US2803613A - Organopolysiloxane composition for rendering cellulosic materials nonadherent and method of applying same - Google Patents

Organopolysiloxane composition for rendering cellulosic materials nonadherent and method of applying same Download PDF

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US2803613A
US2803613A US416422A US41642254A US2803613A US 2803613 A US2803613 A US 2803613A US 416422 A US416422 A US 416422A US 41642254 A US41642254 A US 41642254A US 2803613 A US2803613 A US 2803613A
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paper
weight
organopolysiloxane
emulsion
metallic salt
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William S Kather
Alexander A Litster
Jr Edgar D Brown
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General Electric Co
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General Electric Co
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Priority to GB6486/55A priority patent/GB792845A/en
Priority to FR1153257D priority patent/FR1153257A/fr
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/001—Release paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31993—Of paper
    • Y10T428/31996—Next to layer of metal salt [e.g., plasterboard, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2762—Coated or impregnated natural fiber fabric [e.g., cotton, wool, silk, linen, etc.]
    • Y10T442/277—Coated or impregnated cellulosic fiber fabric

Definitions

  • This invention is concerned with rendering cellulosic materials non-adherent to various organic solids. More particularly, the invention is concerned with compositions capable of rendering paper or paperboard non-adherent to normally adherent materials such as, for instance, asphalt, unvulcanized rubbers, and other high molecular weight organic polymers, said composition of matter comprising an organopolysiloxane fluid and small amounts of an aluminum compound selected from the class consisting of aluminum hydroxide and aluminum silicate.
  • the invention also embodies methods for rendering the above mentioned paper or paperboard nonadherent.
  • Cellulosic fibers in the form of cellulosic papers and paperboard are used extensively as confining and shipping means for various highly adhesive materials including such organic compositions as asphalt or pitch, tar, various unvulcanized rubbers, particularly synthetic rubbers, and other high molecular weight organic polymers.
  • organic compositions as asphalt or pitch, tar, various unvulcanized rubbers, particularly synthetic rubbers, and other high molecular weight organic polymers.
  • the asphalt is generally poured while still hot into a container, such as a carton, bag or drum whose sides are cellulosic in nature. After cooling, the asphalt becomes quite hard and can be readily transported with little difficulty.
  • this paper in whatever form be readily stripped from the asphalt so as to permit easy access to the latter without any extraneous portions of the paper or fibers thereof adhering to the asphalt so as to undesirably affect the constitution of the asphalt.
  • anti-blocking paper Various treatments have been accorded :these types of papers which are often referred to as anti-blocking paper.
  • One method for treating the paper to render it anti-blocking comprises treating the paper in a three-coat operation with (l) finely divided clay and casein, (2) finely divided clay, and (3) polyvinyl acetate. $uch paper provides release by fracture of the clay coating, but the polyvinyl acetate remains on the adhesive material.
  • Another method commonly employed in the art involves applying several thicknesses of polyethylene to the paper, usually by treating the latter with solutions of the polyethylene.
  • a still further method for treating cellulosic materials to render it impermeable, particularly to asphalt and to permit it to be readily removed from direct contact with the latter involves depositing a double coating on the cellulosic material, the first coating being of clay and the second coating being of methyl cellulose and starch.
  • U. S. Patent 2,588,367 describes the use of methyl hydrogen polysiloxanes in combination with water-soluble cellulose ethers for the purpose of treating anti-blocking paper to render it less adherent to ordinarily adhesive organic compositions. Although such combinations of ingredients are ordinarily helpful in reducing the ad hesive properties of the paper, nevertheless much is left to be desired from such treatment of the paper. Often, the release properties are unreliable and the release characteristics are not uniform throughout the surface of the paper. In addition, it is essential that, in order to obtain optimum release properties, the treated paper be aged for extended periods of time, c.
  • cellulosic sheet material is treated with an emulsion comprising a non-resinous, fluid organop-olysiloxane containing a minor proportion of an aluminum compound selected from the class consisting of aluminum hydroxide and aluminum silicate.
  • an aluminum compound selected from the class consisting of aluminum hydroxide and aluminum silicate.
  • metallic salts are also advantageously used in the treating mixture.
  • organopolysiloxanes employed in the practice of the present invention are those which are fluid and stable (resistant to increase in viscosity) at normal temperatures (of 25 to 30 C.) and which do not need a solvent to be liquid at such temperatures. This requires that the organopolysiloxane be non-resinous since: the usual organopolysiloxane resins are solids or relatively unstable in the absence of a solvent.
  • organopolysiloxanes which may be employed in this invention are those having the general formula where R is a monovalent hydrocarbon radical, preferably a monovalent lower alkyl radical (e. g., methyl, ethyl, propyl, etc), x has a value of from 1.0 to 1.5, y has a value from 0.75 to 1.25, and the sum of x and y has a value of from about 2.0 to 2.25, inclusive.
  • R is a monovalent hydrocarbon radical, preferably a monovalent lower alkyl radical (e. g., methyl, ethyl, propyl, etc)
  • x has a value of from 1.0 to 1.5
  • y has a value from 0.75 to 1.25
  • the sum of x and y has a value of from about 2.0 to 2.25, inclusive.
  • organohydrogen polysiloxane fluids employed in the practice of the present invention may contain traces of hydroxy radicals due to the incomplete condensation of the silicols obtained as a result of hydrolysis of the intermediate organohydrogen hydrolyzable silanes, for instance, methyldichlorosilane.
  • organohydrogen polysiloxane fluids may be either cyclic or linear polymers.
  • the linear polymers may be chain-stopped with trimethylsilyl groups, or even with diorganohydrogen silyl units as, for instance, units having the formula (CH3 3Si-O-- or (CHa)2HSi-O- Examples ofsuch organohydrogen polysiloxanes may be found, e. g., in Sauer Patents 2,595,890-891, in Wilcock Patent 2,491,843, and in Barry Patent 2,590,812.
  • R in the instant formula may be, for instance, alkyl (e. g., methyl, ethyl, propyl, isopropyl, butyl, etc.), aryl (e.
  • organopolysiloxanes in addition to the liquid, curable organopolysiloxanes described above, other organopolysiloxanes, or mixtures or blends of these organopolysiloxanes, fulfilling the above-mentioned requirements may be employed without departing from the scope of the invention.
  • the use of fluid organopolysiloxanes appears to be critical, not only for optimum release properties, but also for purposes of employing these liquid organopolysiloxanes in usable form, preferably in the form of emulsions which are advantageously used as the treating medium for the release paper.
  • the organopolysiloxane advantageously contains from 1.75 to 2.2 organic groups or total organic groups and hydrogen atoms per silicon atom.
  • An organopolysiloxane fluid which has been found to be eminently successful for release purposes when applied to paper to be used for anti-blocking purposes is one which comprises a polymerizable, fluid, intercondensed product of hydrolysis comprising a mixture of methylchlorosilanes composed essentially, by weight, of 50 to 75% dimethyldichlorosilane, 1 to trirnethylchlorosilane, 10 to 35% methyltrichlorosilane, and from about 1 to 10% of a methylchlorodisilane (or mixture of methylchlorodisilanes).
  • the methylchlorodisilane or mixture of methylchlorodisilanes may be in the form of tetrachlorodimethyldisilane, pentachloromethyldisilane, trichlorotrimethyldisilane, dichlorotetramethyldisiiane, etc., or mixtures of these methylchlorodisilanes, either alone or with hexachlorodisilane.
  • these methylchlorodisilanes may comprise from about 1 to as high as 12 to 15% of the mixture of methylchlorosilanes in the starting hydrolysis product.
  • a metallic salt which is believed to act as a curing agent for the hydrolysis product.
  • This metallic salt may be either a salt of an organic or inorganic acid.
  • the intermediate hydrolyzable mixture of methylchlorosilanes is generally obtained by passing methyl chloride over silicon in the presence of copper at ele vated temperatures in the manner disclosed and claimed in Rochow Patent 2,380,995 issued August 7, 1945 and assigned to the same assignee as the present invention.
  • the reaction product thus obtained in addition to containing the above-described methylchlorosilanes in the stipulated proportions, also contains small amounts of silicon tetrachloride, tetramethylsilane, hexamethyldisilane, methyl-substituted p-olysilanes (with or without silicon-bonded chloride) containing more than two silicons attached by silicon-silicon linkages, etc.
  • methylpolysiloxane used in combination with the abovedescribed organopolysiloxanes, and in particular the above-identified hydrolysis product of the intermediate mixture of ingredients comprising methyltrichlorosilane, trimethylchlorosilane and a methylchlorodisilane or mixture of methylchlorodisilanes (for brevity this hydrolysis product will hereinafter be referred to as methylpolysiloxane), are those which by themselves are either considered as being capable of effecting cure of the organopolysilovane (e.
  • metallic salts may be eitherwater-soluble or soluble in the organopolysiloxane.
  • the metallic salt should itself be free of extraneous color either when employed in its treating form, for instance, in emulsion or dispersion form, or when present on the treated paper.
  • metallic salts satisfying therequire- .ments recited above may be employed.
  • One class of such salts comprises metallic salts, particularly the watersoluble metallic salts whose metal ion is derived from group IV of the periodic table.
  • metallic salts which may be employed are, for example, water-soluble salts (both inorganic and metalloorganic) of, for instance, titanium, zirconium, tin, lead, etc., such as zirconium tetrachloride, zirconium oxychloride, including its hydrates, zirconium sulfate and its hydrates, zirconium acetate, zirconium nitrate, zirconium ammonium carbonate, zirconium oxybromide, stannous chloride, zinc acetate, zinc nitrate, nickel sulfate, nickel acetate, nickel chloride, titanium oxychloride, titanium nitrate (TiO.N205.6I-I20), titanium oxa
  • water-insoluble metallic salts which are soluble in the organopolysiloxane and which can be readily dispersed or emulsified with the organopolysiloxane, so as to be in intimate contact with the latter in order to exercise their function.
  • metallic salts which are soluble in the organopolysiloxane are, for example, metallic salts of organic acids, for instance, acid radicals yielding the resinate, linoleate, stearate, oleate, or even the lower acid radicals such as those yielding the butyrate, octoate, hexoate, etc.
  • metallic salts may be mentioned, e. g., lead octoate, zinc octoate, zinc naphthenate, tin naphthenate, lead naphthenate, tin ctoate, etc.
  • the prime requisite for such types of metalloorganic salts is that they be soluble in some medium such as the organopolysiloxane or water, or be capable of being intimately dispersed or suspended so as to bring them into intimate contact with the organopolysiloxane so as to permit the metallic salt to exercise its function.
  • the metallic salt is advantageously added just prior to application of the emulsion to the cellulosic material.
  • the amount of metallic salt used may be varied widely without departing from the scope of the invention.
  • the metallic salt (other than the aluminum hydroxide and aluminum silicate) is employed in such an amount that there is present at least 0.1%, preferably from 0.5 to 14%, by weight, of the metal constituent, based on the weight of the organopolysiloxane. Optimum results generally are obtained when the metal ion of the metallic salt is within the weight range of from about 1 to 6%.
  • the amount of metallic salt employed will depend upon such factors as, for instance, the particular metal salt used (including the metal ion), its effect on the emulsion, particularly the stability of the latter, the type of organopolysiloxane employed, the type of paper to which the treating composition will be applied, the solubility of the metallic salt as well as the medium in which the metallic salt will be used, the treating conditions includingtemperature and time of treatment, etc.
  • the aluminum compounds which have been found to be essential in the practice of the present invention for obtaining the unexpectedly outstanding release properties are those selected from the class consisting of aluminum hydroxide and aluminum silicate. Hydrates of these aluminum compounds may be employed where available and in many respects may be preferred because of their increased water solubility. Among such aluminum compounds may be mentioned aluminum hydroxide having the formula Al(OH)3, Al2(OH)s; aluminum silicate (in the pure or somewhat impure state) having the formula AlzSiOs, etc., and hydrates and complexes of these aluminum compounds.
  • Aluminum compounds which are prepared in situ in the treating mixture whereby ingredients designed to form either aluminum hydroxide or aluminum silicate are incorporated in thetreating mixture, and in such mixture theseingredients interact to give either the aluminum hydroxide or the aluminum silicate.
  • reactants may be mentioned, for example, the use of a combination of ingredients composed of an alkali-metal hydroxide (such as sodium hydroxide or potassium hydroxide) or of ammonium hydroxide with an aluminum salt such as, for instance, aluminum nitrate having the formula Al(NOa)s, or aluminum which when employed in the proper molar concentrations designed to yield the aluminum hydroxide under suitable conditions, such as neutral conditions, will give the aluminum compound, in this case aluminum hydroxide, in a form satisfactory for the practice of the present invention.
  • the aluminum silicate may be prepared by effecting reaction between a mixture of ingredients comprising aluminum nitrate and sodium silicate.
  • the preformed aluminum hydroxide or aluminum silicate be employed in the practice of our invention in order to exercise better control on the quality and quantity of the aluminum compound employed.
  • the amount of the aluminum compound employed may be varied within wide limits. Amounts of the aluminum compound equal to as low as 1%, by weight, based on the weight of the organopolysiloxane have been found to exercise an improvement in the release properties. Generally, we prefer to employ the aluminum compound in amounts ranging from about 1.5% to 12% or more, by weight, based on the weight of the organopolysiloxane. Amounts of the aluminum compound in excess of 12% may be used, but care should be exercised that it does not render the aqueous emulsion unstable.
  • the treating mixtures employed in the practice of the instant invention is advantageously in the form of an aqueous emulsion or an emulsion-dispersion.
  • the mixture of active ingredients (other than the water) in the treating mixture (this term treating mixture" will hereinafter be used to include the fluid organopolysiloxane, the metallic salt additive for the latter, the aluminum compound, aqueous medium, and any other ingredients required for obtaining stable emulsions or emulsion-dis' persions) will generally comprise from about 0.5 to 25% of the weight of the total treating mixture.
  • emulsifying'agents such as dispersing or emulsifying'agents
  • dispersing or emulsifying'agents may be used especially where the organopolysiloxane is readily emulsified in the water and where the metallic salt is water-soluble
  • emulsifying agents may be mentioned, for instance, the sulfonated amide condensation products of fatty acids with organic amines, sulfonated aromatic and mixed alkyl aryl sulfonate derivatives, and sulfonated ster derivatives.
  • Nilo-SD is a fatty acid amide condensate manufactured by Sandoz Chemical Works, New York, New York.
  • the actual amount of emulsifying or dispersing agent employed will depend, for instance, upon the type of ingredients present in the treating composition, the type of emulsifying agent'employed, the application intended, etc.- Generally, the amount of emulsifying agent satisfactorily employed may range from about 0.01 to 1%, by weight, based on the weight of the entire treating mixture. The amount used is not critical and persons skilled in the art will have little difficulty in determining readily the amount which gives optimum results. It is preferable that the emulsifying agent used be one which permits the emulsion to be stable under treating conditions but is readily broken within the interstices of the paper fibers to deposit the organopolysiloxane. Another particularly good emulsifying agent is Pluramine 5-100 (manufactured by Kearny Manufacturing Company of Kearney, New Jersey) which is also a sulfonated amide.
  • One method for making the treating compositions herein described and found so eminently useful for treating paper in accordance with our process comprises, first, homogenizing water with the emulsifying agent until a homogeneous suspension of the emulsifying agent and water is obtained, the latter material being generally in the form of a creamy composition. To this is slowly added the organopolysiloxane containing a small amount of an emulsion stabilizer such as, for example, oleic acid, etc. 'Ihis'mixture of ingredients is in turn again thoroughly homogenized until the organopolysiloxane is intimately dispersed throughout the water phase after which an additional amount of water is added. This material is often referred to as a master emulsion.
  • the master emulsion is then diluted with an additional amount of water containing, for instance, the water-soluble metallic salt (assuming that such a salt is employed in this description), a colloid protector such as agar gums, casein, methyl cellulose, sodium carboxy methyl cellulose, etc. These colloid protectors may comprise from 0.1 to 0.5% of the Weight of the water added.
  • the aluminum compound is added after the emulsion is in its ultimately diluted form.
  • Satisfactory aqueous emulsions or dispersions may be employed which comprise, by weight, from 80-99% water, from 1-20% of the organopolysiloxane and from 0.01 to 6% or more of the aluminum compound, incorporating in the said emulsion the desired amount of the metallic salt which is required to be present in combination with the aluminum compound for bringing out optimum anti-blocking characteristics of the cellulosic material when th latter is treated with the emulsion and-subsequently dried.
  • Cellulosic materials which can be treated in accordance with our process include all types of paper, such as kraft paper, linen rag paper, rice paper, glassine, parchment, cellophane, cellulosic cloth, suliite cellulose paper, and the like; and sheeting or box materials, such as paperboard, cardboard, pulpboard, and pasteboard. If desired and practicable, treatment of the cellulosic material may be effected by adding treating compositions described above directly to the paper pulp in the beater.
  • the final treating mixture can be applied to the paper by any convenient means, for instance, with conventional dip or roller coating equipment, by padding, spraying, knife-coating, etc.; alternatively, the emulsion may be applied by means of a size press employed in combination with the paper machine so that the treatment of the paper is on a continuous basis taking place after the paper is formed on, for instance, a Fourdrinier machine.
  • the amount of organopolysiloxane which is picked up by the cellulosic material as a result of the treatment with the emulsion or emulsion-dispersion of the organopolysiloxane depends upon such factors as the absorbency of the cellulosic material, the method of application, the concentration of organopolysiloxane emulsion, etc.
  • One of the unexpected advantages of employing the aluminum compound for the treating mixture is the fact that the organopolysiloxane pickup appears to be improved over the pickup realized employing the same treating material but omitting the aluminum compound.
  • the amount of organopolysiloxane pickup ranges from about 0.30 to about 5% or more, based on the dry weight of the cellulosic material; the preferred pickup being within the range of about 0.5 to about 2% organopolysiloxane pickup.
  • larger amounts of organopolysiloxane pickup may be employed, but generally this is not neces sary and usually serves merely to increase the cost of the treatment.
  • The'ability to obtain maximum pickup with minimum amounts of organopolysiloxane and to realize the maximum release properties is one of the unexpected and unobvious advantages of employing the aluminum compound in combination with the organopolysiloxane release material.
  • the material is advantageously dried.
  • This drying may be carried out at room temperature (e. g., 25-30 C.) for several hours, or by passing the treated paper over heated rolls maintained at temperatures of about 50 to C.
  • This drying step will bring out the optimum release properties of the paper without further heat treatment at the much higher temperatures required with other treatments employing organopolysiloxanes but omitting the aluminum compound.
  • these optimum release properties are immediately available without requiring aging or storage of the treated paper.
  • the higher the temperature the shorter the period of exposure of the paper for removing the water and drying the paper.
  • the time required for drying should be enough to reduce the finished paper to its normal water content which is about 3 to 7%. Times of the order of about 30 seconds to 3 minutes are usually sufficient for the purpose.
  • the organopolysiloxane employed was obtained by hydrolyzing a mixture of ingredients comprising approximately, by weight, about 5% trimethylchlorosilane, 20% methyltrichlorosilane, 70% dimethyldichlorosilane, and about 4 to 8% of a mixture of ingredients composed of chloromethyldisilanes, particularly trichlorotrimethyldisilane and tetrachlorodimethyldisilane.
  • the methylpolysiloxane fluid thus obtained was found to have a viscosity of about 90 to 100 centistokes.
  • An emulsion was prepared composed of 50 parts of the above-obtained stripped methylpolysiloxane, parts of water, 1 part .oleic acid (as a stabilizer), and 2.5 parts of an emulsifying agent, specifically Nilo SD. This mixture of ingredients was thoroughly homogenized until a thick, creamy mixture was obtained. An additional amount o'f 27 parts water were added and the entire mixture again intimately mixed to give homogeneous master emulsion containing about 50%, by weight, of the methyl polysiloxane.
  • this master emulsion To 10 parts of this master emulsion were added 87.8 parts water containing by weight, thereof of a high viscosity sodium carboxy methyl celluluose as a colloid protector. About 0.7 part of an aqueous solution of stannous gluconate containing 14% tin, by weight, was then added slowly while the mixture was being agitated. This provided a padding solution containing about 5% methylpolysiloxane in the treating mixture. Thereafter, 1.7 parts of an aqueous dispersion containing, by weight, 12% aluminum hydroxide, were added while again effecting agitation of the mixture. This treating dispersion was employed inmany of the succeeding examples for treating of various types of paper.
  • the test for determining the effectiveness of the release properties of the paper was carried out as follows. This test comprised heating an asphaltic pitch specifically G :and K roofing compound to about l85 C. and pouring it on the paper being tested to fill a ring 2.5 in diameter. After one hour when the pitch had cooled to room temperature, the paper was stripped from the pitch cylinder by exerting a force at a right angle to the plane of contact. The force was applied from a gear motor through a cord moving at a rate ofabout 4" per minute. A spring balance was employed to indicate the greatest force in grams required to obtain release of the paper from the pitch.
  • Table I describes various means whereby the paper was dried, or cured, and the conditions under which such procedures were carried out.
  • the air-drying condition recited in Table I involved applying a temperature of about 70 to 80 C. for 2 minutes to the treated paper.
  • the elevated temperature cure involved heating the treated paper at about 150 C. for five minutes.
  • trimethyl end blocked methyl hydrogen polysiloxane was substituted for the met-hylpolysiloxane in. the emulsion described in Example 1, employing the same proce- 10 dure and other ingredientsdescribed in this'fexa'mple, including the aluminum hydroxide; a similar emulsion was prepared omitting the aluminum hydroxide.
  • Kraft paper was then treated with these latter two methyl hydrogen polysiloxan'e emulsions. each of the papers prepared as described above.
  • the paper treated with the methyl phenyl polysiloxane emulsion was heated at 150 C. for five minutes while the paper treated with the linear methyl polysiloxan was air-dried for about 2 minutes at 70 to C.
  • Pitch tests on each of the treated papers showed that when the aluminum hydroxide was omitted from the methyl phenyl polysiloxane emulsion, the pitch test resulted in tearing of the paper and no release thereof from the pitch surface; the presence of the aluminum hydroxide markedly reduced the adhesion of the paper to the pitch and gave a value of below 1000 grams for the pull required to separate the treated paper from the pitch ring, with no evidence of fiber adhesion.
  • EXAMPLE 4 In this example, 10 parts of the master methylpolysiloxane emulsion described in Example '1 were mixed with 81 parts water and the mixture thoroughly homogenized. To this mixture was added with stirring 0.7 part of an aqueous stannous gluconate solution (containing 14%, by weight, tin) with stirring,- this being equivalent to 2% tin based on the weight of the methylpolysiloxane. A second solution was prepared composed of 23.2 parts of a 10% sodium hydroxide aqueous solution and 40 parts water. To this solution were added approximately 16 parts aluminum nitrate [Al(N0s)3'9H2O]. This addition was carried out with stirring to give a mixture having a pH of 7.
  • Table II additionally describes results of omitting the aluminum hydroxide and of employing 4% zirconium metal, based on the weight of the methylpolysiloxane, in the form of zirconium acetate.
  • Table II shows the evaluation of an aqueous, chain-stopped methyl hydrogen polysiloxane emulsion presently available on the market for release paper purposes, employing 4% zirconium metal and 2% tin metal, the former in the form of zirconium acetate and the latter in the form of stannous gluconate, each based on the weight of the methylpolysiloxane. Otherwise, the formulations were the same and were prepared in the same way.
  • EXAMPLE 5 This example illustrates the ability of reusing antiblocking paper prepared in accordance with the instant invention for a number of cycles. More particularly, the methylpolysiloxane treating emulsion described in Example 1 containing 0.27% aluminum hydroxide and 2% tin based on the weight of the methylpolysiloxane in the form of stannous gluconate and containing 5%, by weight, of the methylpolysiloxane, was used to treat kraft paper in the manner described above. The paper was thereafter dried for 2 minutes at about 70 to 80 C. A similar treating emulsion was prepared with the exception that the aluminum hydroxide was omitted from the treating material. Thereafter, 35-lb.
  • kraft paper was coated and impregnated with the latter emulsion and the paper was heated for two minutes at about 150 C.
  • Each treated paper was subjected to the pitch test described previously for determining the release force required after a number of cycles. It was found that the paper treated with the emulsion from which the aluminum hydroxide was omitted, after the first test required 650 grams force, after the second test required 1500 grams force and after the third test required 1950 grams force; the last two cycles showed unsatisfactory release due to adhesion of the paper fibers to the pitch. In contrast to these results, the paper treated with the emulsion containing the aluminum hydroxide, after the first test showed 85 grams force, after the second test 240 grams force, after the third test 350 grams'force, and after the fourth test showed 650 grams force.
  • EXAMPLE 6 glassine paper and parchment paper were each treated with the methyl polysiloxane emulsion described in Example 2 containing the stannous gluconate and the aluminum hydroxide, employing the same manner of treatment as described in this latter example. Thereafter the papers were dried for 2 minutes at 70 to C. The release properties of each of the samples of paper were tested by applying Scotch tape (manufactured by the Minnesota Mining and Manufacturing Company) to the various surfaces and stripped from the papers and notation made whether any fibers of paper adhered to the tape. In the case of the untreated papers, removal of the tape was either difficult or else carried with it some of the paper fibers. In contrast to this, the tape could be readily removed from the treated papers without apparent fiber adhesion.
  • Scotch tape manufactured by the Minnesota Mining and Manufacturing Company
  • EXAMPLE 7 In this example, a treating emulsion was prepared similarly as that described in Example 1 with the exception that the sodium carboxy methyl cellulose was omitted and, in addition, the aluminum hydroxide was replaced with varying concentrations of aluminum silicate in amounts ranging from 0.2 to 0.8 part aluminum silicate per parts of the treating emulsion. Otherwise, the emulsion including the stannous gluconate and the proportion of ingredients was the same. Thirty-five pound kraft paper was treated similarly as that described in Example 2 employing the emulsions containing the varying concentrations of aluminum silicate. These treated papers were air-dried at a temperature of about 7080 C. for 2 minutes and thereafter tested by means of the abovedescribed pitch test. The following Table III shows the release force in grams for the various papers treated with the emulsions containing the different concentrations of aluminum silicate.
  • the fluid organopolysiloxane is advantageously one which has a ratio of from about 1.8 to 2.2 organic groups, for instance, hydrocarbon groups per silicon atom.
  • organic groups for instance, hydrocarbon groups per silicon atom.
  • at least 50% of the organic groups are lower alkyl groups, e. g., methyl groups.
  • compositions herein described for the above specified purposes are manifold.
  • it is possible to obtain high quality release characteristics for highly adherent materials such as uncured synthetic rubbers, pitch, asphalt, tar, many adhesives and other type of materials.
  • the anti-blocking properties are effective even at low concentrations of organopolysiloxane pickup; the paper treated can be given an air drying which is usually sufficient to bring out the optimum properties of the release paper without the necessity of employing high temperatures which are often impractical to use in paper making establishments.
  • organopolysiloxanes previously available on the market for the same purpose required aging, that is, storing of the treated paper for times as long as 6 Weeks, in order to bring out the optimum release characteristics of the treated paper.
  • the re-release characteristics of cellulosic materials treated in accordance with our invention are highly attractive and up to as many as six releases have been obtained us ing pitch as a medium before any fiber adhesion of the cellulosic paper to the pitch was noted. f considerable importance is the fact that even at high temperatures, the release characteristics are maintained at optimum levels and elevated temperatures do not destroy the release film.
  • compositions for treating cellulosic materials herein described are readily amenable to a single step procedure and are easily regulated and controlled for adjustable organopolysiloxane pickup by minor variations in the formulations.
  • Standard paper making or paper converting equipment is readily employed in connection with the treating operations and no precautions need be taken for any toxic materials which may be contained in the treating emulsions.
  • this treatment also imparts water repellency to the cellulosic material, especially when using zirconium salts.
  • Cellulosic materials treated as described above have a wide range of usefulness.
  • asphalt or high molecular weight organic polymers such as various synthetic rubbers, can be poured hot into containers fashioned from the treated paper or paperboard, and after cooling it will be found that solidified asphalt or polymer is readily and cleanly separated from container walls.
  • Our invention permits paper treated in accordance with our process to be substituted for various fabrics which have heretofore been used in contact with adhesive surfaces of electricians pressure sensitive tape, adhesive tapes used for surgical purposes, and regenerated cellulose tapes carrying a permanent adhesive upon one surface.
  • Vulcanized or unvulcanized sheets of rubber can be prevented from adhering to each other despite the fact that these sheets of rubber are quite sticky and cohesive when in direct contact with each other.
  • Paper treated in accordance with the instant invenion is also useful in lining various boxes of partially prebaked goods such as buns, rolls, and the like and advantage can be taken of the outstanding release properties at elevated temperatures by completing the baking cycle in the original container in which the baked goods are purchased.
  • a composition of matter for rendering cellulosic fibrous sheet material non-adherent towards materials which normally adhere thereto comprising an aqueous emulsion containing a fluid organopolysiloxane, the organic groups of the organopolysiloxane being selected from the class consisting of monovalent hydrocarbon radicals and chlorinated phenyl radicals, from 1.5 to 12% by weight, of an aluminum compound selected from the class consisting of aluminum hydroxide and aluminum silicate, and a metallic salt which in combination with the aluminum compound is capable of reducing the adhering characteristics of the said sheet material treated with the said emulsion and dried, the metallic salt being selected from the class consisting of water-soluble inorganic salts, water-soluble metallo-organic salts, and organopolysiloxanewsoluble metallo-organic salts, in which the metal ion of the metallic salt is selected from the class consisting of titanium, zirconium, tin, lead, zinc, and nickel, the metallic salt being present,
  • a composition of matter for rendering cellulosic fibrous sheet material non-adherent towards materials which normally adhere thereto comprising an aqueous emulsion containing a fluid methylpolysiloxane, from 1.5 to 12%, by weight, of aluminum hydroxide, and a metallic salt which in combination with the aluminum hydroxide is capable of reducing the adhering characteristics of the said sheet material treated with the said emulsion and dried the metallic salt being selected from the class con sisting of water-soluble inorganic salts, water-soluble metalloorganic salts, and organopolysiloxane-soluble metallo-organic salts, in which the metal ion of the metallic salt is selected from the class consisting of titanium, zirconium, tin, lead, zinc, and nickel, the metallic salt being present, by weight, in an amount equal to at least 0.1% based on the weight of the fluid methylpolysiloxane.
  • a composition of matter for rendering cellulosic fibrous sheet material non-adherent towards materials which normally adhere thereto comprising an aqueous emulsion containing a fluid methylpolysiloxane, from 1.5 to 12%, by weight, of aluminum silicate, and a metallic salt which in combination with the aluminum silicate is capable of reducing the adhering characteristics of the said sheet material treated with the said emulsion and dried
  • the metallic salt being selected from the class consisting of water-soluble inorganic salts, water-soluble metallo-organic salts, and organopolysiloxane-soluble metallo-organic salts, in which the metal ion of the metallic salt is selected from the class consisting of titanium, zirconium, tin, lead, zinc, and nickel, the metallic salt being present, by weight, in an amount equal to at least 0.1% based on the weight of the fluid methylpolysiloxane.
  • a composition of matter for rendering cellulosic fibrous sheet material non-adherent towards materials which normally adhere thereto comprising an aqueous emulsion containing a fluid methylpolysiloxane, from 1.5 to 12%, by weight, of aluminum hydroxide, and at least 0.1%, by Weight, based on the weight of the fluid methylpolysiloxane, of zirconium acetate.
  • a composition of matter for rendering cellulosic fibrous sheet material non-adherent towards materials which normally adhere thereto comprising an aqueous emulsion containing a fluid methylpolysiloxane, from 1.5 to 12%, by weight, of aluminum hydroxide, and at least 0.1%, by weight, based on the weight of the fluid methylpolysiloxane, of stannous gluconate.
  • a composition of matter for rendering cellulosic fibrous sheet material non-adherent towards materials which normally adhere thereto comprising an aqueous emulsion containing a fluid methylpolysiloxane, from 1.5 to 12%, by weight, of aluminum silicate, and at least 0.1%, by weight, based on the weight of the fluid methylpolysiloxane, of zirconium acetate.
  • a composition of matter for rendering cellulosic fibrous sheet material non-adherent towards materials which normally adhere thereto comprising an aqueous emulsion containing a fluid methylpolysiloxane, from 1.5 to 10%, by weight, of aluminum silicate, and at least 0.1%, by weight, based on the weight of the fluid methylpolysiloxane, of stannous gluconate.
  • An aqueous emulsion for rendering cellulosic fibrous sheet material non-adherent towards materials which normally adhere thereto comprising, by weight, (1) from to water, (2) from 1 to 20% of a fluid methylpolysiloxane, (3) from 0.01 to 6% of an aluminum compound selected from the class consisting of aluminum hydroxide and aluminum silicate, and (4) a metallic salt selected from the class consisting of water-soluble inorganic salts, water-soluble metallo-organic salts, and organopolysiloxane-soluble metallo-organic salts, in which the metal ion of the metallic salt is selected from the class consisting of titanium, zirconium, tin, lead, Zinc and nickel, the metallic salt being present, by weight, in an amount equal to at least 0.1%, based on the weight of the fluid methylpolysiloxane.
  • An aqueous emulsion for rendering cellulosic fibrous sheet material non-adherent towards materials which normally adhere thereto comprising, by weight, (1) from 80 to 90% water, (2) from 1 to 20% of a fluid methylpolysiloxane, (3) from 0.01 to 6% aluminum hydroxide and (4) at least 0.1%, by weight, based on the weight of the fluid methylpolysiloxane, of stannous gluconate.
  • the method of rendering cellulosic fibrous sheet material non-adherent to materials which normally adhere thereto comprises treating the sheet material with an aqueous emulsion containing, by weight, (1) from 1 to 20% of a fluid organopolysiloxane, the organic groups of the organopolysiloxane being selected from the class consisting of monovalent hydrocarbon radicals and chlorinated phenyl radicals, (2) from 80 to 90% water, (3) from 0.01 to 6% of an aluminum compound selected from the class consisting of aluminum hydroxide and aluminum silicate, and (4) a metallic salt selected from the class consisting of water-soluble inorganic salts, water-soluble metallo-organic salts, and organopolysilox- .ane-soluble metallo-organic salts, in which the metal ion of the metallic salt is selected from the class consisting of titanium, zirconium, tin, lead, zinc and nickel, the metal ion of the metallic salt is selected from the class consisting of titanium, zi
  • metallic salt being present, by weight, in an amount equal to at least 0.1%, based on the weight of the fluid organopolysiloxane.
  • the method of rendering cellulosic fibrous sheet material non-adherent to materials which normally adhere thereto comprises (a) treating the sheet material with an aqueous emulsion containing, by weight, 1) from 1 to 20% of a fluid methylpolysiloxane, ('2) from to water, (3) from 0.01 to6% of aluminum hydroxide, and (4) a metallic salt which in combination with the aluminum hydroxide efiects optimum-reduction of the sticking characteristics of the treated cellulosic material.
  • the metallic salt selected from therclass consisting of water-soluble inorganic salts, water-soluble metallo-organic salts, and organopolysiloxane soluble metallo-organic salts, in which the metal ion of the metallic salt is selected from the class consisting of titanium, zirconium, tin, lead, zinc and nickel, the metallic salt being present, by weight, in an amount equal to at least 0.1% based on the weight of the fluid methylpolysiloxane and (b) drying the treated cellulosic material.
  • the method of rendering cellulosic fibrous sheet material non-adherent to materials which normally adhere thereto comprises (a) treating the sheet'material with an aqueous emulsion containing, by weight, 1) from 1 to 20% of a fluid methylpolysiloxane, (2) from 80 to 90% water, (3) from 0.01 to 6% of aluminum hydroxide, and (4) at least 0.1%, by weight, based on the weight of the fluid methylpolysiloxane, of stannous gluconate, and (b) drying the treated cellulosic material.

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US416422A 1954-03-15 1954-03-15 Organopolysiloxane composition for rendering cellulosic materials nonadherent and method of applying same Expired - Lifetime US2803613A (en)

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GB6486/55A GB792845A (en) 1954-03-15 1955-03-04 Organopolysiloxane compositions for rendering cellulosic materials non-adherent
FR1153257D FR1153257A (fr) 1954-03-15 1955-03-09 Procédé de traitement des matériaux cellulosiques pour les rendre non adhérisants

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2891920A (en) * 1955-01-26 1959-06-23 Dow Corning Polymerization of organopolysiloxanes in aqueous emulsion
US2927870A (en) * 1956-08-28 1960-03-08 Dow Corning Zirconium acetate-zinc acetate catalyzed organohydrogenosiloxane emulsions and the treatment of fabrics therewith
US3079281A (en) * 1959-03-16 1963-02-26 Dow Corning Silicone resin solutions and method for coating with same
US3098836A (en) * 1963-07-23 Organopolysiloxane rubber stabilized
DE1175066B (de) * 1957-08-22 1964-07-30 Wacker Chemie Gmbh Impraegniermittel fuer Zigarettenpapier zur Verhuetung der Fleckenbildung
US3280732A (en) * 1960-12-06 1966-10-25 Elliott Business Machines Inc Stencil construction
US3300330A (en) * 1962-10-09 1967-01-24 Johnson & Johnson Carrier sheet containing on opposite sides a formaldehyde modified starch release coating and a formaldehyde modified starch tacky coating
US4401498A (en) * 1981-01-23 1983-08-30 A.Kettenbach Fabrik Chemischer Erzeugnisse, Dental-Spezialitaten GmbH & Co. KG. Process for producing reciprocal adhesion at the interface between two contacting layers with aluminum hydroxide being included in one of said layers
EP0396789A1 (de) * 1989-05-09 1990-11-14 Kämmerer Gmbh Verfahren zur Herstellung von Trennrohpapieren mit speziellen Oberflächenstrichen
US5004502A (en) * 1990-08-23 1991-04-02 Ramzan Chaudhary M Non-irritating detackifying composition
EP1566403A3 (en) * 2004-02-20 2005-09-28 Carl Freudenberg KG Silicone gasket compositions
WO2012087661A2 (en) 2010-12-20 2012-06-28 3M Innovative Properties Company Coating compositions comprising non-ionic surfactant exhibiting reduced fingerprint visibility
US9441135B2 (en) 2012-06-19 2016-09-13 3M Innovative Properties Company Additive comprising low surface energy group and hydroxyl groups and coating compositions
US9701850B2 (en) 2012-06-19 2017-07-11 3M Innovative Properties Company Coating compositions comprising polymerizable non-ionic surfactant exhibiting reduced fingerprint visibility
US10731056B2 (en) 2017-03-17 2020-08-04 3M Innovative Properties Company Adhesive articles and methods of making the same
CN119099182A (zh) * 2024-09-04 2024-12-10 江苏耀鸿电子有限公司 一种复合填料填充型高韧性耐腐蚀覆铜板及其制备方法

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* Cited by examiner, † Cited by third party
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DE3422130A1 (de) * 1984-06-14 1985-12-19 Rolf 8000 München Blickling Beschichtetes papier und verfahren zu seiner herstellung

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US2460795A (en) * 1944-10-03 1949-02-01 Corning Glass Works Method for making rubbery polymeric organo-siloxane compositions
US2588828A (en) * 1948-12-11 1952-03-11 Johns Manville Composition for and method of producing coated cement surfaces and the product resulting therefrom

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2460795A (en) * 1944-10-03 1949-02-01 Corning Glass Works Method for making rubbery polymeric organo-siloxane compositions
US2588828A (en) * 1948-12-11 1952-03-11 Johns Manville Composition for and method of producing coated cement surfaces and the product resulting therefrom

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3098836A (en) * 1963-07-23 Organopolysiloxane rubber stabilized
US2891920A (en) * 1955-01-26 1959-06-23 Dow Corning Polymerization of organopolysiloxanes in aqueous emulsion
US2927870A (en) * 1956-08-28 1960-03-08 Dow Corning Zirconium acetate-zinc acetate catalyzed organohydrogenosiloxane emulsions and the treatment of fabrics therewith
DE1175066B (de) * 1957-08-22 1964-07-30 Wacker Chemie Gmbh Impraegniermittel fuer Zigarettenpapier zur Verhuetung der Fleckenbildung
US3079281A (en) * 1959-03-16 1963-02-26 Dow Corning Silicone resin solutions and method for coating with same
US3280732A (en) * 1960-12-06 1966-10-25 Elliott Business Machines Inc Stencil construction
US3300330A (en) * 1962-10-09 1967-01-24 Johnson & Johnson Carrier sheet containing on opposite sides a formaldehyde modified starch release coating and a formaldehyde modified starch tacky coating
US4401498A (en) * 1981-01-23 1983-08-30 A.Kettenbach Fabrik Chemischer Erzeugnisse, Dental-Spezialitaten GmbH & Co. KG. Process for producing reciprocal adhesion at the interface between two contacting layers with aluminum hydroxide being included in one of said layers
EP0396789A1 (de) * 1989-05-09 1990-11-14 Kämmerer Gmbh Verfahren zur Herstellung von Trennrohpapieren mit speziellen Oberflächenstrichen
US5004502A (en) * 1990-08-23 1991-04-02 Ramzan Chaudhary M Non-irritating detackifying composition
EP1566403A3 (en) * 2004-02-20 2005-09-28 Carl Freudenberg KG Silicone gasket compositions
WO2012087661A2 (en) 2010-12-20 2012-06-28 3M Innovative Properties Company Coating compositions comprising non-ionic surfactant exhibiting reduced fingerprint visibility
US9441135B2 (en) 2012-06-19 2016-09-13 3M Innovative Properties Company Additive comprising low surface energy group and hydroxyl groups and coating compositions
US9701850B2 (en) 2012-06-19 2017-07-11 3M Innovative Properties Company Coating compositions comprising polymerizable non-ionic surfactant exhibiting reduced fingerprint visibility
US9803042B2 (en) 2012-06-19 2017-10-31 3M Innovative Properties Co. Additive comprising low surface energy group and hydroxyl groups and coating compositions
US10731056B2 (en) 2017-03-17 2020-08-04 3M Innovative Properties Company Adhesive articles and methods of making the same
CN119099182A (zh) * 2024-09-04 2024-12-10 江苏耀鸿电子有限公司 一种复合填料填充型高韧性耐腐蚀覆铜板及其制备方法

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