US3379546A - Process for improving the surface characteristics of cellulose hydrate films - Google Patents
Process for improving the surface characteristics of cellulose hydrate films Download PDFInfo
- Publication number
- US3379546A US3379546A US405600A US40560064A US3379546A US 3379546 A US3379546 A US 3379546A US 405600 A US405600 A US 405600A US 40560064 A US40560064 A US 40560064A US 3379546 A US3379546 A US 3379546A
- Authority
- US
- United States
- Prior art keywords
- weight
- films
- cellulose hydrate
- aqueous
- bath
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920002678 cellulose Polymers 0.000 title claims description 17
- 239000001913 cellulose Substances 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 22
- 229920002873 Polyethylenimine Polymers 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 11
- 239000004965 Silica aerogel Substances 0.000 claims description 10
- 229910021485 fumed silica Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000007900 aqueous suspension Substances 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 239000002981 blocking agent Substances 0.000 claims description 2
- 238000004873 anchoring Methods 0.000 description 15
- 239000004964 aerogel Substances 0.000 description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 12
- 235000012239 silicon dioxide Nutrition 0.000 description 12
- 239000000314 lubricant Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000298 Cellophane Polymers 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003922 charged colloid Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002737 metalloid compounds Chemical class 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/06—Cellulose hydrate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/922—Colloid systems having specified particle size, range, or distribution, e.g. bimodal particle distribution
Definitions
- cellulose hydrate films In order to improve the physical properties of cellulose hydrate films, such as extension and elasticity, they are normally treated with solutions of softeners such as glycerine or diand triglycols. Depending upon the intended use of the films such films contain in general 12 to 20% softeners. As a result of the use of such softeners, depending upon the quantity contained in the softener baths, certain disadvantagous properties are engendered therein in that the stickiness of such films is greatly increased and such stickiness often can lead to difficulties in the subsequent processing of the softened films.' For example, the surfaces of rolled up film stick together (block) so that it cannot be removed from the roll without difficulty and often tears 0E. Such tendency of rupture of the film is especially disadvantageous and disturbing to production when the film is to be processed on automatic machines such as roller cutters, printing machines or bag making machines.
- anchoring agents and/or lubricants are added in certain quantities either to the bath containing softening agents or to a preceding bath.
- the anchoring agents and/ or lubricants contained in these baths are applied to the surfaces of the cellophane during its passage through the baths and then dried onto such surfaces when the cellophane is subsequently passed through the drier portion of the machine.
- Such bath treatments of the cellulose hydrate films in general cause an increased tendency for blocking. If, for example, an improved anchoring action is sought after, optimal surface sliding characteristics are precluded and the undesired blocking effect occurs when the treated film is rolled and later unrolled for further processing.
- oxide aerogels for example, are those of titanium, zirconium, zinc or aluminum produced in an analogous manner.
- the oxide aerogels need not be employed in pure state as mixtures of such oxides or mixed oxides can also be used.
- These highly disperse colloids expediently are converted into their aqueous dispersons which are then incorporated in the softeners or softener solutions. Care must be taken to ensure a good distribution of these dispersions as the stability of the baths as well as the effect obtained depends to a great extent thereon.
- a cationically active anchoring agent such as polyethylene imine which, for example, can be obtained in a known manner by catalytic acid (cationic) polymerization of ethylene imine, rather than working in the oxide aerogels in the form of an aqueous dispersion containing, for example, a small quantity of dispersed silicic acid, it is possible to disperse surprisingly large quatities of the finely divided oxide aerogels so that, for example, stable, non-coagulating dispersions can be obtained which contain between 80 and 200 parts, preferably, between 120 and 150 parts, by weight of silicic acid and -40 parts, preferably 15-20 parts by weight of polyethylene imine per 1000 parts by weight of the dispersion.
- the stable dispersions produced according to the invention can either be used together with the above mentioned anchoring and/or lubricating agents or these products can be added to a bath preceding the usual softener bath.
- Example 83.5 liters of distilled water were placed in a stirring vessel and 4 kg. of an aqueous 50% polyethylene imine paste dissolved therein. Then 12.5 kg. of a pyrogenic silica aerogel product having a primary particle size of about l040 m and a surface of 6080 m /g. were stirred in in dry form and then intensively dispersed therein with a high capacity stirrer.
- Such dispersion was added to an aqueous softener bath which in addition to 4% of glycerine also contained 0.5 g. per liter of a water soluble urea formaldehyde precondensate as an anchoring agent.
- the quantity of such dispersion incorporated in the softener bath was 5.0 cc. per liter.
- a regenerated cellulose film was passed through such bath at 25 C. and then freed of excess liquid by being passed through rubber squeezing rollers and dried on rollers heated to -90 C. The resulting treated film had good surface characteristics and could be rolled up and stored for longer periods of time without danger of blocking.
- silica aerogel used above was replaced by a mixed oxide aerogel containing about 98.3% of SiO and about 03-13% of A1 0 and the remainder other oxides which may be disregarded and having about the same particle size and surface area as such silica aerogei.
- the polyethylene imine employed was one obtained by catalytic acid polymerization of ethylene imine which was terminated by neutralization just before complete water solubility was lost.
- the 50% aqueous solution was of alkaline reaction.
- Such water soluble polyethylene imine product has already achieved wide use in the paper industry to increase the wet strength of paper and is, for example, available as the well-known product Polymin-P.
- An antiblocking agent for use in baths employed for the processing of cellulose hydrate films consisting essentially of a stable aqueous dispersion containing 8 to 20% by weight of dispersed pyrogenic silica having a particle size of less than 0.15 2 and 1.5 to 4% by weight of polyethylene imine dissolved in the aqueous phase of such dispersion.
- An antiblocking agent for use in baths employed for the processing of cellulose hydrate films comprising a stable aqueous dispersion containing 12 to 15% by weight of dispersed pyrogcnic silica having a particle size of less than 0.15 and 1.5 to 2.0% by weight of polyethylene imine dissolved in the aqueous phase of such dispersion.
- a method of producing a stable aqueous dispersion containing 8 to 20% by weight of a pyrogenic silica having a particle size of less than 0.15 1. which comprises intensively dispersing a pyrogenic silica aerogel having a particle size of less than 0.15 1. in dry form in an aqueous solution of polyethylene imine in such proportions that the aqueous suspension contains 8 to 20% by weight of the silica aerogel and 1.5 to 4.0% by weight of polyethylene imine.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
- Silicon Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED0042847 | 1963-11-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3379546A true US3379546A (en) | 1968-04-23 |
Family
ID=7047160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US405600A Expired - Lifetime US3379546A (en) | 1963-11-02 | 1964-10-21 | Process for improving the surface characteristics of cellulose hydrate films |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3379546A (enrdf_load_stackoverflow) |
| BE (1) | BE655148A (enrdf_load_stackoverflow) |
| CH (1) | CH484947A (enrdf_load_stackoverflow) |
| DE (1) | DE1470784A1 (enrdf_load_stackoverflow) |
| GB (1) | GB1075056A (enrdf_load_stackoverflow) |
| NL (2) | NL6412000A (enrdf_load_stackoverflow) |
| NO (1) | NO125098B (enrdf_load_stackoverflow) |
| SE (1) | SE335614B (enrdf_load_stackoverflow) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4150101A (en) * | 1974-03-26 | 1979-04-17 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for the production of silica with an aerogel type structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB713211A (en) * | 1951-03-01 | 1954-08-04 | Degussa | Production of colloidal solutions |
| US2892730A (en) * | 1948-12-31 | 1959-06-30 | Degussa | Solution of high molecular weight lacquer film former containing oxides of silicon, aluminum, and titanium |
| DE1081410B (de) * | 1956-10-26 | 1960-05-12 | Wit S Textiel Nijverheid N V D | Verfahren zur Erhoehung der Schiebefestigkeit von Cellulosetextilien |
| US3013901A (en) * | 1959-11-30 | 1961-12-19 | Du Pont | Article coated with fibrous boehmite |
-
0
- NL NL133196D patent/NL133196C/xx active
-
1963
- 1963-11-02 DE DE19631470784 patent/DE1470784A1/de active Pending
-
1964
- 1964-08-18 CH CH1078664A patent/CH484947A/de not_active IP Right Cessation
- 1964-08-26 SE SE10250/64A patent/SE335614B/xx unknown
- 1964-09-12 NO NO154742A patent/NO125098B/no unknown
- 1964-09-15 GB GB37657/64A patent/GB1075056A/en not_active Expired
- 1964-10-15 NL NL6412000A patent/NL6412000A/xx unknown
- 1964-10-21 US US405600A patent/US3379546A/en not_active Expired - Lifetime
- 1964-10-30 BE BE655148D patent/BE655148A/xx unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2892730A (en) * | 1948-12-31 | 1959-06-30 | Degussa | Solution of high molecular weight lacquer film former containing oxides of silicon, aluminum, and titanium |
| GB713211A (en) * | 1951-03-01 | 1954-08-04 | Degussa | Production of colloidal solutions |
| DE1081410B (de) * | 1956-10-26 | 1960-05-12 | Wit S Textiel Nijverheid N V D | Verfahren zur Erhoehung der Schiebefestigkeit von Cellulosetextilien |
| US3013901A (en) * | 1959-11-30 | 1961-12-19 | Du Pont | Article coated with fibrous boehmite |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4150101A (en) * | 1974-03-26 | 1979-04-17 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for the production of silica with an aerogel type structure |
Also Published As
| Publication number | Publication date |
|---|---|
| BE655148A (enrdf_load_stackoverflow) | 1965-02-15 |
| DE1470784A1 (de) | 1969-03-27 |
| NL133196C (enrdf_load_stackoverflow) | |
| SE335614B (enrdf_load_stackoverflow) | 1971-06-01 |
| NO125098B (enrdf_load_stackoverflow) | 1972-07-17 |
| GB1075056A (en) | 1967-07-12 |
| NL6412000A (enrdf_load_stackoverflow) | 1965-05-03 |
| CH484947A (de) | 1970-01-31 |
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