US2985545A - Method of rendering cellulosic material non-adherent and article produced thereby - Google Patents
Method of rendering cellulosic material non-adherent and article produced thereby Download PDFInfo
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- US2985545A US2985545A US72396458A US2985545A US 2985545 A US2985545 A US 2985545A US 72396458 A US72396458 A US 72396458A US 2985545 A US2985545 A US 2985545A
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- 239000000463 material Substances 0.000 title claims description 43
- 238000000034 method Methods 0.000 title claims description 29
- 238000009877 rendering Methods 0.000 title claims description 8
- 230000001464 adherent effect Effects 0.000 title description 9
- -1 POLYDIMETHYLSILOXANE Polymers 0.000 claims description 115
- 229920001296 polysiloxane Polymers 0.000 claims description 78
- 239000000839 emulsion Substances 0.000 claims description 77
- 239000001257 hydrogen Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 29
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 25
- 239000003995 emulsifying agent Substances 0.000 claims description 25
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 15
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 15
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000000123 paper Substances 0.000 description 84
- 239000000203 mixture Substances 0.000 description 44
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 25
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 22
- 230000001070 adhesive effect Effects 0.000 description 20
- 239000000853 adhesive Substances 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 17
- 239000010426 asphalt Substances 0.000 description 13
- 239000004615 ingredient Substances 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 239000011088 parchment paper Substances 0.000 description 10
- 238000011282 treatment Methods 0.000 description 10
- 239000008096 xylene Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000013508 migration Methods 0.000 description 9
- 230000005012 migration Effects 0.000 description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011087 paperboard Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000003106 tissue adhesive Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000001617 migratory effect Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940074323 antara Drugs 0.000 description 1
- 235000015173 baked goods and baking mixes Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 235000021438 curry Nutrition 0.000 description 1
- 229920005565 cyclic polymer Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- YMTINGFKWWXKFG-UHFFFAOYSA-N fenofibrate Chemical compound C1=CC(OC(C)(C)C(=O)OC(C)C)=CC=C1C(=O)C1=CC=C(Cl)C=C1 YMTINGFKWWXKFG-UHFFFAOYSA-N 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical class CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/59—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
-
- 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]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
-
- 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
Definitions
- This invention is concerned with rendering cellulosic materials non-adherent to various organic solids. More particularly, the invention is concerned with a process for rendering paper or paperboard non-adherent to normally adherent materials such as, for instance, asphalts, bitumen, tars, waxes, parafiin solids, flour-containing pastes and frozen foodstuffs, and other high molecular weight polymers, which process comprises treating the said cellulosic material with an aqueous emulsion containing as essential ingredients (1) a linear polydimethylsiloxane containing terminal silicon-bonded hydroxy groups, (2) a small amount of a methyl hydrogen polysiloxane having the formula ononnmsio 2 where n has an average value of from 1.0 to 1.5, m has an average value of from 0.75 to 1.25, and the total of m+n is from 2.0 to 2.25, inclusive, and (3) a metallic salt selected from the class consisting of dibuty
- 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, other high molecular weight organic polymers used as adhesives, etc.
- organic compositions as asphalt or pitch, tar, various unvulcanized rubbers, particularly synthetic rubbers, other high molecular weight organic polymers used as adhesives, etc.
- 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 capable of being 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 aifect the constitution of the asphalt.
- anti-blocking paper or release paper
- One method for treating the paper to render it anti-blocking compirses treating the paper in a three-coat operation with (l) finely divided clay and casein, ,(2) finely divided clay, and (3) polyvinyl acetate.
- Su ch 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 material to render it non-adherent, particularly to asphalt, and to permit it to be readily removed from direct contact with the latter involves depositing a double coating of cellulosic material, the first 2,935,545 Patented May 23, 1961 ice coating being of clay and the second coating being of methyl cellulose and starch.
- US. Patent 2,588,367 describes'the use of methyl hydrogen polysiloxanes in combination with water-soluble cellulose others 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 adhesive 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, e.g., by storage before it is useful for release purposes; this is necessary because accelerated aging by high temperature treatment is not usually available commercially in paper-treating establishments.
- paper such as parchment paper cannot be heated above 125 C. Without deleteriously affecting the paper.
- the abhesive characteristics i.e., the release properties
- the abhesive characteristics tend to decrease with time so that, after long term storage, such treated paper no longer shows adhesive characteristics.
- release paper treated in this manner obviates the various difficulties recited above. What is even more important, release paper treated with these compositions shows no evidence of migration of the organopolysiloxane therein to the surface undesirably to contaminate the material with which the release paper may come in contact.
- compositions which I have found to be so eminently suitable in the practice of the present invention comprise an aqueous emulsion composed of (1) a linear polydimethylsiloxane having terminal silicon-bonded hydroxyl groups, (2) a methyl hydrogen polysiloxane, and (3) a small amount of two tin salts, either alone or together, selected from the class consisting of dibutyl tin 'dilaurate and dibutyl tin diacetate.
- hydroxy chain-stopped polydimethylsiloxanes employed in the practice of the present invention are those having the general formula where n is an integer greater than 1, for instance, from 25 to 100,000. These polydimethylsiloxanes containing -poises when measured at 25 C.
- polydirnethylsiloxanes may be prepared by any one of several well-known methods. "When making the highly viscous polydimethylsiloxanes, such compositions may be obtained by hydrolyzing dimethyldichlorosilane with water and thereafter condensing the hydrolysis product with either acidic or alkaline catalysts such as bydrochloric acid, sulfuric acid, potassium hydroxide, etc. Alternatively, one may heat cyclicpolymers of the formula where 'm is an integer equal tofrom 3'to6, for'in stance, 'octamethylcyclotetrasiloxane, with an alkaline catalyst such as potassium hydroxide, cesium hydroxide, etc.
- acidic or alkaline catalysts such as bydrochloric acid, sulfuric acid, potassium hydroxide, etc.
- alkaline catalyst such as potassium hydroxide, cesium hydroxide, etc.
- an amount equal, by Weight, to from about 0.001 to 0.1% based on the weight of theoctamethylcyclotetrasiloxane) at temperatures of from 125 to 175 C. for times ranging from about 15 minutes to 2 hours or more,
- An alternative method for making the linear organo- 'poly siloxane containing terminal silicon-bonded hydroxy groups comprises adding water to the high molecular weight polymer described above in such amount that when heated at elevated temperatures, for instance, 150 to 170 C., the viscosity is reduced to the desired level of 50 to 100,000 c ntip'oises.
- the amount of water used will vary depending upon such factors as the molecular weight of the polymer being treated, the time and temperature at which the mixture of high molecular weight organopolysiloxane and Water will be heated, the ultimate viscosity desired, etc. i
- the amount of water used to reduce the molecular weight can be readily determined. For instance, one can obtain a linear fluid methylpolysiloxane containing terminal silicon-bonded hydroxy groups and having a viscosity of from 1,000 to 2,000 centipoises at 25 C. by heating a high molecular weight methylpolysiloxane (prepared in accordance with the directions above) of about 2,000,000 centipoise viscosity with only 0.5%, by weight, thereof water for about 2 hours at 150 to 170 C.
- methyl hydrogen polysiloxane corresponding to the formula where m and n have the meanings set forth above, may
- methyl hydrogen polysiloxanes may be either linear or cyclic polysiloxanes.
- these methyl hydrogen polysiloxanes if in linear form, may correspond to the general formula LH l. where p'is an integer greater than 1, e.g., 10 to 1,000, or may have intercondensed CH SiO units (in very small molar concentrations) intermediate the trimethylsiloxy units, or even intercondensed dimethylsiloxy units having the formula
- the molar concentration of such dimethylsiloxy units should not exceed more than 10 mol percent, and preferably is of the order of from 0 to 5 mol percent of the total number of siloxy units in the linear polysiloxane.
- the methyl hydrogen polysiloxane may be a cyclic methylpolysiloxane of the formula V (Cl-lgSiI-IO) where q is a whole number equalto from 3 to 10 or more. More particular directions for preparing the linear methyl hydrogen polysiloxane and'the cyclic methyl hydrogen polysiloxane may be found in Wilcock Patent 2,491,843and in Sauer Patents 2,595,890 and 2,595,891, all 10f the aforesaid patents being assigned to the same assignee as the present invention.
- dibutyl tin dilaurate and dibutyl tin diacetate gave minimum migration of the methylpolysiloxane and were able to be used in lower concentrations than when one.
- employed metallicsoaps even tin soaps, such as tin octoate, tin naphthenate, tin "oleate, and even such a metallic salt as butyl tin trioctoate, which is closely akin to dibutyl tin dilaurate and dibutyl tin diacetate.
- the above essential ingredients used'for, treating cellulosic'materials to render them abhesive in the form of a coating material which is non-migratory as far as the linear methylpolysiloxane containing terminal siliconbonde'd hydroXy groups is concerned, are employed in the form of an aqueous emulsion (with or without solvent contained therein), which can be used as a treating bath for cellulosic materials such as cellulosic sheetmaterial, parchment paper, kraft paper, linen rag paper, rice paper,
- sheeting or boxing materials such as paperboard, cardboard, pulpboard, pasteboard.
- aqueous emulsion employed in the practice of the present invention advantageously comprises, by Weight, the following:
- the amount of the specific dibutyl tin salt employed will depend upon such factors as, for instance, its effect on the stability of the emulsion,'the type of polydimethylsiloxane and methyl hydrogen polysiloxa'ne used, the type of paper to which the treating composition will be -applied, the'solubility 'of the tin salt, as well as the medium in which the tin salt willbe' used, the' treating conditions including temperature and time "of'tr'e'atin'ent,
- the emulsifying agent used is important if one is to obtain a stable emulsion which, on application to paper, will provide the release required without migration of the polydimethylsiloxane. It has been found unexpectedly that an emulsifying agent which is advantageously employed comprises polyvinyl alcohol, and this emulsifying agent has given satisfactory properties in the treated paper.
- the usual emulsifying agent such as Triton X-l00 (isooetyl phenyl ether of polyethylene glycol, manufactured and sold by Rohm and Haas Company, Philadelphia, Pa.) and Igepal CO- 530 (polyoxyethylated nonyl phenol containing 7 mols ethylene oxide manufactured and sold by Antara Chemicals, Division of General Aniline & Film, New York, N.Y.) are not satisfactory because they undesirably reduce the release characteristics of the treated paper.
- Triton X-l00 isooetyl phenyl ether of polyethylene glycol, manufactured and sold by Rohm and Haas Company, Philadelphia, Pa.
- Igepal CO- 530 polyoxyethylated nonyl phenol containing 7 mols ethylene oxide manufactured and sold by Antara Chemicals, Division of General Aniline & Film, New York, N.Y.
- 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 0.1 to 3%, by weight, based on the weight of the entire treating aqueous emulsion. 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 preferably 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.
- One method for making the emulsion type treating compositions herein described comprises, first, dissolving the emulsifying agent, e.g., polyvinyl alcohol in water, and then adding slowly the polydimethylsiloxane and the methyl hydrogen polysiloxane. This mixture of ingredients is thoroughly homogenized (or colloided) until the polydimethylsiloxane and methyl hydrogen polysiloxane are intimately dispersed throughout the water phase. This material is often referred to as a master emulsion.
- the emulsifying agent e.g., polyvinyl alcohol
- This mixture of ingredients is thoroughly homogenized (or colloided) until the polydimethylsiloxane and methyl hydrogen polysiloxane are intimately dispersed throughout the water phase.
- This material is often referred to as a master emulsion.
- An aqueous emulsion using, for example, polyvinyl alcohol as the emulsifying agent is prepared of the dibutyl tin salt similarly as above except that preferably some solvent, such as xylene, is added to the tin salt prior to its addition to the solution of water and polyvinyl alcohol.
- This tin salt mixture is also homogenized to form an emulsion and in this form is added to the master emulsion in the preparation of the treating bath.
- the master silicone emulsion is preferably diluted to use concentrations with an additional amount of water prior to incorporation of the catalyst emulsion.
- organic solvents are not precluded and under some circumstances may be desirable. If any organic solvent is employed, it is preferable that one employ those which are easily volatilized at the temperature at which treatment of the paper will take place.
- the emulsion should be kept at a relatively cool temperature, e.g., around room temperature, prior to using in order to maintain its stability.
- 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 a 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 material is advantageously dried by passing the treated paper over heated rolls (or cans) maintained at temperatures of about to 175 C. for from about 10 seconds to 3 minutes or more.
- heated rolls or cans
- the use of circulating hot air at temperatures of from to 160 C. may also be used for times of from 30 seconds to 5 minutes to effect curing of the treated paper.
- This drying step will bring out the optimum release properties of the paper without further heat treatment. Of equal significance is the fact that these optimum release properties are immediately available without requiring aging or storage of the treated paper. Obviously, the higher the temperature, the shorter the period of exposure of the paper for removing the water and drying the paper.
- polydimethylsiloxane containing terminal siliconbonded hydroxyl groups (hereinafter referred to as polydimethylsiloxane) used in the following examples had a viscosity of about 3,000 centipoises when measured at 25 C. and had a ratio of approximately two methyl groups per silicon atom.
- This high viscosity composition was obtained by heating octamethylcyclotetrasiloxane with about 0.001%, by weight, thereof of potassium hydroxide for about 2 to 4 hours at about C. until a highly viscous (about 3,000,000 centipoises) benzene-soluble product was obtained having slight flow at room temperature. About 0.5% thereof water was added and the mixture heated for about two hours at to C.
- This material was a linear fluid polydimethylsiloxane having terminal silicon-bonded hydroxyl groups.
- a devolatilized polydimethylsiloxane (so designated) was also used wherein all volatiles up to at most 1% were removed by heating the polydimethylsiloxane under vacuum of about 15 mm. at 135 C.
- the methyl hydrogen polysiloxane used in the following examples was a linear trimethyl silyl chain-stopped polysiloxane described in Wilcock Patent 2,491,843, and had a viscosity of 100 centipoises when measured at 25 C. This material was obtained by cohydrolyzing 5 parts (OH SiCl and 95 parts CH SiHCl
- the release characteristics of the treated paper were determined by pressing (by hand) a strip of surgical adhesive tape on the surface of the treated paper and lifting the tape from the paper; evaluation of the release was deter mined by assigning numerical values as follows:
- the pull required to separate the adhesive surface from itself (evaluated subjectively as to poor, fair, fair-good, and good tack) compared with tape which had not been in contact with release paper, was used as a measure of detackification of the tape and thus as a measure of migration of the silicone material.
- the methylpolysiloxane pickup was within the range from about 0.4% to 2%, by weight, based on the weight of the parchment paper which was treated in every instance in the following examples.
- EXAMPLE 1 This example illustrates the preparation of treating baths in the form of emulsions employing a high viscosity polyvinyl alcohol manufactured and sold-by E. I. du Pont de Nemours Co., Wilmington, Delaware, under the name Elvanol 50-42, and made by partially hydrolyzing polyvinyl acetate (8689% hydrolyzed).
- a master emulsion was prepared by mixing together on a weight basis, based on the total weight of the emulsion, amounts of the devolatilized hydroxy chain-stopped polydimethylsiloxane ranging from 28.5 to 30%, from 0.3 to 1.5% of the methyl hydrogen polysiloxane, and from 0.63 to 1.26% polyvinyl alcohol (as the emulsifying agent).
- xylene was added to the mixture of ingredients. This mixture was then diluted further with Water to make the total percent weight equal to 100%, and passed through a homogenizer to obtain a homogeneous creamy emulsion.
- Each emulsion was thereafter mixed with an aqueous emulsion of the organometallic salt employed in each instance, and this mixture was further diluted with water and intimately mixed to give a homogeneous emulsion treating bath in which the total weight of the polydimethylsiloxane and the methyl hydrogen polysiloxane comprised about by weight, of the total emulsion treating bath.
- the particular dibutyl tin salt used was employed in such amount that there was present in the treating bath composition from 0.2 to 0.4% tin, based on the total weight of the polydimethylsiloxane and methyl hydrogen polysiloxane.
- Tables IA and IB below show the effects on treated parchment paper which was immersed in the emulsion bath, the treated paper removed and passed between squeeze rolls to remove excess treating composition, and thereafter the paper was dried by passing it over a heated cylindrical roll maintained at a temperature of from l10113 C.-for about 3 minutes. This method for treatment of parchment paper was followed in all the following examples as well:
- EXAMPLE 2 In this example, a master emulsion was prepared similarly as in Example 1, employing on a weight basis 28.5% of the devolatilized hydroxy chain-stopped polydimethylsiloxane, 1.5% of the trimethyls'ilyl chain-stopped methyl hydrogen polysiloxane, 7.5% xylene, 1.26% polyvinyl alcohol, and the balance (up to water.
- the treating bath composition (made by diluting the master emulsion) used to treat the parchment paper again comprised, as in Example 1, 10 weight percent of the mixture of the hydroxy chain-stopped methylpolysiloxane and the methyl hydrogen polysiloxane, and dibutyl tin dilaurate as a catalyst.
- Three treating bath compositions were prepared, of which the emulsions used for treating purposes contained varying amounts of catalyst concentration of dibutyl tin dilaurate, which was added in the form of an emulsion similarly as in Example 1.
- the amounts of catalyst used were 0.2% tin, 0.4% tin, and 4.0% tin, each in the form of dibutyl tin dilaurate.
- the treated paper was treated and dried similarly as was done in Example 1, and its performance asto release and tack were determined. It was found that regardless of the catalyst concentration, the release in each of the three instances was 0, and the tack was Good. This example illustrates the Wide range of catalyst concentration which can be employed in the practice of the present invention.
- the following example illustrates that the incorporation of a solvent such as xylene (benzene, toluene, 'etc., can also be used) in the treating emulsion improves the stability of the emulsion, and thus allows the treating bath to remain effective over a longer period of time with retention of optimum properties in the treated paper.
- a solvent such as xylene (benzene, toluene, 'etc., can also be used
- EXAMPLE 3 In this example, master silicone emulsions were prepared similarly as in Example 1, and each of these master silicone emulsions was mixed with a catalyst emulsion in which the catalyst was dibutyl tin dilaurate; this emulsion mixture was diluted with water to give a treating bath emulsion composition which was used to treat parchment paper similarly as was done in Example 1. In all the master emulsions, 1.26% polyvinyl alcohol was used as the emulsifying agent, based on the weight of the emulsion.
- Table IIA shows the composition of the master silicone emulsion, the balance of the emulsion being water.
- Table 1113 shows the performance data on paper treated with the emulsions after the emulsion baths had been allowed to remain at room temperature for various lengths of time; also Table IIB shows the condition of" the baths, i.e., their stability, after they were pumped through pumping equipment as might be encountered in plant usage where the emulsion may be prepared in one part of the plant and then pumped to another part of the plant where it is to be used.
- Table IIB TREATING BATH COMPOSITION This example illustrates the importance of choosing the proper emulsifying agent.
- polyvinyl alcohol is admirably suited for the purpose.
- all non-ionic emulsifiers, of which polyvinyl alcohol is an example are not satisfactory.
- EXAMPLE 4 In this example, master silicone emulsions were prepared similarly as was done in Example 1 and the other examples, employing on a weight basis 28.5% of the devolatilized hydroxy chain-stopped polydimethy1siloxane, 1.5% of the trimethylsiloxy chain-stopped methyl hydrogen polysiloxane, and 7.5% xylene, the balance being water with the exception of the emulsifying agent which was used in small, stipulated amounts. Various emulsifying agents were employed to make the-master silicone emulsion.
- Table III shows the particular emulsifier used, the concentration of the emulsifier in the master silicone emulsion, as well as the performance data of the particular treating baths, depending upon the specific emulsifying agent employed.
- the diluted master silicone emulsions contained by weight, of the mixture of the devolatilized polydimethylsiloxane and the methyl hydrogen polysiloxane, together with 0.2%, by weight,
- nonyl phenols non-ionic. 34 Fatty alcohol amine sulfate 1.0 0 Do.
- EXAMPLE 5 This example illustrates the versatility of using various concentrations of the mixture of the hydroxy chainstopped methylpolysiloxane and the methyl hydrogen polysiloxane in a treating bath composition. More particularly, a master silicone emulsion was prepared similarly as was done in Example 1, by mixing together 28.5% of the devolatilized hydroxy chain-stopped methylpolysiloxane, 1.5% of the methyl hydrogen polysiloxane, 7.5% xylene, 1.26% polyvinyl alcohol, and the balance (up to 100%) water.
- This master silicone emulsion was then diluted further with water in such quantities that the mixture of the two polysiloxanes in the master silicone emulsion ranged from about 6 to 30%, by weight, of the total weight of the treating emulsion, employing in each instance 0.2%, by weight, tin'based on the weight of the two polysiloxanes, in the form of 'dibutyl tin dilaurate.
- Parchment paper was treated similarly as was done in Example 1 and the performance of the treated paper was determined as evidenced -by its release and tack.
- Table IV shows the concentration of the mixture of polysiloxanes in the treating bath composition as well as the release and tack of the treated paper.
- the following example illustrates that good release with no silicone migration is obtained over a wide range of viscosity of the hydroxy chain-stopped polydimethylsiloxane polymers.
- the range of viscosity evaluated, 600 centipoisesto 94,500 centipoises, measured at about 25 C., is not intended to exclude lower and higher viscosities.
- EXAMPLE 6 various master silicone emulsions were prepared from the devolatilized hydroxy chainstopped methyl polysiloxanes employing in each instance on a weight basis 28.5% of the hydroxy chain-stopped methylpolysiloxane, 1.5% of the methyl hydrogen polysiloxane, 7.5 xylene, and 1.26% polyvinyl alcohol as the emulsifying agent, the balance being water.
- various viscosities of the hydroxy chain-stopped methylpolysiloxanes were employed.
- Each master silicone emulsion was thereafter diluted further with water to obtain a treating bath composition, of which 10%, by weight, comprised the mixture of the devolatilized polydimethylsiloxane and the methyl hydrogen polysiloxane; to this was added about 0.2%, by weight, tin based on the combined Weight of Table V Test No. Viscosity, Release Tack Oentipoises 600 -Gocd 1 This polydimcthylsiioxane was not devolatilizcd...
- the master emulsion may generally comprise the following ingredients, by weight:
- the tin salt emulsion may comprise the following ingredients, by weight:
- the treating bath emulsion-in general used to treat the parchment paper may comprise thefollowing:
- the concentration of the dibutyl tin dilaurate or dibutyl tin diacetate (or mixturesof such tin salts) also maybe varied within wide limits depending onthefactors recited previously.
- the amount of organopolysiloxane which is picked up by the cellulosic paper material as a result of the treatment with the emulsion of the organopolysiloxanes dependsupon'such factors as'the absorbency of the cellulosic material, the method of application, the concentration of organopolysiloxanes in the emulsion, etc.
- the amount of organopolysiloxane pickup ranges from about 0.1 to about 5%, or mo-re, based on the dry weight of the cellulosic material, the preferred pickup being within the range of about 0.4 to 2%organopolysiloxane.
- larger amounts or organopolysiloxane pickup may be employed,'bujt generally this is not necessary and usually serves merelyto increase the cost of the treatment.
- compositions hereindescribed for the above specified purposes are'manifold. 'Of particular importance is the fact that when the above combination of ingredients is applied to paper, in, addition to imparting adhesive characteristics thereto, the organepolysiloxane (that is, the polydime'thylsiloxane and the methyl hydrogen polysiloxane) vcontent in the paper is substantially non-migratory and will not affect or be transferred to the surfaces of compositions from which the adhesive paper must be readily separated.
- organepolysiloxane that is, the polydime'thylsiloxane and the methyl hydrogen polysiloxane
- the adhesive characteristics of the treated paper are substantially the same even after the paper is stored for long periods of time; in contrast to this, paper treated with prior organopolysiloxane compositions used to render the paper adhesive have suifered severe losses in their abhesive properties after storage for any length of time, for instance, even after only 6 months.
- 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 formulations.
- Standard paper makingor 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.
- My invention permits paper treated in accordance with my process to be substituted for various materialswhich 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 invention is also useful in lining various boxes of partially prebaked goods, such 13 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.
- the method for rendering cellulosic fibrous sheet material non-adherent to surfaces which normally adhere thereto comprises treating the cellulosic fibrous sheet material with an aqueous emulsion treating bath containing, by weight, the following sole active ingredients:
- the method for rendering cellulosic fibrous sheet material non-adherent to surfaces which normally adhere thereto comprises treating cellulosic fibrous sheet material with an aqueous emulsion treating bath containing, by weight, the following sole active ingredicuts:
- the method for rendering cellulosic fibrous sheet material non-adherent to surfaces which normally adhere thereto comprises treating the cellulosic fibrous sheet material with an aqueous emulsion treating bath containing, by Weight, the following sole active ingredients:
Description
METHOD OF RENDERING 'CELLULOSIC MATE- RIAL NON-ADHERENT AND ARTICLE PRO- DUCED THEREBY Herbert J. Leavitt, Schenectady, N.Y., assignor to General Electric Company, a corporation of New York No Drawing. Filed Mar. 26, 1958, Ser. No. 723,964
4 Claims. ((Jl. 117-143) This invention is concerned with rendering cellulosic materials non-adherent to various organic solids. More particularly, the invention is concerned with a process for rendering paper or paperboard non-adherent to normally adherent materials such as, for instance, asphalts, bitumen, tars, waxes, parafiin solids, flour-containing pastes and frozen foodstuffs, and other high molecular weight polymers, which process comprises treating the said cellulosic material with an aqueous emulsion containing as essential ingredients (1) a linear polydimethylsiloxane containing terminal silicon-bonded hydroxy groups, (2) a small amount of a methyl hydrogen polysiloxane having the formula ononnmsio 2 where n has an average value of from 1.0 to 1.5, m has an average value of from 0.75 to 1.25, and the total of m+n is from 2.0 to 2.25, inclusive, and (3) a metallic salt selected from the class consisting of dibutyl tin dilaurate and dibutyl tin diacetate.
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, other high molecular weight organic polymers used as adhesives, etc. For optimum use of these cellulosic containers, it is essential that they be capable of being readily separated or stripped from the cargo contained therein. Thus, in the transportation and shipment of asphalt used for roofing purposes, 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. At its destination of use, it is essential that this paper, in whatever form, be capable of being 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 aifect the constitution of the asphalt.
Various treatments have been accorder these types of papers which are often referred to as anti-blocking paper (or release paper). One method for treating the paper to render it anti-blocking compirses treating the paper in a three-coat operation with (l) finely divided clay and casein, ,(2) finely divided clay, and (3) polyvinyl acetate. Su ch 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 material to render it non-adherent, particularly to asphalt, and to permit it to be readily removed from direct contact with the latter, involves depositing a double coating of cellulosic material, the first 2,935,545 Patented May 23, 1961 ice coating being of clay and the second coating being of methyl cellulose and starch.
However, all the foregoing methods have been excedingly expensive and in many respects have not been too satisfactory, since too often it has been found that these adhesive materials, particularly asphalt, which apparently has a high affinity for cellulosic fibers, stick to the anti-blocking paper so that great difficulty is encountered in attempting to separate the latter from the asphalt.
US. Patent 2,588,367 describes'the use of methyl hydrogen polysiloxanes in combination with water-soluble cellulose others 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 adhesive 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, e.g., by storage before it is useful for release purposes; this is necessary because accelerated aging by high temperature treatment is not usually available commercially in paper-treating establishments. Furtheremore, paper such as parchment paper cannot be heated above 125 C. Without deleteriously affecting the paper. Moreover, after treatment of paper with the methyl hydrogen polysiloxane, the abhesive characteristics (i.e., the release properties) tend to decrease with time so that, after long term storage, such treated paper no longer shows adhesive characteristics.
In addition to the difficulties described above, particularly when using methylpolysiloxanes for anti-adhesion (abhesive) purposes, and even when using the-more currently employed methyl hydrogen polysiloxanes for this purpose, it has been found that although release properties are improved, nevertheless there is an undesirable tendency of the organopolysiloxane in the abhesive paper to migrate to the surface of the paper, thereby coming in contact with the material which it is desired to rereduced as a result of this migration of the organopolysiloxane from the treated release paper to the adhesive.
Unexpectedly, I have discovered that a certain mixture of ingredients can be used to treat release paper, and paper treated in this manner obviates the various difficulties recited above. What is even more important, release paper treated with these compositions shows no evidence of migration of the organopolysiloxane therein to the surface undesirably to contaminate the material with which the release paper may come in contact. The compositions which I have found to be so eminently suitable in the practice of the present invention comprise an aqueous emulsion composed of (1) a linear polydimethylsiloxane having terminal silicon-bonded hydroxyl groups, (2) a methyl hydrogen polysiloxane, and (3) a small amount of two tin salts, either alone or together, selected from the class consisting of dibutyl tin 'dilaurate and dibutyl tin diacetate.
The hydroxy chain-stopped polydimethylsiloxanes employed in the practice of the present invention are those having the general formula where n is an integer greater than 1, for instance, from 25 to 100,000. These polydimethylsiloxanes containing -poises when measured at 25 C.
. These polydirnethylsiloxanes may be prepared by any one of several well-known methods. "When making the highly viscous polydimethylsiloxanes, such compositions may be obtained by hydrolyzing dimethyldichlorosilane with water and thereafter condensing the hydrolysis product with either acidic or alkaline catalysts such as bydrochloric acid, sulfuric acid, potassium hydroxide, etc. Alternatively, one may heat cyclicpolymers of the formula where 'm is an integer equal tofrom 3'to6, for'in stance, 'octamethylcyclotetrasiloxane, with an alkaline catalyst such as potassium hydroxide, cesium hydroxide, etc. (in "an amount equal, by Weight, to from about 0.001 to 0.1% based on the weight of theoctamethylcyclotetrasiloxane) at temperatures of from 125 to 175 C. for times ranging from about 15 minutes to 2 hours or more,
'andthereafter, if desired, removing or neutralizing the alkaline catalyst to yield a polydimethylsiloxane of Formula Ihaving a viscosity of from about 700,000 to 2,000,000 centipoises or more when measured at 25 C.
blowing steam across the surface of'the high molecular weight product or through the polymer for a sufiicient time to givethe lower viscosity material having the desired silanol content.- Such compositions and various methods "for preparing the same are more particularly described 'in U.S. Patents 2,607,792 and 2,779,776. The use of steam in this-fashion will cause a decrease in the viscosity of the polymer. while at'the same time the formed linear polysiloxane will have terminal silicon-bonded hy- -droxy groups.
An alternative method for making the linear organo- 'poly siloxane containing terminal silicon-bonded hydroxy groups comprises adding water to the high molecular weight polymer described above in such amount that when heated at elevated temperatures, for instance, 150 to 170 C., the viscosity is reduced to the desired level of 50 to 100,000 c ntip'oises. The amount of water used will vary depending upon such factors as the molecular weight of the polymer being treated, the time and temperature at which the mixture of high molecular weight organopolysiloxane and Water will be heated, the ultimate viscosity desired, etc. i
The amount of water used to reduce the molecular weight can be readily determined. For instance, one can obtain a linear fluid methylpolysiloxane containing terminal silicon-bonded hydroxy groups and having a viscosity of from 1,000 to 2,000 centipoises at 25 C. by heating a high molecular weight methylpolysiloxane (prepared in accordance with the directions above) of about 2,000,000 centipoise viscosity with only 0.5%, by weight, thereof water for about 2 hours at 150 to 170 C.
The methyl hydrogen polysiloxane corresponding to the formula where m and n have the meanings set forth above, may
be prepared .by any one of several ways. -In general,
:methyl hydrogen polysiloxanes may be either linear or cyclic polysiloxanes. Thus, these methyl hydrogen polysiloxanes, if in linear form, may correspond to the general formula LH l. where p'is an integer greater than 1, e.g., 10 to 1,000, or may have intercondensed CH SiO units (in very small molar concentrations) intermediate the trimethylsiloxy units, or even intercondensed dimethylsiloxy units having the formula Generally, when there are dimethylsiloxy units in the methyl hydrogen polysiloXane, the molar concentration of such dimethylsiloxy units should not exceed more than 10 mol percent, and preferably is of the order of from 0 to 5 mol percent of the total number of siloxy units in the linear polysiloxane. Alternatively, the methyl hydrogen polysiloxane may be a cyclic methylpolysiloxane of the formula V (Cl-lgSiI-IO) where q is a whole number equalto from 3 to 10 or more. More particular directions for preparing the linear methyl hydrogen polysiloxane and'the cyclic methyl hydrogen polysiloxane may be found in Wilcock Patent 2,491,843and in Sauer Patents 2,595,890 and 2,595,891, all 10f the aforesaid patents being assigned to the same assignee as the present invention.
I have unexpectedly found that contrary to what might be expected, dibutyl tin dilaurate and dibutyl tin diacetate gave minimum migration of the methylpolysiloxane and were able to be used in lower concentrations than when one. employed metallicsoaps, even tin soaps, such as tin octoate, tin naphthenate, tin "oleate, and even such a metallic salt as butyl tin trioctoate, which is closely akin to dibutyl tin dilaurate and dibutyl tin diacetate.
. The above essential ingredients used'for, treating cellulosic'materials to render them abhesive in the form of a coating material which is non-migratory as far as the linear methylpolysiloxane containing terminal siliconbonde'd hydroXy groups is concerned, are employed in the form of an aqueous emulsion (with or without solvent contained therein), which can be used as a treating bath for cellulosic materials such as cellulosic sheetmaterial, parchment paper, kraft paper, linen rag paper, rice paper,
. glassine, cellophane,'sulfite cellulose paper, and the like,
as well as sheeting or boxing materials, such as paperboard, cardboard, pulpboard, pasteboard.
The aqueous emulsion employed in the practice of the present invention advantageously comprises, by Weight, the following:
The amount of the specific dibutyl tin salt employed will depend upon such factors as, for instance, its effect on the stability of the emulsion,'the type of polydimethylsiloxane and methyl hydrogen polysiloxa'ne used, the type of paper to which the treating composition will be -applied, the'solubility 'of the tin salt, as well as the medium in which the tin salt willbe' used, the' treating conditions including temperature and time "of'tr'e'atin'ent,
The emulsifying agent used is important if one is to obtain a stable emulsion which, on application to paper, will provide the release required without migration of the polydimethylsiloxane. It has been found unexpectedly that an emulsifying agent which is advantageously employed comprises polyvinyl alcohol, and this emulsifying agent has given satisfactory properties in the treated paper. It has further been found that the usual emulsifying agent, such as Triton X-l00 (isooetyl phenyl ether of polyethylene glycol, manufactured and sold by Rohm and Haas Company, Philadelphia, Pa.) and Igepal CO- 530 (polyoxyethylated nonyl phenol containing 7 mols ethylene oxide manufactured and sold by Antara Chemicals, Division of General Aniline & Film, New York, N.Y.) are not satisfactory because they undesirably reduce the release characteristics of the treated paper.
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 0.1 to 3%, by weight, based on the weight of the entire treating aqueous emulsion. 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 preferably 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.
One method for making the emulsion type treating compositions herein described comprises, first, dissolving the emulsifying agent, e.g., polyvinyl alcohol in water, and then adding slowly the polydimethylsiloxane and the methyl hydrogen polysiloxane. This mixture of ingredients is thoroughly homogenized (or colloided) until the polydimethylsiloxane and methyl hydrogen polysiloxane are intimately dispersed throughout the water phase. This material is often referred to as a master emulsion. An aqueous emulsion using, for example, polyvinyl alcohol as the emulsifying agent, is prepared of the dibutyl tin salt similarly as above except that preferably some solvent, such as xylene, is added to the tin salt prior to its addition to the solution of water and polyvinyl alcohol. This tin salt mixture is also homogenized to form an emulsion and in this form is added to the master emulsion in the preparation of the treating bath. The master silicone emulsion is preferably diluted to use concentrations with an additional amount of water prior to incorporation of the catalyst emulsion.
The procedure described above for preparing water emulsions of the treating compositions herein described may, of course, be varied within wide limits and it is not M intended that the description be limiting in any manner.
Theapresence of small amounts of organic solvents is not precluded and under some circumstances may be desirable. If any organic solvent is employed, it is preferable that one employ those which are easily volatilized at the temperature at which treatment of the paper will take place. The emulsion should be kept at a relatively cool temperature, e.g., around room temperature, prior to using in order to maintain its stability.
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 a 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.
Following treatment of the cellulosic material with the emulsion or emulsion-disperson, the material is advantageously dried by passing the treated paper over heated rolls (or cans) maintained at temperatures of about to 175 C. for from about 10 seconds to 3 minutes or more. The use of circulating hot air at temperatures of from to 160 C. may also be used for times of from 30 seconds to 5 minutes to effect curing of the treated paper. This drying step will bring out the optimum release properties of the paper without further heat treatment. Of equal significance is the fact that these optimum release properties are immediately available without requiring aging or storage of the treated paper. Obviously, the higher the temperature, the shorter the period of exposure of the paper for removing the water and drying the paper.
-*In order that those skilled in the art may better understand how the present invention may be practiced, the following examples are given by way of illustration and not by way of limitation. All parts and percents are by weight.
The polydimethylsiloxane containing terminal siliconbonded hydroxyl groups (hereinafter referred to as polydimethylsiloxane) used in the following examples had a viscosity of about 3,000 centipoises when measured at 25 C. and had a ratio of approximately two methyl groups per silicon atom. This high viscosity composition was obtained by heating octamethylcyclotetrasiloxane with about 0.001%, by weight, thereof of potassium hydroxide for about 2 to 4 hours at about C. until a highly viscous (about 3,000,000 centipoises) benzene-soluble product was obtained having slight flow at room temperature. About 0.5% thereof water was added and the mixture heated for about two hours at to C. until a product having a viscosity of about 3,000 centipoises (when measured at 25 C.) was obtained. This material was a linear fluid polydimethylsiloxane having terminal silicon-bonded hydroxyl groups. A devolatilized polydimethylsiloxane (so designated) was also used wherein all volatiles up to at most 1% were removed by heating the polydimethylsiloxane under vacuum of about 15 mm. at 135 C.
The methyl hydrogen polysiloxane used in the following examples was a linear trimethyl silyl chain-stopped polysiloxane described in Wilcock Patent 2,491,843, and had a viscosity of 100 centipoises when measured at 25 C. This material was obtained by cohydrolyzing 5 parts (OH SiCl and 95 parts CH SiHCl In the following tests, the release characteristics of the treated paper (parchment paper was used) were determined by pressing (by hand) a strip of surgical adhesive tape on the surface of the treated paper and lifting the tape from the paper; evaluation of the release was deter mined by assigning numerical values as follows:
O-No lifting of paper whatever 1One edge of paper lifted up to A" 2One edge of paper lifted A" to 1" 3--One edge of paper lifted 1 to 2" 4-Paper falls off after being lifted by tape 5Paper shakes off after being lifted by tape 6Paper will not shake ofi Migration of the silicone from the treated paper to the surface with which it came in contact was determined by observing the detackification of a surgical adhesive tape (loss of tack of the adhesive) caused by migration of the silicone from the surface of the paper to the adhesive on the tape. This was accomplished by pressing (by hand) a strip of adhesive tape onto the surface of the treated paper five times in five different areas. This technique greatly accelerated determination of migration because the adhesive would be expected to pull off silicone which, if given sufiicient time, might migrate of its own accord to the material with which it came in contact. Surgical adhesive tape was used because a major application of release paper is its use as interleaving sheets where the treated paper is in intimate contact with adhesives and 2 no loss of tack can be tolerated in such an application. A strip of the adhesive tape was then lifted from the paper and folded over so that the adhesive surface (which had been in contact with the release paper) was brought into contact with itself. The pull required to separate the adhesive surface from itself (evaluated subjectively as to poor, fair, fair-good, and good tack) compared with tape which had not been in contact with release paper, was used as a measure of detackification of the tape and thus as a measure of migration of the silicone material. The methylpolysiloxane pickup was within the range from about 0.4% to 2%, by weight, based on the weight of the parchment paper which was treated in every instance in the following examples.
EXAMPLE 1 This example illustrates the preparation of treating baths in the form of emulsions employing a high viscosity polyvinyl alcohol manufactured and sold-by E. I. du Pont de Nemours Co., Wilmington, Delaware, under the name Elvanol 50-42, and made by partially hydrolyzing polyvinyl acetate (8689% hydrolyzed). A master emulsion was prepared by mixing together on a weight basis, based on the total weight of the emulsion, amounts of the devolatilized hydroxy chain-stopped polydimethylsiloxane ranging from 28.5 to 30%, from 0.3 to 1.5% of the methyl hydrogen polysiloxane, and from 0.63 to 1.26% polyvinyl alcohol (as the emulsifying agent). In some instances, xylene was added to the mixture of ingredients. This mixture was then diluted further with Water to make the total percent weight equal to 100%, and passed through a homogenizer to obtain a homogeneous creamy emulsion. Each emulsion was thereafter mixed with an aqueous emulsion of the organometallic salt employed in each instance, and this mixture was further diluted with water and intimately mixed to give a homogeneous emulsion treating bath in which the total weight of the polydimethylsiloxane and the methyl hydrogen polysiloxane comprised about by weight, of the total emulsion treating bath. The particular dibutyl tin salt used was employed in such amount that there was present in the treating bath composition from 0.2 to 0.4% tin, based on the total weight of the polydimethylsiloxane and methyl hydrogen polysiloxane. Tables IA and IB below show the effects on treated parchment paper which was immersed in the emulsion bath, the treated paper removed and passed between squeeze rolls to remove excess treating composition, and thereafter the paper was dried by passing it over a heated cylindrical roll maintained at a temperature of from l10113 C.-for about 3 minutes. This method for treatment of parchment paper was followed in all the following examples as well:
a This was.the.nonfdevolatilizedhydroxy chain-stopped polydimethyl-.-
siloxane.
. Performance on Catalyst Paper Concentration Test No. Catalyst Release Tack Dibutyl tin dilaurate.... Poor. d0 Good.
Poor. Good.
Do. Poor. Good. Poor. Good. Poor. Good. Poor. Good.
do Dibgtyl tin (liacetate o b All treating baths contained 10%, by weight, methylpolysiloxane of the combined devolatilized polydimethylsiloxane and themethyl hydrogen polysiloxaue.
EXAMPLE 2 In this example, a master emulsion was prepared similarly as in Example 1, employing on a weight basis 28.5% of the devolatilized hydroxy chain-stopped polydimethylsiloxane, 1.5% of the trimethyls'ilyl chain-stopped methyl hydrogen polysiloxane, 7.5% xylene, 1.26% polyvinyl alcohol, and the balance (up to water. The treating bath composition (made by diluting the master emulsion) used to treat the parchment paper again comprised, as in Example 1, 10 weight percent of the mixture of the hydroxy chain-stopped methylpolysiloxane and the methyl hydrogen polysiloxane, and dibutyl tin dilaurate as a catalyst. Three treating bath compositions were prepared, of which the emulsions used for treating purposes contained varying amounts of catalyst concentration of dibutyl tin dilaurate, which was added in the form of an emulsion similarly as in Example 1. The amounts of catalyst used were 0.2% tin, 0.4% tin, and 4.0% tin, each in the form of dibutyl tin dilaurate. The treated paper was treated and dried similarly as was done in Example 1, and its performance asto release and tack were determined. It was found that regardless of the catalyst concentration, the release in each of the three instances was 0, and the tack was Good. This example illustrates the Wide range of catalyst concentration which can be employed in the practice of the present invention.
The following example illustrates that the incorporation of a solvent such as xylene (benzene, toluene, 'etc., can also be used) in the treating emulsion improves the stability of the emulsion, and thus allows the treating bath to remain effective over a longer period of time with retention of optimum properties in the treated paper.
EXAMPLE 3 In this example, master silicone emulsions were prepared similarly as in Example 1, and each of these master silicone emulsions was mixed with a catalyst emulsion in which the catalyst was dibutyl tin dilaurate; this emulsion mixture was diluted with water to give a treating bath emulsion composition which was used to treat parchment paper similarly as was done in Example 1. In all the master emulsions, 1.26% polyvinyl alcohol was used as the emulsifying agent, based on the weight of the emulsion. The concentration of the tin catalyst, 0.2% tin in the form of dibutyl tin dilaurate, was based on the total weight of the two polysiloxanes in the emulsion. The following Table IIA shows the composition of the master silicone emulsion, the balance of the emulsion being water. Table 1113 shows the performance data on paper treated with the emulsions after the emulsion baths had been allowed to remain at room temperature for various lengths of time; also Table IIB shows the condition of" the baths, i.e., their stability, after they were pumped through pumping equipment as might be encountered in plant usage where the emulsion may be prepared in one part of the plant and then pumped to another part of the plant where it is to be used.
Table IIA MASTER SILICONE EMULSION Weight Weight Per- Percent cent Methyl Weight Test N0. Devolatilized Hydrogen Percent Polydimeth- Polysiloxane Xylene ylsiloxane 28. 5 1. 5 28. 5 l. 5 28. 5 1. 5 28.5 1. 5 28. 5 1. 5 5 28. 5 1. 5 5 28. 5 l. 5 5 28.5 1. 5 5 I 28. 5 1. 5 .0 28. 5 1. 5 .0 28. 5 1. 5 28. l. 5 0 28. 5 1. 5 5 28. 5 1. 5 5 28v 5 1. 5 5 28. 5 1. 5 .5
a The solvent used in these instances was mineral spirits.
Table IIB TREATING BATH COMPOSITION This example illustrates the importance of choosing the proper emulsifying agent. As pointed out above, polyvinyl alcohol is admirably suited for the purpose. However, it should be noted from the following example that all non-ionic emulsifiers, of which polyvinyl alcohol is an example, are not satisfactory.
EXAMPLE 4 In this example, master silicone emulsions were prepared similarly as was done in Example 1 and the other examples, employing on a weight basis 28.5% of the devolatilized hydroxy chain-stopped polydimethy1siloxane, 1.5% of the trimethylsiloxy chain-stopped methyl hydrogen polysiloxane, and 7.5% xylene, the balance being water with the exception of the emulsifying agent which was used in small, stipulated amounts. Various emulsifying agents were employed to make the-master silicone emulsion. The following Table III shows the particular emulsifier used, the concentration of the emulsifier in the master silicone emulsion, as well as the performance data of the particular treating baths, depending upon the specific emulsifying agent employed. In making the treating bath emulsion compositions (pursuant to the procedure in Example 1), the diluted master silicone emulsions contained by weight, of the mixture of the devolatilized polydimethylsiloxane and the methyl hydrogen polysiloxane, together with 0.2%, by weight,
based on the weight of the mixture of the methylpolysiloxanes of tin, in the form of dibutyl tin dilaurate.
Table 111 Weight Performance on Percent Paper Test No. Emulsitler Ertriiulsi- Release Tack 3O Polyvinyl alcohol (non- 0.68 0 Good.
ionic). -11 rio 1.26 0 D0. 2. 52 0 D0. 33 Mixtureofpolyoxyethylated 1.0 4 Do.
nonyl phenols (non-ionic). 34 Fatty alcohol amine sulfate 1.0 0 Do.
(anionic). 35 d0 2.0 0 Do. 36 Sulfonated methyl oleate 1.0 1-3 Fair.
(anionic). 37 Alkyl quaternary ammoni- 1.0 4 Good.
um chloride (cationic). 38 Dialkyl quaternary ammo- 1.0 1 Do.
nium chloride (cationic).
EXAMPLE 5 This example illustrates the versatility of using various concentrations of the mixture of the hydroxy chainstopped methylpolysiloxane and the methyl hydrogen polysiloxane in a treating bath composition. More particularly, a master silicone emulsion was prepared similarly as was done in Example 1, by mixing together 28.5% of the devolatilized hydroxy chain-stopped methylpolysiloxane, 1.5% of the methyl hydrogen polysiloxane, 7.5% xylene, 1.26% polyvinyl alcohol, and the balance (up to 100%) water. This master silicone emulsion was then diluted further with water in such quantities that the mixture of the two polysiloxanes in the master silicone emulsion ranged from about 6 to 30%, by weight, of the total weight of the treating emulsion, employing in each instance 0.2%, by weight, tin'based on the weight of the two polysiloxanes, in the form of 'dibutyl tin dilaurate. Parchment paper was treated similarly as was done in Example 1 and the performance of the treated paper was determined as evidenced -by its release and tack. The following Table IV shows the concentration of the mixture of polysiloxanes in the treating bath composition as well as the release and tack of the treated paper.
Table -I V Weight Percent Test No. Polysiloxanes in Release Tack Treating Bath Emulsion 6 1 Good. 10 0 D0. 15 0 D0. 30 0 Do.
The following example illustrates that good release with no silicone migration is obtained over a wide range of viscosity of the hydroxy chain-stopped polydimethylsiloxane polymers. The range of viscosity evaluated, 600 centipoisesto 94,500 centipoises, measured at about 25 C., is not intended to exclude lower and higher viscosities.
EXAMPLE 6 In this example, various master silicone emulsions were prepared from the devolatilized hydroxy chainstopped methyl polysiloxanes employing in each instance on a weight basis 28.5% of the hydroxy chain-stopped methylpolysiloxane, 1.5% of the methyl hydrogen polysiloxane, 7.5 xylene, and 1.26% polyvinyl alcohol as the emulsifying agent, the balance being water. In making the master silicone emulsions, various viscosities of the hydroxy chain-stopped methylpolysiloxanes were employed. Each master silicone emulsion was thereafter diluted further with water to obtain a treating bath composition, of which 10%, by weight, comprised the mixture of the devolatilized polydimethylsiloxane and the methyl hydrogen polysiloxane; to this was added about 0.2%, by weight, tin based on the combined Weight of Table V Test No. Viscosity, Release Tack Oentipoises 600 -Gocd 1 This polydimcthylsiioxane was not devolatilizcd...
Although the preceding examples have given formula- .tions which can advantageously he used in the practice of the present invention, the following general formulations may also be helpful in determining" the relationship of the master emulsion system, the'catalyst emulsion, and the actual treating emulsion. Thus, the master emulsion may generally comprise the following ingredients, by weight:
28.50 parts of the hydroxy chain-stopped polydimethylsiloxane (whether devolatilized or non-devolatilized) i 1.50 parts of the trimethyls'iloxy.chain-stopped methyl hydrogen polysiloxane (or cyclic methyl hydrogen polysiloX-ane) 1.26 parts'polyvinyl alcohol. (or varied as the case may be) 7.50 parts xylene or mineral spirits (or varied case may be) 61.24 parts water 100.00 parts total The tin salt emulsion may comprise the following ingredients, by weight:
70.0 parts of the tin salt, for instance, dibutyl tin V dilaurate (18% tin) 30.0 parts xylene 2.1 parts polyvinyl alcohol 107.9 parts water 210.0 parts total The treating bath emulsion-in general used to treat the parchment paper may comprise thefollowing:
33.30 parts of the master siliconeemulsion 0.33 parts of the catalyst emulsion 66.37 parts water 100.00 parts total It will be apparent that theabove relationship of ingredients in the master emulsion, the catalyst emulsion, and the treating bath emulsion may "be varied pursuant to the modifications and variations defined in the preceding" examples.
It will, of course, be apparent .to those skilled in the art that in addition to the hydroxy chain-stopped methylpolysiloxane of the viscosities recited in the'foregoing examples, other linear hydroxy chain-stopped polydimethylsiloxanes (both devolatilized 'and 'non-devolatilized) containing terminal silicon-bonded hydroxyl groups of other viscosities within the range of50 to 2,000,000 centipoises, when measured at 25 C., can be employed without departing from the scope of the invention. The concentration of the hydroxy chain-stopped'polydimethylsiloxane, the methyl hydrogenpolysiloxane;the type of methyl hydrogen 'polysiloxane .employed, 'as well' as the concentration of the "catalyst, emulsifying agent, 'etc.,
may'vary within the ranges 'previously'recited within the as the 'wide range of usefulness.
scope of the present invention. The concentration of the dibutyl tin dilaurate or dibutyl tin diacetate (or mixturesof such tin salts) also maybe varied within wide limits depending onthefactors recited previously.
The amount of organopolysiloxane which is picked up by the cellulosic paper material as a result of the treatment with the emulsion of the organopolysiloxanes dependsupon'such factors as'the absorbency of the cellulosic material, the method of application, the concentration of organopolysiloxanes in the emulsion, etc. Generally, the amount of organopolysiloxane pickup ranges from about 0.1 to about 5%, or mo-re, based on the dry weight of the cellulosic material, the preferred pickup being within the range of about 0.4 to 2%organopolysiloxane. Obviously, larger amounts or organopolysiloxane pickup may be employed,'bujt generally this is not necessary and usually serves merelyto increase the cost of the treatment. I
Advantages of using the compositions hereindescribed for the above specified purposes are'manifold. 'Of particular importance is the fact that when the above combination of ingredients is applied to paper, in, addition to imparting adhesive characteristics thereto, the organepolysiloxane (that is, the polydime'thylsiloxane and the methyl hydrogen polysiloxane) vcontent in the paper is substantially non-migratory and will not affect or be transferred to the surfaces of compositions from which the adhesive paper must be readily separated. Moreover, the adhesive characteristics of the treated paper are substantially the same even after the paper is stored for long periods of time; in contrast to this, paper treated with prior organopolysiloxane compositions used to render the paper adhesive have suifered severe losses in their abhesive properties after storage for any length of time, for instance, even after only 6 months.
Of equal significance is the fact that papertreated'in accordance with my process can be employed at once for its anti-release purposes with realization of essentially optimum properties; 'Heretofore, organopolysiloxaues previously available on the: market for the same purpose required aging, that -is, storing of the treated paper-for times as long as six weeks, in order to bring out the optimum release characteristics of the treated paper. of considerable importance is the fact that even at' high temperatures, the release characteristics are maintained at optimum "levels "and 'elevatedtemperatures "do not "destroy the release film. p a
The 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 formulations. Standard paper makingor 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.
Cellulosic materials treated as described above have a Thus, asphalt or highmolecular weight organic polymers, such a various synthetic rubbers, canbe poured hot into containers fashioned from thetreated paper or paperboard, and after cooling it will be found that solidified asphalt or polymer is readily and cleanly separated from container Walls.
My invention permits paper treated in accordance with my process to be substituted for various materialswhich 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 invention is also useful in lining various boxes of partially prebaked goods, such 13 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.
What I claim as new and desire to secure by Letters Patent of the United States is:
1. The method for rendering cellulosic fibrous sheet material non-adherent to surfaces which normally adhere thereto, which process comprises treating the cellulosic fibrous sheet material with an aqueous emulsion treating bath containing, by weight, the following sole active ingredients:
(a) from 1 to 35% of a linear polydimethylsiloxane containing terminal silicon-bonded hydroxy groups,
(b) from 65 to 98% water,
(a) from 0.1 to 5% of a methyl hydrogen polysiloxane,
based on the weight of (a),
(d) from 0.05 to 10% tin in the form of a metallic salt selected from the class consisting of dibutyl tin dilaurate and dibutyl tin diacetate, based on the weight of (a),
(e) from to 10% of an organic solvent, and
(1) from 0.1 to 3% of polyvinyl alcohol as an emulsifying agent, and thereafter drying the treated material.
2. The method for rendering cellulosic fibrous sheet material non-adherent to surfaces which normally adhere thereto, which process comprises treating cellulosic fibrous sheet material with an aqueous emulsion treating bath containing, by weight, the following sole active ingredicuts:
(a) from 1 to 35% of a linear polydimethylsiloxane containing terminal silicon-bonded hydroxy groups,
(b) from 65 to 98% water,
(0) from 0.1 to 5% of a linear methyl hydrogen polysiloxane, based on the weight of (a),
'14 (d) from 0.05 to 10% tin as dibutyl tin dilaurate, based on the weight of (a), (e) from 0 to 10% of an organic solvent, and from 0.1 to 3% of polyvinyl alcohol as an emulsifying agent, and thereafter drying the treated material.
3. The method for rendering cellulosic fibrous sheet material non-adherent to surfaces which normally adhere thereto, which process comprises treating the cellulosic fibrous sheet material with an aqueous emulsion treating bath containing, by Weight, the following sole active ingredients:
(a) from 1 to 35% of a linear polydirnethylsiloxane containing terminal silicon-bonded hydroxy groups,
(b) from to 98% water,
(0) from 0.1 to 5% of a linear methyl hydrogen polysiloxane, based on the weight of (a),
(d) from 0.05 to 10% tin as dibutyl tin diacetate, based on the weight of (a),
(e) from 0 to 10% of an organic solvent, and (1) from 0.1 to 3% of polyvinyl alcohol as an emulsifying agent, and thereafter drying the treated material.
4. Cellulosic material treated in accordance with the method described in claim 2.
References Cited in the file of this patent UNITED STATES PATENTS 2,504,388 Braley Apr. 18, 1950 2,588,367 Dennett Mar. 11, 1952 2,588,393 Kauppi Mar. 11, 1952 2,612,482 Rasmussen Sept. 30, 1952 2,807,601 Dennett Sept. 24, 1957 2,814,601 Currie et al Nov. 26, 1957
Claims (1)
1. THE METHOD FOR RENDERING CELLULOSIC FIBROUS SHEET MATERIAL NON-ADHERENT TO SRUFACES WHICH NORMALLY ADHERE THERETO, WHICH PROCESS COMPRISES TREATING THE CELLULOSIC FIBROUS SHEET MATERIAL WITH ANQUEOUS EMULSION TREATING BATH CONTAINING, BY WEIGHT, THE FOLLOWING SOLE ACTIVE INGREDIENTS: (A) FROM 1 TO 35% OF A LINEAR POLYDIMETHYLSILOXANE CONTAINING TERMINAL SILICON-BONDED HYDROXY GROUPS, (B) FROM 65 TO 98% WATER. (C) FROM 0.1 TO 5% OF A METHYL HYDROGEN POLYSILOXANE, BASED ON THE WEIGHT OF (A), (D) FROM 0.05 TO 10% TIN IN THE FORM OF A METALLIC SALT SELECTED FROM THE CLASS CONSISTING OF DIBUTYL TIN DILAURATE AND DIBUTYL TIN DIACETATE, BASED ON THE WEIGHT OF (A), (E) FROM 0 TO 10% OF AN ORGANIC SOLVENT, AND (F) FROM 0.1 TO 3% OF POLYVINYL ALCOHOL AS AN EMULSIFYING AGENT, AND THEREAFTER DRYING THE TREATED MATERIAL.
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US72396458 US2985545A (en) | 1958-03-26 | 1958-03-26 | Method of rendering cellulosic material non-adherent and article produced thereby |
US723963A US2985544A (en) | 1958-03-26 | 1958-03-26 | Method of rendering cellulosic material non-adherent and article produced thereby |
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US3116002A (en) * | 1961-06-22 | 1963-12-31 | Ex Cell O Corp | Container with pouring lip |
US3194680A (en) * | 1961-04-25 | 1965-07-13 | Bayer Ag | Process for the production of siloxanecoated separating paper |
US3305502A (en) * | 1963-12-16 | 1967-02-21 | Gen Electric | Process for curing diorgano polysiloxanes at room temperature |
US3307956A (en) * | 1963-10-28 | 1967-03-07 | Union Carbide Corp | Process of making a sausage casing with an organosiloxane |
US3327920A (en) * | 1965-10-23 | 1967-06-27 | David A Hynes | Container for liquids |
US3328482A (en) * | 1965-01-08 | 1967-06-27 | Dow Corning | Silicone controlled release agents |
US3385727A (en) * | 1964-09-01 | 1968-05-28 | Gen Electric | Siloxane paper release coatings |
US3418162A (en) * | 1963-12-07 | 1968-12-24 | Shinetsu Chem Ind Co | Composition of waterproof agent and process for manufacture of waterproof cloth using the same |
US3419653A (en) * | 1965-01-04 | 1968-12-31 | Du Pont | Prevention of filament twinning in dry spinning |
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US3442663A (en) * | 1966-01-24 | 1969-05-06 | Tee Pak Inc | Method of treating a sausage casing with a release coating and product resulting therefrom |
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US3076773A (en) * | 1958-10-17 | 1963-02-05 | Diamond Alkali Co | Aqueous emulsion of an organic solvent-siloxane mixture |
US3061567A (en) * | 1958-11-28 | 1962-10-30 | Dow Corning | Aqueous dispersions of a mixture of siloxanes and an aminoplast resin, method of coating, and article obtained |
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US3116002A (en) * | 1961-06-22 | 1963-12-31 | Ex Cell O Corp | Container with pouring lip |
US3307956A (en) * | 1963-10-28 | 1967-03-07 | Union Carbide Corp | Process of making a sausage casing with an organosiloxane |
US3418162A (en) * | 1963-12-07 | 1968-12-24 | Shinetsu Chem Ind Co | Composition of waterproof agent and process for manufacture of waterproof cloth using the same |
US3305502A (en) * | 1963-12-16 | 1967-02-21 | Gen Electric | Process for curing diorgano polysiloxanes at room temperature |
US3436251A (en) * | 1964-08-04 | 1969-04-01 | Midland Silicones Ltd | Process for rendering paper abrasion resistant,adhesive and water-repellent employing siloxane composition |
US3385727A (en) * | 1964-09-01 | 1968-05-28 | Gen Electric | Siloxane paper release coatings |
US3419653A (en) * | 1965-01-04 | 1968-12-31 | Du Pont | Prevention of filament twinning in dry spinning |
US3328482A (en) * | 1965-01-08 | 1967-06-27 | Dow Corning | Silicone controlled release agents |
US3445418A (en) * | 1965-04-05 | 1969-05-20 | Ici Ltd | Organosilicon compositions |
US3327920A (en) * | 1965-10-23 | 1967-06-27 | David A Hynes | Container for liquids |
US3463661A (en) * | 1966-01-14 | 1969-08-26 | Scott Paper Co | Process for preparing paper with silicone release coating |
US3442663A (en) * | 1966-01-24 | 1969-05-06 | Tee Pak Inc | Method of treating a sausage casing with a release coating and product resulting therefrom |
US3522202A (en) * | 1966-09-12 | 1970-07-28 | Shinetsu Chem Ind Co | Release coatings consisting of three polyorganosiloxanes |
US3668228A (en) * | 1968-06-13 | 1972-06-06 | Ciba Ltd | Solutions of curing catalysts for polysiloxanes |
US3649349A (en) * | 1968-12-13 | 1972-03-14 | Gen Electric | Siloxane paper release coatings |
US3628996A (en) * | 1969-06-27 | 1971-12-21 | Dow Corning | Polydimethylsiloxane release agent |
US3658560A (en) * | 1969-08-20 | 1972-04-25 | Tee Pak Inc | Easily peeled synthetic casing |
US3658561A (en) * | 1969-09-22 | 1972-04-25 | Henry J Rose | Treatment of sausage casing for easy peeling |
US3922443A (en) * | 1972-05-01 | 1975-11-25 | Ici Ltd | Process for coating a substrate with a polysiloxane composition |
US3900617A (en) * | 1973-11-27 | 1975-08-19 | Gen Electric | Method of rendering flexible sheet material non-adherent and article produced thereby |
DE2455483A1 (en) * | 1973-11-27 | 1975-05-28 | Gen Electric | METHOD FOR TREATMENT OF FLEXIBLE FILM MATERIAL |
DE2550744A1 (en) * | 1974-11-14 | 1976-05-26 | Gen Electric | POLYSILOXANE COMPOSITION AND METHOD OF MANUFACTURING THEREOF |
US4071644A (en) * | 1974-11-14 | 1978-01-31 | General Electric Company Silicone Products Department | Method for rendering flexible sheet material non-adherent |
US4042168A (en) * | 1976-08-31 | 1977-08-16 | Minnesota Mining And Manufacturing Company | Packaging container blank |
US4441613A (en) * | 1982-09-01 | 1984-04-10 | Champion International Corporation | Container with resealable closure |
US4460091A (en) * | 1982-09-01 | 1984-07-17 | Champion International Corporation | Bag resealing clip |
US5543082A (en) * | 1988-05-09 | 1996-08-06 | Dow Corning Corporation | Silicone foam control compositions |
US5439677A (en) * | 1989-07-24 | 1995-08-08 | The Dial Corp. | Compositions and methods for treating hair using a mixture of polysiloxanes |
US5083702A (en) * | 1990-03-22 | 1992-01-28 | Minnesota Mining And Manufacturing Company | Gable-top container and method and apparatus for construction thereof |
US5629095A (en) * | 1993-05-18 | 1997-05-13 | Dow Corning Corporation | Radiation curable compositions containing vinyl ether functional polysiloxanes and methods for the preparation |
US5861467A (en) * | 1993-05-18 | 1999-01-19 | Dow Corning Corporation | Radiation curable siloxane compositions containing vinyl ether functionality and methods for their preparation |
US5824761A (en) * | 1995-05-18 | 1998-10-20 | Dow Corning Corporation | Radiation curable compositions containing vinyl ether functionality and methods for their preparation |
US20100173069A1 (en) * | 2007-09-27 | 2010-07-08 | Henkel Corporation | Two-component high gloss semi-permanent water based release agent for polyester substrates |
US8436107B2 (en) * | 2007-09-27 | 2013-05-07 | Henkel Corporation | Two-component high gloss semi-permanent water based release agent for polyester substrates |
US9096776B2 (en) | 2011-10-17 | 2015-08-04 | Shin-Etsu Chemical Co., Ltd. | Silicone release coating composition of condensation reaction curing type |
RU2610764C1 (en) * | 2016-02-03 | 2017-02-15 | Акционерное общество "Научно-исследовательский институт полимерных материалов" | Method of preparang technological equipment for multiple use thereof when producing special-purpose products at armouring stage |
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