a 10% aqueous aluminum sulfate solution, and 73 grams of distilled water. The resulting mixture contained 40% resin solids.
  • the stripped fabric was heated to a temperature of C. to C. by contact with steam for 1 minute, and then dried in an air oven at 100 C.
  • the dried fabric had an average resin loading of 73.9 weight percent.
  • Pieces of the impregnated fabric were then tested for solvent absorption using as a solvent a mixture'of 70% masses methyl ethyl ketone and 30% 'cyclohexahone. "Of ⁇ four pieces tested the average solvent absorptionwas 264% by'we'ight.
  • Example 5 In a manner similar to that described in Example 4, 600 grams of a vinyl chloride/vinylidene chloride latex, containing about 55% solids and sold by B. F. Goodrich Company under the name of (icon 352, was mixed with grams of dodecylphenyl polyglycol ether, 151.3 grams of a 10% aqueous solution of aluminum sulfate, and 69 grams of water. The resulting mixture contained 40% resin solids.
  • a piece of cotton fiannel weighing 0.36 pound per square yard was impregnated by dipping into the above mixture and stripped between rolls spaced .049 inch apart.
  • the stripped fabric was heated to 95 C. to 100 C. by contact with steam for two minutes and then dried in an air oven at 100 C.
  • the dried fabric had an average resin loading of 67.2 weight percent.
  • Pieces of this impregnated fabric were then tested for solvent absorption, made into a simulated shoe toe laminate, and tested for rigidity and stiffness as described in Example 4.
  • the average solvent absorption was 169%
  • the resin migration was very good and the adhesion between adjacent layers of the laminate was good in each case.
  • the average ASTM stiffness was 68,000 p. s. i. and the average rigidity was 3.8 inch-pounds per inch of deflection.
  • Example 6.l.'n a manner similar to that described in Examples 4 and 5, 600 grams of a vinyl chloride/vinylidene chloride latex containing about 53% solids and sold by the B. F. Goodrich Company under the name, Geon 251, was mixed with 9.7 grams of dodecylphenyl polyglycol ether, 124.5 grams of a 10% aqueous solution of aluminum sulfate, and 64 grams of water. The resulting mixture contained 40% resin solids.
  • a piece of cotton flannel weighing 0.36 pound per square yard was dipped in the above mixture and stripped between rolls spaced .049" apart.
  • the stripped fabric was then heated at 95 C. to 100 C. by contact with steam for 2 minutes and then dried in an air oven at 807 C.
  • the dried fabric had an average resin loading of 75.2 weight percent.
  • Pieces of this impregnated fabric were then heated for solvent absorption, made into a simulated shoe toe laminate, and tested for ASTM stiffness and rigidity by the methods described in Example 4.
  • the average solvent absorption was 125%.
  • the resin migration in the shoe toe laminate was good and the adhesion between adjacent layers of the laminate was good in each case.
  • the average ASTM stiffness was 82,000 p. s. i.
  • the average rigidity was 3.9 inch-pounds per inch of deflection.
  • Example 7 For comparative purposes, similar pieces of flannel were impregnated by three different processes. The first two methods are known to the public and the third method is identical with that described in Example I. In each case, the techniques used were intended to produce the highest quality shoe stifl ener possible with theparticular ingredients used.
  • the impregnating medium was a solution of cellulose nitrate.
  • the impregnating medium was a' mixture of 3 parts of aqueous polystyrene latex and 1 part of an aqueous latex of an 80/20 copolymer of styrene/butadiene and 1% by weight of resin solids of an organic phosphate saltsold by Victor Chemical Works under the name of Victor Stabilizer-53. The total resin solids content amounted easilyby the latex.
  • the third-methodathermosensitive 6 latex im'pregn'atiiin identical with that described in example lwas utilized. p
  • the laminate prepared with a stiffener made by 'the'secorfd method above had a Compression Number of 51.
  • the laminate made by the process of this invention, called'the third method above had a Compression Number'of 95.
  • laminates prepared by the third method above utilizing very light flannel, 0.121 pound per square yard, had a Compression Number of 48, illustrating that :a higher degree of stiffness can beachieved bythe process off the present invention even when utilizing 'flannelof one-third the weight required to produce the same stiffness .by the known cellulose nitrate process.
  • any of several kinds of synthetic resins having eleci trostatic properties may be used as the major ingredient in the impregnating latex, although the vinyl resins are preferred, such as polystyrene, polymethyl styrene, polyvinylhalides, polyvinylidene halides, polyacrylates, .poly-' acrylonitrile, and 'polyallcylacrylates. It is desirable in many instances to employ .a plasticized resin, such as a. mixture of polystyrene and a copolymer of high styrene content and low butadiene content, the.
  • plasticizers such as organic esters, and other non-volatile; non-hardening liquids-may be incorporated with the base resin to reduce brittleness in the same manner as the styrene/butadiene copolymer is used above.
  • plasticizers such as organic esters, and other non-volatile; non-hardening liquids-may be incorporated with the base resin to reduce brittleness in the same manner as the styrene/butadiene copolymer is used above.
  • styrene or of vinyl halides are particularly desirable because of their availability and low cost; 7
  • One useful group of resins is a copolymer of styrene/butadiene containing 4% to 20% by weight of butadiene.
  • a preferred formulation is a mixture of 3 parts polystyrene with 1 part of an 20 copolymer of styrene/butadiene; which mixture has a total composition of styrene and 5% butadiene.
  • the proportions of polystyrene and the styrene/butadiene copolymer can be varied within the general: range of 420% by weight of butadiene'zin the total mixture to produce slightly stiffer and harder compositions as the butadiene proportion is reduced and softer more elastic compositions as the butadiene proportion is increased;
  • the same variety of compositions can be obtained by mixing wellrknown plasticizers with polystyrene or other hard plastic materials, particularly the vinyl polymers such as vinyl halide, vinylidene halide; alkyl acrylates, and other resins known to those skilled in'the art.
  • the latexused as a starting material in the prepara tion of the impregnating bath ofthis invention is a colloidal dispersion of one or more of the above resins in an aqueous medium;
  • the dispersion contains from about 40% to about 60% resin solids, while th'e remainder is essentially all water.
  • These dispersions-or, latices are available commercially on the open market in concentrations of 40% to 60% solids, or they maybe prepared by known methods, such asv dispersionpolw meri'zation.
  • the latex of resin andwater constitutes the largest portion of theirnpr'egnating mixture of this in; vention' and the additives described below constitute less; than" abbut .l5%' of the total weight of the impregna mixture, although there are some embodiments of this Polymers invention wherein a large amount of filler is employed.
  • the latex After all additives are incorporated into the latex, it may then be diluted if desired, and in any case will contain about 20% to 60% resin solids in the final form as an impregnating bath.
  • Dispersing agents are required additives to the latex utilized in this invention so as to stabilize the latex against premature coagulation.
  • the dispersing agent is non-ionic and must be one which is soluble in the latex medium at room temperature and increasingly insoluble at higher temperatures.
  • the solubility of these substances should be such that it is soluble in water at some temperature from about room temperature (20 C.) to about 40 C. and that the substance is insoluble in water at some temperature from about 40 C. to about 100 C.
  • solubility of chemical substances normally changes rather slowly with temperature and it is not intended to limit this invention to those dispersing agents which are completely soluble at room temperature and completely insoluble at 40 C., but rather to include those non-ionic dispersing agents which can be dissolved in an aqueous medium at room temperatures or thereabout and which have inverse solubility characteristics and will therefore become insoluble as the temperature is increased up to about 100 C.
  • the solubility requirement of the dispersing agents used in this invention is such that the impregnating latex may be prepared at ordinary temperatures (20 C. to 40 C.) and the dispersing agent will be soluble and thus prevent any gross coagulation or premature agglomeration of the latex but as the temperature is raised to some convenient point (40 C. to 100 C.)
  • the dispersing agent becomes insoluble and allows agglomeration to occur.
  • the preferred compounds which function as non-ionic dispersing agents and have inverse solubility characteristics include the polyglycol ethers such as octylphenyl polyglycol ether, dodecylphenyl polyglycol ether, and ethers formed as the condensation product of ethylene oxide and rosin.
  • the alkylphenyl polyglycol ethers are preferred in this invention.
  • the amount of dispersing agent employed is at least about 0.5 and normally not more than by weight of the resin solids present in the latex. If the liquid latex constitutes about 20% to about 60% resin solids, then the dispersing agent will be present from about 0.1% to about 3.0% by weight of the total latex. Greater amounts than 5% by weight of the resin solids may be used without affecting the process other than increasing the costs involved. Generally, about 3% of dispersing agent is recommended for the preferred embodiments of this invention since this amount effectively inhibits coagulation or agglomeration of the latex at room temperature as well as reducing the surface tension of the latex liquid and thus permit rapid penetration of the latex into the sheet material.
  • Coagulants which may be employed in the process of this invention are the water-soluble polyvalent metal salts which may be chlorides, nitrates, sulfates, acetates, etc. of aluminum, magnesium, calcium, iron, tin, copper, cobalt, chromium, cadmium, strontium, etc.
  • water-soluble polyvalent metal salts which may be chlorides, nitrates, sulfates, acetates, etc. of aluminum, magnesium, calcium, iron, tin, copper, cobalt, chromium, cadmium, strontium, etc.
  • calcium chloride, ferric sulfate, magnesium sulfate, and aluminum sulfate are desirable, although the latter two are preferred because of their lower costs, better solubility characteristics, and the fact that they do not impart undesirable color to the finished product.
  • the alums such as the potassium, sodium, or ammonium aluminum sulfates are as desirable as aluminum sulfate as the
  • the amount of coagulant required will vary slightly with the chemical nature of the coagulant salt, the type and amount of resin employed, and other reaction conditions.
  • aluminum sulfate approximately 0.5% by weight of the resin solids present in the latex is suflicient to accomplish the desired result, although in the preferred embodiment of this invention about 1% is normally employed.
  • the amount employed may be as high as 10% or 15% by weight of the resin solids.
  • the coagulant salts of this invention are capable of causing the colloidal resin particles in the latex to change into a dense curdlike mass if there is no protective effect of a dispersing agent.
  • a change into such a dense curdlike mass is referred to herein as coagulation.
  • the colloidal resin particles of the latex are protected from the action of the coagulant salt by the presence of a dispersing agent which gradually becomes insoluble as the temperature of the latex'is raised.
  • the dispersing agent becomes insoluble the resin particles form small clusters of the original colloidal particles and these clusters deposit in the impregnated material in the form of a porous mass as distinguished from the coagulated, dense curdlike mass referred to above.
  • the formation of the porous clusters is referred to herein as agglomeration.
  • the material which is to be stiffened may, in general, be any fibrous sheet material such as any of the varieties of fabrics, textiles, felted materials, mats, papers, or the like.
  • the sheet material may be made of natural or synthetic fibers or a mixture of the two.
  • the material commonly employed is a cotton flannel, although non-woven sheet material or even paper may be used in some cases.
  • Filler materials may be incorporated into the impregnating medium of this invention to serve several useful purposes.
  • the filler may be used to reduce the cost of the materials used in the impregnating bath.
  • the use of a filler in many instances causes the impregnated material to be more porous and therefore to be able to absorb more solvent and achieve a greater stifiness.
  • the use of a filler enhances the adhesiveness of the impregnated material to an adjacent laminating layer.
  • Some filler materials serve many purposes in addition to their diluent elfect, for example, they may act as a buffering agent as will be explained later, they may improve fire resistance, improve adhesiveness and solvent absorption and other uses apparent to those skilled in the art.
  • filler material permits the shoestifiener to be handled easily when it is wet with solvent and ready to be incorporated into the shoe part and, furthermore, after the shoe part has been assembled there is less likelihood that resin solids will migrate from the shoe stiffener and cause visible spotting on the leather surfaces of the shoes.
  • Filler materials which may be used include water insoluble salts such as calcium carbonate and calcium sulfate, infusorial earths, bentonite clays, and other inert materials known to those skilled in the art.
  • the amount of filler material which may be used may be as much as about by weight of the resin solids present and a range of values of about 20% to 50% is preferable for most embodiments of this invention.
  • Thickeners have utility in this invention when it is desired to impregnate a fabric with greater and greater amounts of resin solids, and when fillers and other ingredients of the latex have a tendency to settle out.
  • Thickeners which have been used successfully include methyl cellulose and methyl carboxy cellulose. Other equally useful thickeners are well known to those skilled in the art.
  • Latices containing a mixture of polystyrene and a copolymer of styrene/butadiene, a dispersing agent, and a coagulant salt as described above have been found to have a pH of 3.5 to 4.5, and, because of such acidity, to damage the flannel impregnated by such latices. It is therefore preferable to add a buffer material to adjust the pH to a value of 6.0 to 7.0.
  • any of a large variety of salts may be added to the latex to perform the buffering function, such as the alkali metal and alkaline earth metal carbonates, bicarbonates and hydroxides.
  • Calcium carbonate has been found to be desirable for this purpose, and approximately 1% by weight of the resin solids is sufi'icient to raise the pH to 6.0 or 7.0.
  • hydroxides such as calcium hydroxide, in very small amounts to adjust the pH to the desired level of 6.0 to 7.0.
  • water may be added to form the desired concentration of resin solids, which for most embodiments of this invention will be from about 20% to about 60% by weight of solids.
  • concentration of resin solids for most embodiments of this invention will be from about 20% to about 60% by weight of solids.
  • a concentration of about 40% solids has been found to be preferable.
  • the impregnating composition be prepared by mixing the ingredients in a specific order; namely, that the resin latex and the dispersing agent be, thoroughly mixed before adding the coagulant. Furthermore, it is helpful to add the coagulant slowly, and in a diluted condition, to the latex while the latex is being agitated. Such precautions as these assist in preventing any localized coagulation of the resin solids in the latex.
  • the excess liquid is removed from the wet impregnated material by a suitable means such as coacting stripping rolls, a wiper knife, or the like.
  • a suitable means such as coacting stripping rolls, a wiper knife, or the like.
  • Such an operation is capable of loading the supporting material to the desired amount of about 50% or more by weight of impregnating solids if the original impregnating latex contains about 40% solids.
  • Some shoe stiffeners are prepared with much less than 50% resin solids and this process is capable of preparing such shoe stilfeners by loading the material with less than 50% solids.
  • the stripped, impregnated material is then heated to cause agglomeration of the resin solids and to evaporate the remaining water from the material. Any method of heating may be utilized although it has been found that the most desirable results are obtained if the material is heated in a humid atmosphere, for example, 95 C.
  • the dried impregnated material by the above treatment, contains small agglomerates of resin particles uniformly dispersed throughout the sheet material.
  • this material may be stored if desired, or it may be used in the production of a stiffened article of manufacture, such as a box toe or counter in a shoe, a laminate with other materials, shaped molds, and other similar objects.
  • the stiffening process is accomplished by treating the dry, impregnated material with a solvent for the resin, forming the solvent-treated material into the desired shape and allowing the solvent to evaporate leaving a stiff, self-supporting, article.
  • the solvent for the poly" styrene resin may be methyl ethyl ketone, toluene, or mixtures of these materials,and the solvent for the polyvinyl chloride resin may be methyl ethyl ketone, cyclohexanone, or mixtures of these materials with each other or with diluents.
  • Other solvents for these and other operable resins are known to those skilled in the art.
  • the process of this invention is particularly useful in the preparation of shoe stiffening materials such asbox toe or shoe counters and it also finds a wide variety of uses in the preparation of impregnated materials which are used to stilfen or otherwise strengthen materials with which it is laminated.
  • the impregnated material of this invention may be used to repair sheet metal articles such as roof gutters, downspouts, fenders and bodies of automobiles. This material also finds use in covering the decks and hulls of small boats, in the preparation of artificial limbs, in the manufacture of mannikins, and various display devices and in any of a variety of laminating applications.
  • a process for preparing sheet materials cap-able of being stiffened consisting essentially of preparing an aqueous latex containing (1) 20% to 60% by weight of a vinyl polymer, (2) 0.5% to 5% by weight of said: vinyl polymer of a non-ionic dispersing agent which is soluble in water at some temperature from about room temperature to about 40 C. and is substantially insoluble in water at some temperature from about 40 C. to about 100 C., and (3) from about 0.5% to about 15% by weight of said vinyl polymer of a water-soluble polyvalent metal salt; impregnating a fibrous sheet material with said aqueous latex, removing excess latex from said sheet material, heating said sheet material at a temperature of 40 C. to 100 C. until the liquid latex particles agglomerate, and thereafter drying the sheet material.
  • a process for preparing sheet materials capable of being stiffened consisting essentially of preparing an aqueous latex containing (1) 20% to 60% by weight of a mixture of a major portion of polystyrene and a minor portion of a copolymer of styrene/butadiene, (2) 0.5% to 5% by weight of said vinyl polymer of a nonionic dispersing agent which is soluble in water at some temperature from about room temperature to about 40 C., and insoluble in water at some temperature from about 40 C.
  • the process for preparing a shoe stiffener consisting essentially of preparing an aqueous latex containing (1) 30% to 50% by weight of resin solids comprising 3 parts by weight of polystyrene and 1 part by weight of an 80/20 copolymer of styrene/butadiene, (2) 0.5% to by weight of said resin solids of an alkyl phenyl polyglycol ether dispersing agent, (3) about 1% of aluminum sulfate, and (4) adding suflicient bufier material to adjust the pH of said latex to a value of about 6.0 to 7.0; impregnating a cotton flannel sheet material with said aqueous latex, removing excess latex from said sheet material until at least 50% of the weight of the impregnated sheet material comprises latex solids, heating said sheet material to a temperature of 95 C.
  • the process for preparing a shoe stiffener consisting essentially of preparing an aqueous latex containing (1) 30% to 50% by weight of resin solids comprising 3 parts by weight of polystyrene and 1 part by Weight of an 80/20 copolymer of styrene/butadiene, (2) 0.5 to 5% by weight of said resin solids of an alkylphenyl polyglycol ether dispersing agent, (3) about 1% of aluminum sulfate, and (4) 20% to by weight of said resin solids of calcium carbonate, impregnating a cotton flannel sheet material with said aqueous latex, removing excess latex from said sheet material unit at least 50% of the weight of the impregnated sheet material comprises latex solids, agglomerating the liquid latex particles in the resulting sheet material by heating said sheet material to a temperature of 95 C.
  • a liquid composition consisting essentially of (1) 20% to by weight of a vinyl polymer, (2) 0.5% to 5.0% by weight of said vinyl polymer of a non-ionic dispersing agent which is soluble in water at some temperature from about room temperature to about 40 C. and is insoluble in Water at some temperature from about 40 C. to about 100 C., (3) 0.5% to 15% by weight of said vinyl polymer of a water-soluble polyvalent metal salt, and (4) suflicient water such that the sum of all components equals 100%.
  • a liquid composition consisting essentially of (1) 20% to 60% by weight of colloidal resinous particles of polymeric styrene and polymeric butadiene in the proportions of 4% to 20% by weight of polymeric butadiene and 96% to by weight of polymeric styrene, (2) 0.5 to 5.0% by weight of said resinous particles of an alkylphenyl polyglycol ether dispersing agent, (3) about 1% by weight of said resinous particles of aluminum sulfate, (4) 20% to 50% by weight of said resinous particles of calcium carbonate, and (5) sufficient water such that the sum of all components equals 100%.

Description

2,760,884 ON OF SHEET Aug. 28. 1956 MATERIALS WITH SYNTHETIC RESIN LATICES Filed July 22, 1954 .5633 5 5:3 2; E 35:25 25m B 35.20
R E m RD GRAF, 113.
A 25:28 292 M 52 22:2 262 5 $35.: 5.5: 5.; .L o 2w 2 s :5 $32: 2.5: M $5 Um IE 5%: 55 E -532 a 3838 e 2 a5: 25% I 22 e: 0.3 5225 252% 52E; :5: 2 53 2 52:3: :3 5:: N 2528 :5 e: 0.3 2 5E 25;: 5:; E: :25: 5 52:3 52 5.52 5.; $252 23:: 233 55 2.55% 227:: a E: 232:
t run 2,760,884 7 COMPOSITION AND METHOD FOR IMPREGNA- TION F SHEET MATERIALS WITH SYNTHETIC RESIN LATICES George Leonard Graf, Jr., Wilmington, Del., assignor to The C a fic C p at n, lin n, 1-,, a c rpustion of Delaware f Application July 22, 1954, Serial No. 445,133 Claims. (Cl. 117 65) This invention relates to a method for stiiiening a fibrous sheet material,v and more particularly, it relates to a method of preparing shoe stiffeners by treating a sheet material with a synthetic resin'latex.
High quality shoe stiffeners in the past have been made by impregnating a flannel sheet material with finely (livided particles of cellulose nitrate. After product was stored until ready for use, at which time the impregnated flannel was dipped into a solvent for the cellulose nitrate, applied to the appropriate shoe part and allowed to dry to a stifiened condition.
It is also known that sheet materials such as flannel may be impregnated by dipping the flannel into an aqueous dispersion of synthetic resin, such as a synthetic rubber latex. However in all the known processes there are operating difliculties which arise because of the tendency of such a latex to deposit in a dense impervious form. As a result of such a formation, the porosity of the impregnated material is low and the ability of the material to absorb solvents is poor. The low porosity and poor solvent absorption prevents the achievement of the greatest stifiness for a given composition of impregnated fabric. ing to known processes, heavier flannels or'other supporting materials, must be impregnated with a greater amount of resin, and such procedures are commercially unattractive.
It has now been found that certain relatively cheap synthetic resin latices maybe impregnated in the form-of finely divided particles into a flannel sheet material, which has a long storage life, and which may thereafter be treated with a solvent for the synthetic resin, applied to the shoe part, and allowed .to dry and form a high quality shoe stiffener. The sheet material utilized in this ingenr tion may be of the lightest grade and yet be impregr nated with a sufiicient amount of resin to bestifiened j a very high degree, because'the present process produces a highly porous impregnated fabric having the ability to e s bl s r Perc nta e o olven tha h e eribs chiev d y t e u of syn t e n la ex imprs aat ea- The attached drawing illustrates,,by means of a self.-
.explanatory flow sheet, the process of this invent on.
It is an object of this invention to providea noyel method for stifiening fibrous materials. It is another ob ject'of vthis invention to prepare high quality shoes, 11T- ne s y using a s thet e i latex s the m ssna in medium. It is still another object to provide a; ngle p process for e na n b sh et 1.1a.
wh ch a ab fbeias t f en .b sub sa s t tr atm n h r e i t il ecome eaparentit ga the mo l explan cn'Qfi h s inysmi a .v I -abo -pbie a e. cp l hedi ac qrdanc w the process of this invention .by impregnating asheet material with van aqueous latex containing g0 60% by weight vof vinyl polymer particles andJibQ SeQ Q}? the weight of vinyl polymer particles 05% to 5% nondoni spers n a n which s ll le in We room temperature and becomes substantially insoluble, in
Therefore to obtain a desired stiffness, accord- 2,760,384 Patented Aug. 28, 19,56
ice
and 0.5% to 15% of a Water-soluble polyvalent metal salt mployed as the latex coagulant. After stripping the impregnated sheet material of excess liquid, the sheet mateis heated to a temperature above from about 40 C tofabout 100 C., causing the dispersing agent to insolubilize and allowing the coagulant to cause the resin particles toforrn small agglomerates dispersed through.- .out the sheet material, which as a result of this treatment has a non-tacky, but somewhat moist surface. The renaming moisture is then removed by drying the sheet material by any known means. At any later time the dry impregnated sheet material may be treated with a volatile solvent for the resin agglomerates, the sheet may then be formed into the desired shape, and dried by e apora n e s P a or on of he salien the sheet material stifiens. p
In the preferred embodiment of this invention an intresnatiae med s P a b XiPsat mom .peratur ef3 parts by weight of an aqueous polystyrene latex containing about 50% solids, 1 part of an aqueous later; of a copolymer of styrene and butadiene (in the approximate proportion of 80 parts styrene to 20 parts butadiene) containing about solids, and about 3% by weight of resin solids of dodecylphenyi polyg lycol eth r l r i s agent- A Fl pe eias a en h s ed;' by ht af esh; s lidscf a uminum i l te -the t m o a 1 a eous slut s. a de slowly a d wm w anc e t e i atisa to Pree t 9 l z s' s la o Th P 9f t e xture t en-amu ed th a ge of 6.01. 7.0 by addm ah u 1% by weight of resin solids of calcium carbonate and water is added to provide a latex containing about"A0% solids. The desired sheet'materialis then dipped into the aboye mixture and stripped between rolls to give aloading of at least by weight of impregnating solids; The pregnated sheet material is then heated to about 25 G. or more by direct contact with steam. this period he sy t t c resin P t e in h wp e lflisd shee material agglomerate to the desired and are dispersed evenly throughout the sheet material. The agglomeration occurs because the heat causes the dispersing agent (dodecylphenyl polyglycol ether in this case) to precipitate thusremoving the substance which inhibits the tend,- ens s the r n P r i le a u te The mete? .the'n dried to remove the remaining moisture. After this treatment the impregnated sheet material is dry and I stiifener, it is blanked into the desired shape, treated .with
a yolatile solvent for the resin, such as methyl ethyl ketone, toluene, mixtures of these materials wi-t-h diluents, 9. th k wn Solvents, ap d o hease hih s 19 be stitfened, and the solvent is allowed to evap0rate, tl 1 us producing. a stifiened sheet material. I
The following examples are given to illustrate various embodiments of this invention. Parts and percentages are by weight unless otherwise specified. v Example 1.A latex blend was prepared by mixing 3 Parts I a Pol styrene qus uslat x containing 5.0% resin solids and 1 part of aqueous latex of a copolymer of styrene and butadiene in the proportions of /20, this latex contained 45% resin solids. Into 600 grams of this latex blend there were added'the following water at temperatures from about 40 C. to about '65; s
the order named: v
8.8 grams of dodecylphenyl polyglycol ether 29.2grams of 10% aqueous solution of aluminum-sulfate 2.92'grams ofcalcium carbonate 92 grams of distilled Water The resulting mixture had a resin solids content of 40% and apH of 6.35.
This latex mixture was used to impregnate pieces of cotton flannel having a twill weave and a thickness caliper of 0.033 inch to 0.039 inch and a weight per square yard of 0.35 to 0.38 pound. A piece of this flannel measuring 10 x 15 inches was impregnated by dipping the flannel into the above latex mixture followed by stripping the wet material between rolls placed 0.049 inch apart. The impregnated fabric was then placed in a chamber filled with steam at 95 C. to 100 C. in such a manner that both sides of the fabric were exposed to the steam. After the fabric had been in the steam chamber for 1 minute it was removed and placed in a circulating air oven at 110 C. for 1% hours. Of the total weight of the impregnated fabric, 72.8% by weight was resin. This figure is called the percent resin loading hereinafter.
Two small portions, 3 x 5 inches, of the above impregnated fabric were then tested for solvent absorption and stiffness. These pieces were dipped into a solvent comprising a mixture of 90% by weight of toluene and by weight of a commercial petroleum naphtha fraction boiling in the range of 100 to 167 C. The two pieces, designated as A and B, were found to have absorbed 123% and 122% by weight respectively of solvent, based on the dry weight of the impregnated fabric before solvent treatment.
These pieces were then laminated into a simulated shoe toe portion comprising, in the order named, shoe leather, doubler cloth, stiffener, and liner cloth. The resin migration as observed from the liner cloth was very good and there was no indication of spotty adhesion. The adhesion between the liner and the stiffener, between the stiifener and the doubler, and between the doubler and the leather, was good.
These laminates were then cut into strips measuring 1 x 3 inches, and two strips from each laminate were tested according to The Standard Method of Testing for Stiffness in Flexure in Plastics ASTM D747-50 (adopted 1950). The stiffness values for each of the two pieces (specimens 1 and 2) cut from the A laminate was 145,000 and 165,000 pounds per square inch respectively giving an average of 155,000 pounds per square inch for the two pieces. The stiffness value for each of the two pieces (specimens 1 and 2) cut from the B laminate was 173,000 and 137,000 pounds per square inch respectively giving an average value of 155,000 pounds per square inch for the two pieces.
Because the thickness of the leather varied slightly from one laminate to another, the value of stifiness by the above ASTM testing method was subject to wide variations which were believed to be due principally to the leather thickness. Accordingly, from the data obtained from the ASTM test there was calculated a value called rigidity which was independent of the leather thickness. This value is the inch-pounds of work required to deflect a one inch wide specimen with a lever arm of two inches through a deflection angle of 30. The total distance through which the free end of the specimen moved was one inch. Thus the value of rigidity is reported in terms of inch-pounds of work per inch of deflection. The rigidity of these specimens is compared with the ASTM stiflness for each specimen in the following table.
Rigidity ASTM (in .lbs./ Stiffness in.) (p. s. i.)
Specimen 1, Laminate A 9. 5 145,000 Specimen 2, Laminate A 11.0 165, 000 Specimen 1, Laminate B 9. 7 173,000 Specimen 2, Laminate B 9. 5 137,000
Example 2.A latex blend was prepared in all reaspects similar to Example 1 except the calcium carbonate was omitted and replaced with additional water to prepare a 40% resin solids latex. Identical pieces of flannel were impregnated and were subjected to steam treatment and were dried in an air oven in the same manner as described in Example 1 with the single exception that in this case the temperature of the air oven was 120 C. The percent resin loading in the impregnated fabric was 71.8%. Two small pieces A and B were treated with solvent as described in Example 1 and were found to have a percent solvent absorption of 130% and 129% respectively. Laminates were prepared from leather, doubler cloth, stiifener, and liner cloth as described in Example 1 and were found to exhibit good adhesion between all adjacent layers of the laminate and the resin migration was found to be good. From each of the two pieces A and B specimens were cut and subjected to tests to determine the ASTM stiffness and the rigidity as defined in Example 1. The following results were obtained:
ASTM Rigidity (in.1bS./ in.)
Specimen 2, Laminate B Example 3.A latex mixture was prepared in the same manner as described in Example 1 with the exception that 1.25% by weight of resin solids of methyl cellulose was added as a thickening agent and various amounts of calcium carbonate were added as a filler to determine the effect upon solvent absorption of the impregnated fabric and thereby the effect upon its rigidity. The addition of methyl cellulose is advantageous in maintaining the large amounts of filler in a dispersed condition. By increasing the filler concentration the amount of resin picked up by the fabric was decreased although the total solids (resin plus filler) remained relatively constant. The following table shows the results obtained from the impregnation of flannel and the preparation and testing of laminates in the same manner as described in Example 1.
Wt. Percent Solvent Absorption Percent of Calcium Carbonate Filler Based on Weight of Resin Solids Rigidity Wt. Per- (in.-1bs./in.)
Specimen 2 Example 4.An impregnating mixture was prepared by mixing 600 grams of an aqueous latex, the solid material comprising essentially a copolymer of vinyl chloride and vinylidene chloride (the latex containing approximately 56% resin solids and being sold commercially by the B. F. Goodrich Company under the name Geon 351) with 9.7 grams of dodecylphenyl polyglycol ether, 124.5 grams of a 10% aqueous aluminum sulfate solution, and 73 grams of distilled water. The resulting mixture contained 40% resin solids.
A piece of cotton flannel weighing 0.36 pound per square yard and measuring about 10 inches by 17 inches was dipped into the above mixture and stripped between rolls spaced .049 inch apart. The stripped fabric was heated to a temperature of C. to C. by contact with steam for 1 minute, and then dried in an air oven at 100 C. The dried fabric had an average resin loading of 73.9 weight percent.
Pieces of the impregnated fabric were then tested for solvent absorption using as a solvent a mixture'of 70% masses methyl ethyl ketone and 30% 'cyclohexahone. "Of {four pieces tested the average solvent absorptionwas 264% by'we'ight.
In the lamination of simulated shoe toes, the resin migration was found to 'be very good, and the adhesion between adjacent layers 'of the laminate "was good in each case. The average ASTM stiffness was 85,500 p. 's. i. and the average rigidity was 5.3 inch-pounds per inch of deflection measured as described in Example 1.
Example 5."In a manner similar to that described in Example 4, 600 grams of a vinyl chloride/vinylidene chloride latex, containing about 55% solids and sold by B. F. Goodrich Company under the name of (icon 352, was mixed with grams of dodecylphenyl polyglycol ether, 151.3 grams of a 10% aqueous solution of aluminum sulfate, and 69 grams of water. The resulting mixture contained 40% resin solids.
A piece of cotton fiannel weighing 0.36 pound per square yard was impregnated by dipping into the above mixture and stripped between rolls spaced .049 inch apart. The stripped fabric was heated to 95 C. to 100 C. by contact with steam for two minutes and then dried in an air oven at 100 C. The dried fabric had an average resin loading of 67.2 weight percent.
Pieces of this impregnated fabric were then tested for solvent absorption, made into a simulated shoe toe laminate, and tested for rigidity and stiffness as described in Example 4. The average solvent absorption was 169% The resin migration was very good and the adhesion between adjacent layers of the laminate was good in each case. The average ASTM stiffness was 68,000 p. s. i. and the average rigidity was 3.8 inch-pounds per inch of deflection.
Example 6.l.'n a manner similar to that described in Examples 4 and 5, 600 grams of a vinyl chloride/vinylidene chloride latex containing about 53% solids and sold by the B. F. Goodrich Company under the name, Geon 251, was mixed with 9.7 grams of dodecylphenyl polyglycol ether, 124.5 grams of a 10% aqueous solution of aluminum sulfate, and 64 grams of water. The resulting mixture contained 40% resin solids.
A piece of cotton flannel weighing 0.36 pound per square yard was dipped in the above mixture and stripped between rolls spaced .049" apart. The stripped fabric was then heated at 95 C. to 100 C. by contact with steam for 2 minutes and then dried in an air oven at 807 C. The dried fabric had an average resin loading of 75.2 weight percent.
Pieces of this impregnated fabric were then heated for solvent absorption, made into a simulated shoe toe laminate, and tested for ASTM stiffness and rigidity by the methods described in Example 4. The average solvent absorption was 125%. The resin migration in the shoe toe laminate was good and the adhesion between adjacent layers of the laminate was good in each case. The average ASTM stiffness was 82,000 p. s. i. The average rigidity was 3.9 inch-pounds per inch of deflection.
Example 7.For comparative purposes, similar pieces of flannel were impregnated by three different processes. The first two methods are known to the public and the third method is identical with that described in Example I. In each case, the techniques used were intended to produce the highest quality shoe stifl ener possible with theparticular ingredients used.
In the first method the impregnating medium was a solution of cellulose nitrate. In the second method the impregnating medium was a' mixture of 3 parts of aqueous polystyrene latex and 1 part of an aqueous latex of an 80/20 copolymer of styrene/butadiene and 1% by weight of resin solids of an organic phosphate saltsold by Victor Chemical Works under the name of Victor Stabilizer-53. The total resin solids content amounted easilyby the latex. In the third-methodathermosensitive 6 latex im'pregn'atiiin identical with that described in example lwas utilized. p
In each case identical pieces of'cottonflannel weighing 0.36 pound per square yard were impregnated, made into simulated shoe toes, and were tested according to erican Standards Assoc. Bulletin on Mars Safety Shoes No. Z4l.ll944. The values-obtained were reported as a Compression Number which is the total number of pounds required to depress the shoe toe to a distance of 0.5 inch from the insole. Thus higher Compression Numbers are equivalent to a greater -de'gree of stiffness. The laminate made from the cellulose nitrate impregnated shoe stiffener, called the first methodabove, had a Compression Number of 31. The laminate prepared with a stiffener made by 'the'secorfd method above had a Compression Number of 51. The laminate made by the process of this invention, called'the third method above, had a Compression Number'of 95. Furthermore, laminates prepared by the third method above, utilizing very light flannel, 0.121 pound per square yard, had a Compression Number of 48, illustrating that :a higher degree of stiffness can beachieved bythe process off the present invention even when utilizing 'flannelof one-third the weight required to produce the same stiffness .by the known cellulose nitrate process.
Any of several kinds of synthetic resins having eleci trostatic properties may be used as the major ingredient in the impregnating latex, although the vinyl resins are preferred, such as polystyrene, polymethyl styrene, polyvinylhalides, polyvinylidene halides, polyacrylates, .poly-' acrylonitrile, and 'polyallcylacrylates. It is desirable in many instances to employ .a plasticized resin, such as a. mixture of polystyrene and a copolymer of high styrene content and low butadiene content, the. copolymer acting as a plasticizer and thereby causing the polystyreneito be; less brittle although retaining its stiffness.- Other known plasticizers such as organic esters, and other non-volatile; non-hardening liquids-may be incorporated with the base resin to reduce brittleness in the same manner as the styrene/butadiene copolymer is used above. of styrene or of vinyl halides are particularly desirable because of their availability and low cost; 7
Many varieties of resins and; combinations of polymers have been found to be useful in this process. One useful group of resins is a copolymer of styrene/butadiene containing 4% to 20% by weight of butadiene. A preferred formulation is a mixture of 3 parts polystyrene with 1 part of an 20 copolymer of styrene/butadiene; which mixture has a total composition of styrene and 5% butadiene. The proportions of polystyrene and the styrene/butadiene copolymercan be varied within the general: range of 420% by weight of butadiene'zin the total mixture to produce slightly stiffer and harder compositions as the butadiene proportion is reduced and softer more elastic compositions as the butadiene proportion is increased; The same variety of compositions can be obtained by mixing wellrknown plasticizers with polystyrene or other hard plastic materials, particularly the vinyl polymers such as vinyl halide, vinylidene halide; alkyl acrylates, and other resins known to those skilled in'the art. a
The latexused as a starting material in the prepara tion of the impregnating bath ofthis inventionis a colloidal dispersion of one or more of the above resins in an aqueous medium; Preferably, the dispersion contains from about 40% to about 60% resin solids, while th'e remainder is essentially all water. These dispersions-or, latices are available commercially on the open market in concentrations of 40% to 60% solids, or they maybe prepared by known methods, such asv dispersionpolw meri'zation. The latex of resin andwater constitutes the largest portion of theirnpr'egnating mixture of this in; vention' and the additives described below constitute less; than" abbut .l5%' of the total weight of the impregna mixture, although there are some embodiments of this Polymers invention wherein a large amount of filler is employed.
After all additives are incorporated into the latex, it may then be diluted if desired, and in any case will contain about 20% to 60% resin solids in the final form as an impregnating bath.
,Dispersing agents are required additives to the latex utilized in this invention so as to stabilize the latex against premature coagulation. The dispersing agent is non-ionic and must be one which is soluble in the latex medium at room temperature and increasingly insoluble at higher temperatures. The solubility of these substances should be such that it is soluble in water at some temperature from about room temperature (20 C.) to about 40 C. and that the substance is insoluble in water at some temperature from about 40 C. to about 100 C. Of course, the solubility of chemical substances normally changes rather slowly with temperature and it is not intended to limit this invention to those dispersing agents which are completely soluble at room temperature and completely insoluble at 40 C., but rather to include those non-ionic dispersing agents which can be dissolved in an aqueous medium at room temperatures or thereabout and which have inverse solubility characteristics and will therefore become insoluble as the temperature is increased up to about 100 C. The solubility requirement of the dispersing agents used in this invention is such that the impregnating latex may be prepared at ordinary temperatures (20 C. to 40 C.) and the dispersing agent will be soluble and thus prevent any gross coagulation or premature agglomeration of the latex but as the temperature is raised to some convenient point (40 C. to 100 C.)
the dispersing agent becomes insoluble and allows agglomeration to occur. The preferred compounds which function as non-ionic dispersing agents and have inverse solubility characteristics include the polyglycol ethers such as octylphenyl polyglycol ether, dodecylphenyl polyglycol ether, and ethers formed as the condensation product of ethylene oxide and rosin. The alkylphenyl polyglycol ethers are preferred in this invention.
The amount of dispersing agent employed is at least about 0.5 and normally not more than by weight of the resin solids present in the latex. If the liquid latex constitutes about 20% to about 60% resin solids, then the dispersing agent will be present from about 0.1% to about 3.0% by weight of the total latex. Greater amounts than 5% by weight of the resin solids may be used without affecting the process other than increasing the costs involved. Generally, about 3% of dispersing agent is recommended for the preferred embodiments of this invention since this amount effectively inhibits coagulation or agglomeration of the latex at room temperature as well as reducing the surface tension of the latex liquid and thus permit rapid penetration of the latex into the sheet material.
Coagulants which may be employed in the process of this invention are the water-soluble polyvalent metal salts which may be chlorides, nitrates, sulfates, acetates, etc. of aluminum, magnesium, calcium, iron, tin, copper, cobalt, chromium, cadmium, strontium, etc. Of these various salts calcium chloride, ferric sulfate, magnesium sulfate, and aluminum sulfate are desirable, although the latter two are preferred because of their lower costs, better solubility characteristics, and the fact that they do not impart undesirable color to the finished product. The alums such as the potassium, sodium, or ammonium aluminum sulfates are as desirable as aluminum sulfate as the coagulant in this process.
The amount of coagulant required will vary slightly with the chemical nature of the coagulant salt, the type and amount of resin employed, and other reaction conditions. For the preferred coagulant, aluminum sulfate, approximately 0.5% by weight of the resin solids present in the latex is suflicient to accomplish the desired result, although in the preferred embodiment of this invention about 1% is normally employed. For other coagulants, some of which are known to be less active and less eflicient than aluminum sulfate, the amount employed may be as high as 10% or 15% by weight of the resin solids. There may be other variables of this process which will affect the amount of coagulant required to achieve the most eflicient operation; these variables including the temperature employed to insolubilize the dispersing agent, the chemical nature of the impregnating medium, and other factors known to those skilled in the art, and it is therefore intended to include other concentrations of coagulant in this invention since it is not a critical feature thereof and is generally well understood by those skilled in the art.
The coagulant salts of this invention are capable of causing the colloidal resin particles in the latex to change into a dense curdlike mass if there is no protective effect of a dispersing agent. A change into such a dense curdlike mass is referred to herein as coagulation. In the process of this invention the colloidal resin particles of the latex are protected from the action of the coagulant salt by the presence of a dispersing agent which gradually becomes insoluble as the temperature of the latex'is raised. As the dispersing agent becomes insoluble the resin particles form small clusters of the original colloidal particles and these clusters deposit in the impregnated material in the form of a porous mass as distinguished from the coagulated, dense curdlike mass referred to above. The formation of the porous clusters is referred to herein as agglomeration.
The material which is to be stiffened may, in general, be any fibrous sheet material such as any of the varieties of fabrics, textiles, felted materials, mats, papers, or the like. The sheet material may be made of natural or synthetic fibers or a mixture of the two. In the case of shoe stirfeners the material commonly employed is a cotton flannel, although non-woven sheet material or even paper may be used in some cases.
Filler materials may be incorporated into the impregnating medium of this invention to serve several useful purposes. For example, the filler may be used to reduce the cost of the materials used in the impregnating bath. The use of a filler in many instances causes the impregnated material to be more porous and therefore to be able to absorb more solvent and achieve a greater stifiness. In some cases, the use of a filler enhances the adhesiveness of the impregnated material to an adjacent laminating layer. Some filler materials serve many purposes in addition to their diluent elfect, for example, they may act as a buffering agent as will be explained later, they may improve fire resistance, improve adhesiveness and solvent absorption and other uses apparent to those skilled in the art. In the manufacture of shoe parts using the impregnated shoe stiffner of this invention it has been found that the incorporation of filler material permits the shoestifiener to be handled easily when it is wet with solvent and ready to be incorporated into the shoe part and, furthermore, after the shoe part has been assembled there is less likelihood that resin solids will migrate from the shoe stiffener and cause visible spotting on the leather surfaces of the shoes. Filler materials which may be used include water insoluble salts such as calcium carbonate and calcium sulfate, infusorial earths, bentonite clays, and other inert materials known to those skilled in the art. The amount of filler material which may be used may be as much as about by weight of the resin solids present and a range of values of about 20% to 50% is preferable for most embodiments of this invention.
Thickeners have utility in this invention when it is desired to impregnate a fabric with greater and greater amounts of resin solids, and when fillers and other ingredients of the latex have a tendency to settle out. Thickeners which have been used successfully include methyl cellulose and methyl carboxy cellulose. Other equally useful thickeners are well known to those skilled in the art.
In the preparation of high quality shoe stiifeners and in certain other embodiments of this invention it is highly desirable to adjust the pH of the impregnating latex so that there will be no injury to the supporting fibrous sheet material due to acidic attack. Latices containing a mixture of polystyrene and a copolymer of styrene/butadiene, a dispersing agent, and a coagulant salt as described above have been found to have a pH of 3.5 to 4.5, and, because of such acidity, to damage the flannel impregnated by such latices. It is therefore preferable to add a buffer material to adjust the pH to a value of 6.0 to 7.0. Any of a large variety of salts may be added to the latex to perform the buffering function, such as the alkali metal and alkaline earth metal carbonates, bicarbonates and hydroxides. Calcium carbonate has been found to be desirable for this purpose, and approximately 1% by weight of the resin solids is sufi'icient to raise the pH to 6.0 or 7.0. It is also possible to utilize hydroxides, such as calcium hydroxide, in very small amounts to adjust the pH to the desired level of 6.0 to 7.0.
As a final step in the preparation of the impregnating latex, water may be added to form the desired concentration of resin solids, which for most embodiments of this invention will be from about 20% to about 60% by weight of solids. For the preparation of most shoe stifieners, a concentration of about 40% solids has been found to be preferable.
Because of the sensitivity of synthetic resin latices toward coagulation, it is recommended that the impregnating composition be prepared by mixing the ingredients in a specific order; namely, that the resin latex and the dispersing agent be, thoroughly mixed before adding the coagulant. Furthermore, it is helpful to add the coagulant slowly, and in a diluted condition, to the latex while the latex is being agitated. Such precautions as these assist in preventing any localized coagulation of the resin solids in the latex. It may be desirable in some embodiments of this invention to employ a stepwise process in which the coagulant is in a bath separate from the latex bath, and the cloth which is to be impregnated is contacted with one bath containing the latex particles and a second bath containing the coagulant.
In the process of preparing a stiffened material such as a shoe stiffener, cotton flannel or other supporting sheet material is dipped, sprayed, covered, or otherwise treated with the impregnating latex, which is prepared according to the above description.
The excess liquid is removed from the wet impregnated material by a suitable means such as coacting stripping rolls, a wiper knife, or the like. Such an operation is capable of loading the supporting material to the desired amount of about 50% or more by weight of impregnating solids if the original impregnating latex contains about 40% solids. Some shoe stiffeners are prepared with much less than 50% resin solids and this process is capable of preparing such shoe stilfeners by loading the material with less than 50% solids. The stripped, impregnated material is then heated to cause agglomeration of the resin solids and to evaporate the remaining water from the material. Any method of heating may be utilized although it has been found that the most desirable results are obtained if the material is heated in a humid atmosphere, for example, 95 C. by contact with steam at about 95 C. to about 120 C. The steam treatment is followed by drying to produce a dry, impregnated material having better solvent absorption characteristics, and thereby, a greater stiffness, than can be produced by using other methods. In some cases it may be desirable to subject the dried impregnated sheet material to the action of calendering rolls to produce an accurate caliper thickness in the material.
The dried impregnated material, by the above treatment, contains small agglomerates of resin particles uniformly dispersed throughout the sheet material. As such this material may be stored if desired, or it may be used in the production of a stiffened article of manufacture, such as a box toe or counter in a shoe, a laminate with other materials, shaped molds, and other similar objects. The stiffening process is accomplished by treating the dry, impregnated material with a solvent for the resin, forming the solvent-treated material into the desired shape and allowing the solvent to evaporate leaving a stiff, self-supporting, article. The solvent for the poly" styrene resin may be methyl ethyl ketone, toluene, or mixtures of these materials,and the solvent for the polyvinyl chloride resin may be methyl ethyl ketone, cyclohexanone, or mixtures of these materials with each other or with diluents. Other solvents for these and other operable resins are known to those skilled in the art.
The process of this invention is particularly useful in the preparation of shoe stiffening materials such asbox toe or shoe counters and it also finds a wide variety of uses in the preparation of impregnated materials which are used to stilfen or otherwise strengthen materials with which it is laminated. The impregnated material of this invention may be used to repair sheet metal articles such as roof gutters, downspouts, fenders and bodies of automobiles. This material also finds use in covering the decks and hulls of small boats, in the preparation of artificial limbs, in the manufacture of mannikins, and various display devices and in any of a variety of laminating applications.
I claim:
l. A process for preparing sheet materials cap-able of being stiffened consisting essentially of preparing an aqueous latex containing (1) 20% to 60% by weight of a vinyl polymer, (2) 0.5% to 5% by weight of said: vinyl polymer of a non-ionic dispersing agent which is soluble in water at some temperature from about room temperature to about 40 C. and is substantially insoluble in water at some temperature from about 40 C. to about 100 C., and (3) from about 0.5% to about 15% by weight of said vinyl polymer of a water-soluble polyvalent metal salt; impregnating a fibrous sheet material with said aqueous latex, removing excess latex from said sheet material, heating said sheet material at a temperature of 40 C. to 100 C. until the liquid latex particles agglomerate, and thereafter drying the sheet material.
2. The process of claim 1 in which the heating of said sheet material at a temperature of 40 C. to 100 C. is accomplished in a humid atmosphere.
3. A process for preparing sheet materials capable of being stiffened consisting essentially of preparing an aqueous latex containing (1) 20% to 60% by weight of a mixture of a major portion of polystyrene and a minor portion of a copolymer of styrene/butadiene, (2) 0.5% to 5% by weight of said vinyl polymer of a nonionic dispersing agent which is soluble in water at some temperature from about room temperature to about 40 C., and insoluble in water at some temperature from about 40 C. to 100 C., and (3) from about 0.5% to about 15% by weight of said vinyl polymer of a watersoluble polyvalent metal salt; impregnating a fibrous sheet material with said aqueous latex, removing excess latex from said sheet material, heating said sheet material to a temperature of at least 95 C. by direct contact with steam until the liquid latex particles agglomerate, and thereafter drying the sheet material.
4. The process of claim 3 in which the weight ratio of said major portion to said minor portion is about 3:1 and said copolymer contains styrene and butadiene in the Weight ratio of about :20.
5. The process of claim 4 in which said polyvalent metal salt is aluminum sulfate.
6. The process for preparing a shoe stiffener consisting essentially of preparing an aqueous latex containing (1) 30% to 50% by weight of resin solids comprising 3 parts by weight of polystyrene and 1 part by weight of an 80/20 copolymer of styrene/butadiene, (2) 0.5% to by weight of said resin solids of an alkyl phenyl polyglycol ether dispersing agent, (3) about 1% of aluminum sulfate, and (4) adding suflicient bufier material to adjust the pH of said latex to a value of about 6.0 to 7.0; impregnating a cotton flannel sheet material with said aqueous latex, removing excess latex from said sheet material until at least 50% of the weight of the impregnated sheet material comprises latex solids, heating said sheet material to a temperature of 95 C. to 120 C. in a humid atmosphere until the liquid latex particles agglomerate, removing the remaining moisture in said sheet material, and recovering a dr flexible, impregnated fiannel sheet material capable of being stiffened by subjecting it to the action of a solvent for said resin solids.
7. The process for preparing a shoe stiffener consistw ing essentially of preparing an aqueous latex containing 1) 30% to 50% by weight of resin solids comprising 3 parts by weight of polystyrene and 1 part by weight of an 80/20 copolymer of styrene/butadiene, (2) 0.5% to 5% by weight of said resin solids of an alkyl phenyl polyglycol ether dispersing agent, (3) about 1% of aluminum sulfate, and (4) 20% to 50% by Weight of said resin solids of calcium carbonate; impregnating a cotton flannel sheet material with said aqueous latex, removing excess latex from said sheet material until at least 50% of the weight of the impregnated sheet material comprises latex solids, agglomerating the liquid latex particles in the resulting sheet material by heating said sheet material to a temperature of 95 C. to 120 C. by direct contact with steam, removing the remaining moisture in said sheet material, and recovering a dry, flexible, impregnated flannel sheet material capable of being stiffened. by subjecting it to the action of a solvent for said resin solids.
8. The process for preparing a shoe stiffener consisting essentially of preparing an aqueous latex containing (1) 30% to 50% by weight of resin solids comprising 3 parts by weight of polystyrene and 1 part by Weight of an 80/20 copolymer of styrene/butadiene, (2) 0.5 to 5% by weight of said resin solids of an alkylphenyl polyglycol ether dispersing agent, (3) about 1% of aluminum sulfate, and (4) 20% to by weight of said resin solids of calcium carbonate, impregnating a cotton flannel sheet material with said aqueous latex, removing excess latex from said sheet material unit at least 50% of the weight of the impregnated sheet material comprises latex solids, agglomerating the liquid latex particles in the resulting sheet material by heating said sheet material to a temperature of 95 C. to 120 C. by direct contact with steam, removing the remaining moisture in said sheet material, and recovering a dry, flexible, impregnated flannel sheet material capable of being stifiened by subjecting it to the action of a solvent for said resin solids.
9. A liquid composition consisting essentially of (1) 20% to by weight of a vinyl polymer, (2) 0.5% to 5.0% by weight of said vinyl polymer of a non-ionic dispersing agent which is soluble in water at some temperature from about room temperature to about 40 C. and is insoluble in Water at some temperature from about 40 C. to about 100 C., (3) 0.5% to 15% by weight of said vinyl polymer of a water-soluble polyvalent metal salt, and (4) suflicient water such that the sum of all components equals 100%.
10. A liquid composition consisting essentially of (1) 20% to 60% by weight of colloidal resinous particles of polymeric styrene and polymeric butadiene in the proportions of 4% to 20% by weight of polymeric butadiene and 96% to by weight of polymeric styrene, (2) 0.5 to 5.0% by weight of said resinous particles of an alkylphenyl polyglycol ether dispersing agent, (3) about 1% by weight of said resinous particles of aluminum sulfate, (4) 20% to 50% by weight of said resinous particles of calcium carbonate, and (5) sufficient water such that the sum of all components equals 100%.
References Cited in the file of this patent UNITED STATES PATENTS

Claims (1)

1. A PROCESS FOR PREPARING SHEET MATERIALS CAPABLE OF BEING STIFFENED CONSISTING ESSENTIALLY OF PREPARING AN AQUEOUS LATEX CONTAINING (1) 20% TO 60% BY WEIGHT OF A VINYL POLYMER, (2) 0.5% TO 5% BY WEIGHT OF SAID VINYL POLYMER OF A NON-IONIC DISPERSING AGENT WHICH IS SOLUBLE IN WATER AT SOME TEMPERATURE FROM ABOUT ROOM TEMPERATURE TO ABOUT 40* C. AND IS SUBSTANTIALLY INSOLUBLE IN WATER AT SOME TEMPERATURE FROM ABOUT 40* C. TO ABOUT 100* C., AND (3) FROM ABOUT 0.5% TO ABOUT 15% BY WEIGHT OF SAID VINYL POLYMER OF A WATER-SOLUBLE POLYVALENT METAL SALT; IMPREGNATING A FIBROUS SHEET MATERIAL WITH SAID AQUEOUS LATEX, REMOVING EXCESS LATEX FROM SAID SHEET MATERIAL, HEATING SAID SHEET MATERIAL AT A TEMPERATURE 40*C. TO 100*C. UNTIL THE LIQUID LATEX PARTICLES AGGLOMERATE, AND THEREAFTER DRYING THE SHEET MATERIAL.
US445183A 1954-07-22 1954-07-22 Composition and method for impregnation of sheet materials with synthetic resin latices Expired - Lifetime US2760884A (en)

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US445183A US2760884A (en) 1954-07-22 1954-07-22 Composition and method for impregnation of sheet materials with synthetic resin latices
US445184A US2805962A (en) 1954-07-22 1954-07-22 Impregnation of sheet materials with synthetic resin latices
GB8871/55A GB766866A (en) 1954-07-22 1955-03-25 Improvements in or relating to synthetic resin dispersions and the preparation of impregnated sheet material therefrom
GB8872/55A GB785058A (en) 1954-07-22 1955-03-25 Improvements in or relating to the impregnation of sheet materials with synthetic resin latices
FR1139582D FR1139582A (en) 1954-07-22 1955-07-08 Aqueous dispersion and method for impregnating a sheet material with a synthetic resin
FR1139583D FR1139583A (en) 1954-07-22 1955-07-08 Process for preparing a sheet material with a view to subsequently making it more rigid
DEC11589A DE1024481B (en) 1954-07-22 1955-07-22 Impregnation of sheet material with synthetic resin dispersions

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US2819179A (en) * 1954-01-18 1958-01-07 American Cyanamid Co Textile finishing process
US2873199A (en) * 1956-03-23 1959-02-10 Exxon Research Engineering Co Emulsion coating composition containing synthetic drying oil and process of making it
US2917405A (en) * 1956-08-28 1959-12-15 Du Pont Non-woven fabric impregnated with a foamed plastic
US2923641A (en) * 1955-04-18 1960-02-02 Celastic Corp Composition and method for impregnation of sheet materials with synthetic resin latices utilizing coagulants of water-soluble amine or quaternary ammonium salts
US3081197A (en) * 1959-09-10 1963-03-12 Du Pont Nonwoven fabrics bonded with interpolymer and process of preparing same
US3146128A (en) * 1960-04-18 1964-08-25 Peter Stoll Coating apparatus
US3392133A (en) * 1962-08-22 1968-07-09 Dow Chemical Co Antifogging coatings for alkenyl aromatic resinous substrates
US3396135A (en) * 1964-07-02 1968-08-06 Monsanto Co Coating composition containing styrenemaleic anhydride partial ester copolymer as emulsifier
US3401058A (en) * 1964-10-16 1968-09-10 Westinghouse Electric Corp Method of coating electrical conductors
US3622447A (en) * 1969-04-17 1971-11-23 Goodrich Co B F Process for the manufacture of bonded fiber sheets
US3649330A (en) * 1967-03-10 1972-03-14 Johnson & Johnson Composition containing metal salts and method of utilizing the same to control resin deposition
US3889024A (en) * 1973-02-01 1975-06-10 Johnson & Johnson Method of controlling the migration of resin compositions in the manufacture of porous materials
US4452939A (en) * 1983-02-28 1984-06-05 The Goodyear Tire & Rubber Company Process for the preparation of high molecular weight polymeric antidegradants
US4452831A (en) * 1979-07-24 1984-06-05 Isovolta Osterreichische Isolierstoffwerke Aktiengesellschaft Method for the production of foils from elastomeric material
US5112651A (en) * 1988-11-09 1992-05-12 Fuji Photo Film Co., Ltd. Method and apparatus an image-receiving element in diffusion transfer photography including drying and heating stages
US6391380B1 (en) 2000-08-03 2002-05-21 Stanbee Company, Inc. Stiffener material with self adhesive properties
WO2021224277A3 (en) * 2020-05-08 2021-12-16 Philip Morris Products S.A. Package of a tobacco or nicotine containing product comprising a moisture regulating product

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DE1954687C3 (en) * 1969-10-30 1985-05-30 Giulini Chemie Gmbh, 6700 Ludwigshafen Process for the production of a shoe cap material
DE102018100264B3 (en) 2018-01-08 2019-05-09 Knorr-Bremse Gesellschaft Mit Beschränkter Haftung Sieve element for sieving and conveying grit for receiving to a sanding device of a sanding plant for a vehicle, sanding device with a sieve element, method for producing and method for operating a Siebelements

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US2656222A (en) * 1951-03-26 1953-10-20 Westinghouse Air Brake Co Combined pneumatic and dynamic brake apparatus
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US2343095A (en) * 1940-08-03 1944-02-29 Du Pont Resin dispersion useful in the textile and paper industries
US2514517A (en) * 1945-11-28 1950-07-11 Montclair Res Corp Wool shrinkproofing baths containing butadiene copolymers and their utilization
US2650163A (en) * 1947-05-21 1953-08-25 Hercules Powder Co Ltd Butadiene-styrene sized paper and method
US2635055A (en) * 1948-07-08 1953-04-14 Hans G Figdor Water repellent composition
US2554899A (en) * 1949-12-20 1951-05-29 Us Rubber Co Grease-proof paper and process of making the same

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2819179A (en) * 1954-01-18 1958-01-07 American Cyanamid Co Textile finishing process
US2923641A (en) * 1955-04-18 1960-02-02 Celastic Corp Composition and method for impregnation of sheet materials with synthetic resin latices utilizing coagulants of water-soluble amine or quaternary ammonium salts
US2873199A (en) * 1956-03-23 1959-02-10 Exxon Research Engineering Co Emulsion coating composition containing synthetic drying oil and process of making it
US2917405A (en) * 1956-08-28 1959-12-15 Du Pont Non-woven fabric impregnated with a foamed plastic
US3081197A (en) * 1959-09-10 1963-03-12 Du Pont Nonwoven fabrics bonded with interpolymer and process of preparing same
US3146128A (en) * 1960-04-18 1964-08-25 Peter Stoll Coating apparatus
US3392133A (en) * 1962-08-22 1968-07-09 Dow Chemical Co Antifogging coatings for alkenyl aromatic resinous substrates
US3396135A (en) * 1964-07-02 1968-08-06 Monsanto Co Coating composition containing styrenemaleic anhydride partial ester copolymer as emulsifier
US3401058A (en) * 1964-10-16 1968-09-10 Westinghouse Electric Corp Method of coating electrical conductors
US3649330A (en) * 1967-03-10 1972-03-14 Johnson & Johnson Composition containing metal salts and method of utilizing the same to control resin deposition
US3622447A (en) * 1969-04-17 1971-11-23 Goodrich Co B F Process for the manufacture of bonded fiber sheets
US3889024A (en) * 1973-02-01 1975-06-10 Johnson & Johnson Method of controlling the migration of resin compositions in the manufacture of porous materials
US4452831A (en) * 1979-07-24 1984-06-05 Isovolta Osterreichische Isolierstoffwerke Aktiengesellschaft Method for the production of foils from elastomeric material
US4452939A (en) * 1983-02-28 1984-06-05 The Goodyear Tire & Rubber Company Process for the preparation of high molecular weight polymeric antidegradants
US5112651A (en) * 1988-11-09 1992-05-12 Fuji Photo Film Co., Ltd. Method and apparatus an image-receiving element in diffusion transfer photography including drying and heating stages
US6391380B1 (en) 2000-08-03 2002-05-21 Stanbee Company, Inc. Stiffener material with self adhesive properties
US6475619B2 (en) 2000-08-03 2002-11-05 Stanbee Company, Inc. Stiffener material with self adhesive properties
WO2021224277A3 (en) * 2020-05-08 2021-12-16 Philip Morris Products S.A. Package of a tobacco or nicotine containing product comprising a moisture regulating product

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FR1139583A (en) 1957-07-02
GB785058A (en) 1957-10-23
FR1139582A (en) 1957-07-02
GB766866A (en) 1957-01-23
DE1024481B (en) 1958-02-20

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