EP0629741B1 - Use of fine paper sized with alkyl ketene multimers in high speed precision converting or reprographic operations - Google Patents
Use of fine paper sized with alkyl ketene multimers in high speed precision converting or reprographic operations Download PDFInfo
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- EP0629741B1 EP0629741B1 EP94304136A EP94304136A EP0629741B1 EP 0629741 B1 EP0629741 B1 EP 0629741B1 EP 94304136 A EP94304136 A EP 94304136A EP 94304136 A EP94304136 A EP 94304136A EP 0629741 B1 EP0629741 B1 EP 0629741B1
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- Prior art keywords
- paper
- mixture
- per minute
- saturated
- converting
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Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/17—Ketenes, e.g. ketene dimers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/16—Pure paper, i.e. paper lacking or having low content of contaminants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0035—Uncoated paper
-
- 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
- B65D27/00—Envelopes or like essentially-rectangular containers for postal or other purposes having no structural provision for thickness of contents
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
Definitions
- This invention relates to the use of fine paper sized with a sizing agent comprising a mixture of 2-oxetanone compounds in high speed precision converting on reprographic operations.
- ASA alkenyl succinic anhydride
- ALD alkyl ketene dimer
- AKD's containing one ⁇ -lactone ring
- AKD's are prepared by the dimerization of the alkyl ketenes made from two saturated, straight-chain fatty acid chlorides; the most widely used being prepared from palmitic and/or stearic acid.
- Other ketene dimers such as the alkenyl-based ketene dimer (Aquapel® 421, available from Hercules Incorporated, Wilmington, DE, U.S.A.), have also been used commercially.
- ASA-based sizing agents can be prepared by the reaction of maleic anhydride with a 14 to 18 carbon olefin.
- ASA and AKD sizing agents are commercially successful, they have disadvantages. Both types of sizing agents, particularly the AKD type, have been associated with handling problems in the typical high-speed conversion operations required for the current uses of fine paper made under alkaline conditions (referred to as alkaline fine paper). The problems include reduced operating speed in forms presses and other converting machines, double feeds or jams in high-speed copiers, and registration errors on printing and envelope-folding equipment that operate at high speeds.
- alkaline fine paper produced under acid conditions
- the types of filler and filler addition levels used to make alkaline fine paper differ significantly from those used to make acid fine paper, and can cause differences in paper properties such as stiffness and coefficient of friction, which affect paper handling.
- Sodium chloride is often added to the surface of alkaline fine paper to improve its end-use performance.
- the paper properties affected by papermaking under alkaline conditions that can affect converting and end-use performance include:
- Such billowing involves a divergence of the paper path from the straight line between the rolls, which is two inches (5 cm) above the base plate, causing registration errors and dropped folds in the stacker.
- Typical alkaline AKD sized fine paper using a size furnish of 2.2 lbs. per ton (1 kg per 0.9 metric ton) of paper shows an unacceptable rate-of-billowing, typically of the order of 20 to 80.
- Paper handling rates on other high-speed converting machinery, such as the Hamilton-Stevens continuous forms press, or the Winkler & Dunnebier CH envelope folder also provide numerical measures of convertibility.
- Ketene multimers containing more than one beta-lactone ring have also been disclosed as sizing agents for paper in Japanese Kokai 168991/89 and 168992/89.
- the ketene multimers are said to show improved sizing compared to the ketene dimers previously used.
- the multimers are prepared from a mixture of mono- and dicarboxylic acids. The advantage of a combination of good sizing and good performance on high speed converting or reprographic equipment is not disclosed. These references also do not disclose the specific multimers claimed in the present invention.
- the mixture of 2-oxetanone compounds to be used is the reaction product of a reaction mixture comprising at least one 10-26 carbon linear, saturated alkyl monocarboxylic acid and at least one 8-44 carbon linear, saturated alkyl dicarboxylic acid, wherein the mole ratio of mono- to dicarboxylic acids is 1.0 to 3.5, at least 50% by weight of the 2-oxetanone compounds in the mixture having at least two 2-oxetanone rings.
- the paper used in this invention can be made into sheets of 8 1/2 x 11 inch (21.6 x 28 cm) reprographic cut paper having a basis weight of 15-24 lb/1300 ft 2 (6.8 to 10.9 kg/121 m 2 ) and is capable of running on a high speed laser printer or copier without causing misfeeds or jams at a rate of 5 or less in 10,000.
- the paper used in this invention having a basis weight of 20-24 lb/3000 ft 2 (9.1 to 10.9 kg/279 m 2 ) can be converted to a standard perforated continuous form on a continuous forms press at a press speed of 1300 to 2000 feet (390 m to 600 m) per minute.
- the preferred paper used according to the invention having a basis weight of 20-24 lb/3000 ft 2 (9.1 to 10.9 kg/279 m 2 ) is sized at an addition rate of at least 2.2 lb/ton (1 kg/0.9 metric ton) and can be converted to a standard perforated continuous form on the Hamilton-Stevens continuous forms press at a press speed of at least 1775 feet (541 m) per minute, preferably 1900 feet (579 m) per minute.
- the paper to be used having a basis weight of 20-24 lb/1300 ft 2 (9.1 to 10.9 kg/121 m 2 ) can be converted into at least 900 envelopes per minute, preferably at least 1000 per minute, on a Winkler & Dunnebier CH envelope folder.
- Machine-feed problems on high speed converting machines or during reprographic operations are defined as significant in any specific conversion or reprographic application if they cause misfeeds, poor registration, or jams to a commercially unacceptable degree as will be discussed below, or cause machine speed to be reduced.
- the use according to this invention for making paper under alkaline conditions exhibits levels of sizing comparable to those obtained with current AKD and ASA sizing technology, and gives improved handling performance in typical end-use and converting operations.
- the used 2-oxetanone sizing agents of this invention are a mixture of saturated, linear alkyl ketene dimers and 2-oxetanone multimers of varying molecular weights, at least 50 mole %, preferably 60 mole %, of the compounds in the mixture having at least two 2-oxetanone rings.
- the sizing agent therefore has more reactive sites for covalently bonding with cellulose fibers than conventional AKD and ASA alkaline sizes.
- the mole % of compounds having two or more 2-oxetanone rings increases as the mole ratio of mono- to dicarboxylic acids decreases.
- acid chlorides are formed from a mixture of at least one linear, saturated alkyl monocarboxylic acid and at least one linear, saturated alkylene dicarboxylic acid, using phosphorous trichloride or another conventional chlorinating agent.
- the mole ratio of mono- to dicarboxylic acids is 1.0 to 3.5, preferably 2.5, and more preferably 2.0.
- the acid chlorides are then dehydrochlorinated in the presence of triethylamine or another suitable base, in propylene dichloride or another anhydrous, aprotic solvent, to form the mixture of 2-oxetanone compounds.
- the monocarboxylic acid can be a mixture of C 16 and C 18 linear, saturated alkyl monocarboxylic acids, for example, Emery 135 fatty acids, available from Henkel-Emery, Cincinnati, Ohio, U.S.A. Stable emulsions of these sizing agents can be prepared in the same way as standard AKD emulsions.
- the linear, saturated alkyl monocarboxylic acids used to prepare the 2-oxetanone compounds of this invention have 10-26 carbon atoms, preferably 14-22 carbon atoms, and most preferably 16-18 carbon atoms.
- These acids include, for example, stearic, myristic, palmitic, margaric, pentadecanoic, decanoic (capric), undecanoic, dodecanoic (lauric), tridecanoic, nonadecanoic, arachidic, and behenic acids.
- One or more of these monocarboxylic acids can be used.
- the linear, saturated alkylene dicarboxylic acids used to alkylene prepare the 2-oxetanone multimers of this invention have 8-44 carbon atoms, preferably 9-10, 22 or 36 carbon atoms.
- Dicarboxylic acids with 9-10 carbon atoms are most preferred.
- Such dicarboxylic acids include, for example, sebacic, azelaic, dodecanedioic, suberic, brazylic, and docosanedioic acids, and EMPOL 1008 dimer acids (C 36 ), available from Henkel-Emery, Cincinnati, Ohio, U.S.A.
- EMPOL 1008 dimer acids C 36
- One or more of these dicarboxylic acids can be used.
- the alkaline fine paper used according to the invention contains a water soluble inorganic salt of an alkali metal, preferably sodium chloride (NaCl), as well as alum and precipitated calcium carbonate.
- an alkali metal preferably sodium chloride (NaCl)
- NaCl sodium chloride
- the paper used in this invention will often be made without NaCl.
- the sizing agents used in this invention can be applied as internal sizing agents or surface sizing agents.
- Internal sizing involves adding the size to the paper pulp slurry before sheet formation, while surface sizing involves immersion of the paper in the sizing agent or spraying the sizing agent on the paper, followed by drying at elevated temperatures using know drying techniques.
- the paper used in this invention is generally sized at a size addition rate of at least 0.5 lb (0.23 kg), preferably at least 1.5 lb (0.68 kg), and more preferably at least 2.2 lb/ton (1 kg/0.9 metric tons) or higher. It may be, for example, in the form of continuous forms bond paper, perforated continuous forms paper, adding machine paper, or envelope-making paper, as well as converted products, such as copy paper and enyelopes.
- the paper used in this invention is capable of performing effectively in tests that measure its convertibility on state-of-the-art converting equipment and its performance on high speed end-use machinery.
- the paper used in the invention that can be made into a roll of continuous forms bond paper having a basis weight of 30 to 60 lb/3000 ft 2 (13.6 to 27.2 kg/279 m 2 ), preferably 40 to 50 lb/3000 ft 2 (18 to 22.6 kg/279 m 2 ), is capable of running on a high speed, continuous forms laser printer.
- the preferred paper used according to the invention that can be made into sheets of 8 1/2 x 11 inch (21.6 cm x 28 cm) reprographic cut paper having a basis weight of 15-24 lb/1300 ft 2 (6.8 to 10.9 kg/121 m 2 ) is capable of running on a high speed laser printer or copier.
- the paper is sized at an addition rate of at least 1.5 lb/ton (0.68 kg/0.9 metric ton, preferably at least 2.2 lb/ton (1 kg/0.9 metric ton), it is capable of running on the IBM model 3825 high-speed copier without causing misfeeds or jams at a rate of 5 or less in 10,000, preferably at a rate of 1 or less in 10,000.
- paper sized with standard AKD has a much higher rate of double feeds on the IBM 3825 high speed copier (14 double feeds in 14,250 sheets).
- 10 double feeds in 10,000 is unacceptable.
- a machine manufacturer considers 1 double feed in 10,000 sheets to be unacceptable.
- the paper used in this invention in the form of a roll of continuous forms bond paper having a basis weight of 20-24 lb/3000 ft 2 (9.1 to 10.9 kg/279 m 2 ) can be converted to a standard perforated continuous form on a continuous forms press at a press speed of 1300 to 2000 feet (390 m to 600 m) per minute.
- the preferred paper used according to the invention in the form of a roll of continuous forms bond paper having a basis weight of 20-24 lb/3000 ft 2 (9.1 to 10.9 kg/279 m 2 ), and that is sized at an addition rate of at least 2.2 lb/ton (1 kg per 0.9 metric ton) can be converted to a standard perforated continuous form on the Hamilton-Stevens continuous forms press at a press speed of at least 1775 feet (541 m) per minute, preferably at least 1900 feet (579 m) per minute.
- the paper used in this invention can also be made into a roll of envelope paper having a basis weight of 20-24 lb/1300 ft 2 (9.1 to 10.9 kg/121 m 2 ) that is sized at an addition rate of at least 2.2 lb/ton (1 kg/0.9 metric ton).
- the paper can be converted into at least 900 envelopes per minute, preferably at least 1000 per minute on a Winkler & Dunnebier CH envelope folder.
- the paper used in this invention can be run at a speed of at least 58 sheets per minute on a high speed IBM 3825 sheet-fed copier with less than 1 in 10,000 double feeds or jams.
- the paper used in this invention is capable of running on a high speed, continuous-forms laser printer with a rate of billowing at least 10% less, preferably 20% less, than that produced when running on the same printer, a roll of continuous forms bond paper having the same basis weight and sized at the same level with an AKD size made from a mixture of stearic and palmitic acids, after 10 minutes of running time.
- the paper used in this invention is capable of running on a high speed IBM 3825 sheet-fed copier at a speed of 58 sheets per minute with at least 50% fewer, preferably 70% fewer, double feeds or jams than the number of double feeds or jams caused when running on the same copier, sheets of paper having the same basis weight and sized at the same level with an AKD size made from a mixture of stearic and palmitic acids.
- the paper used in this invention is also capable of being converted to a standard perforated continuous form on a continuous forms press at a press speed at least 3% higher, preferably at least 5% higher, than paper having the same basis weight and sized at the same level with an AKD size made from a mixture of stearic and palmitic acids.
- Paper for evaluation on the IBM 3800 was prepared on a pilot paper machine.
- the pulp furnish (three parts Southern hardwood kraft pulp and one part Southern softwood kraft pulp) was refined to 425 ml Canadian Standard Freeness (C.S.F.) using a double disk refiner.
- C.S.F. Canadian Standard Freeness
- the filler to the pulp furnish (10% medium particle-size precipitated calcium carbonate)
- the pH (7.8-8.0) the alkalinity (150-200 p.p.m.), and hardness (100 p.p.m.) of the papermaking stock were adjusted using the appropriate amounts of NaHCO 3 , NaOH, and CaCl 2 .
- the mixture of 2-oxetanone compounds was prepared by methods used conventionally to prepare commercial alkyl ketene dimers, i.e, acid chlorides from a mixture of a linear, saturated fatty acid and a linear, saturated alkylene dicarboxylic acid are formed, using a conventional chlorination agent, and the acid chlorides are dehydrochlorinated in the presence of a suitable base.
- Emulsions of the mixture of 2-oxetanone compounds were prepared according to the disclosure of U.S. Patent 4,317,756, with particular reference to Example 5 of the patent.
- the wet presses were set at 40 p.s.i. (2.8 kg/cm 2 ) gauge. A dryer profile that gave 1-2% moisture at the size press and 4-6% moisture at the reel was used (77 feet (23.4 m) per minute).
- HST Hercules Size Test
- a 35 minute roll of paper was collected and converted on a commercial forms press to two boxes of standard 8 1/2" x 11" (21.6 x 28 cm) forms. Samples were also collected before and after each 35 minute roll for natural aged size testing basis weight (46 lb/3000 ft 2 , 20.8 kg/279 m 2 ), and smoothness testing.
- the converted paper was allowed to equilibrate in the printer room for at least one day prior to evaluation. Each box of paper allowed a 10-14 minute (220 feet (66.7 m) per minute) evaluation on the IBM 3800. All samples were tested in duplicate. A standard acid fine paper was run for at least two minutes between each evaluation to reestablish initial machine conditions.
- the Hercules Size Test is a standard test in the industry for measuring the degree of sizing. This method employs an aqueous dye solution as the penetrant to permit optical detection of the liquid front as it moves through the sheet. The apparatus determines the time required for the reflectance of the sheet surface not in contact with the penetrant to drop to a predetermined percentage of its original reflectance. All HST testing data reported measure the seconds to 80% reflection with 1% formic acid ink mixed with naphthol green B dye unless otherwise noted. The use of formic acid ink is a more severe test than neutral ink and tends to give faster test times. High HST values are better than low values. The amount of sizing desired depends upon the kind of paper being made and the system used to make it.
- This example describes the preparation of a mixture of 2-oxetanone compounds from a blend of stearic and sebacic acids at a molar ratio of 2.5.
- a blend of stearic acid (227.2 g, 0.8 mole) and sebacic acid (64.64 g, 0.32 mole) with a molar ratio of 2.5 was heated to melt at a temperature in the range of 110 to 116°C under a nitrogen atmosphere.
- the molten acid blend was then poured into a pyrex jacketed vessel equipped with a mechanical stirrer, condenser, nitrogen purge, and thermocouple and preheated to 95°C.
- PCl 3 130.5 g was dropped into the reactor all at one time. After 3 hours of chlorination and settling, phosphorous acid was separated from the acid chloride blend.
- This example describes the preparation of a mixture of 2-oxetanone compounds from a blend of palmitic/azelaic acids at a molar ratio of 2.5.
- a blend of palmitic acid (204.8 g, 0.8 mole) and azelaic acid (60.16 g, 0.32 mole) with a molar ratio of 2.5 was heated to melt at a temperature of 80° to 85°C under a nitrogen atmosphere.
- the molten acid blend was then poured into a pyrex glass jacketed vessel equipped with a mechanical stirrer, condenser, nitrogen purge and thermocouple, and preheated to the chlorination temperature (70 ⁇ 2°C).
- the chlorinating agent, PCl 3 (97.9 g) was added to the vessel all at one time.
- the vessel temperature dropped 2° to 5°C initially, but eventually stabilized at 70 ⁇ 2°C.
- sizing agents were tested for their effects on the IBM 3800 runnability of a difficult-to-convert grade of alkaline fine paper.
- the control was a standard AKD sizing agent made from a mixture of stearic and palmitic acids using the method described in Examples 1 and 2.
- the mixture of 2-oxetanone compounds used in samples 2-6 was prepared using the method described in Examples 1 and 2, using the following mixtures of mono- and dicarboxylic acids at the mole ratio indicated in the table: Sample 2 - palmitic acid/dodecanedioic acid; Sample 3 - palmitic acid/sebacic acid; Sample 4 - palmitic acid/azelaic acid; Sample 5 - stearic acid/sebacic acid; Sample 6 - stearic acid/EMPOL 1008 C 36 dimer acids, available from Henkel-Emery, Cincinnati, Ohio, U.S.A.
- the percentage of 2-oxetanone compounds containing two or more rings is: Sample 2, 58.2%; Sample 3, 64.7%; Sample 4, 58.2%; Sample 5, 54.7%, and Sample 6, 63.1%.
Abstract
Description
- This invention relates to the use of fine paper sized with a sizing agent comprising a mixture of 2-oxetanone compounds in high speed precision converting on reprographic operations.
- The amount of fine paper produced under alkaline conditions has been increasing rapidly, encouraged by cost savings, the ability to use precipitated calcium carbonate, an increased demand for improved paper permanence and brightness, and an increased tendency to close the wet end of the paper machine.
- Current applications for fine paper require particular attention to sizing before conversion or end-use, such as high-speed photocopies, envelopes, forms bond including computer printer paper, and adding machine paper. The most common sizing agents for fine paper made under alkaline conditions are alkenyl succinic anhydride (ASA) and alkyl ketene dimer (AKD). Both types of sizing agents have a reactive functional group that covalently bonds to cellulose fiber and hydrophobic tails that are oriented away from the fiber. The nature and orientation of these hydrophobic tails cause the fiber to repel water.
- Commercial AKD's, containing one β-lactone ring, are prepared by the dimerization of the alkyl ketenes made from two saturated, straight-chain fatty acid chlorides; the most widely used being prepared from palmitic and/or stearic acid. Other ketene dimers, such as the alkenyl-based ketene dimer (Aquapel® 421, available from Hercules Incorporated, Wilmington, DE, U.S.A.), have also been used commercially. ASA-based sizing agents can be prepared by the reaction of maleic anhydride with a 14 to 18 carbon olefin.
- Although ASA and AKD sizing agents are commercially successful, they have disadvantages. Both types of sizing agents, particularly the AKD type, have been associated with handling problems in the typical high-speed conversion operations required for the current uses of fine paper made under alkaline conditions (referred to as alkaline fine paper). The problems include reduced operating speed in forms presses and other converting machines, double feeds or jams in high-speed copiers, and registration errors on printing and envelope-folding equipment that operate at high speeds.
- These problems are not normally associated with fine paper produced under acid conditions (acid fine paper). The types of filler and filler addition levels used to make alkaline fine paper differ significantly from those used to make acid fine paper, and can cause differences in paper properties such as stiffness and coefficient of friction, which affect paper handling. Alum addition levels in alkaline fine paper, which contribute to sheet conductivity and dissipation of static charge, also differ significantly from those used in acid fine paper. This is important because the electrical properties of paper affect its handling performance. Sodium chloride is often added to the surface of alkaline fine paper to improve its end-use performance.
- The typical problems encountered with the conversion and end-use handling of alkaline fine paper involve:
- 1. Paper properties related to the composition of the furnish;
- 2. Paper properties developed during paper formation; and
- 3. Problems related to sizing.
-
- The paper properties affected by papermaking under alkaline conditions that can affect converting and end-use performance include:
- Curl
- Variation in coefficient of friction
- Moisture content
- Moisture profile
- Stiffness
- Dimensional stability
- MD/CD strength ratios
- One such problem has been identified and measured as described in "Improving the Performance of Alkaline Fine Paper on the IBM 3800 Laser Printer," TAPPI Paper Makers Conference Proceedings (1991). The problem occurs when using an IBM 3800 high speed continuous forms laser printer that does not have special modifications intended to facilitate handling of alkaline fine paper. This commercially-significant laser printer therefore can serve as an effective testing device for defining the convertibility of various types of sized paper on state-of-the-art converting equipment and its subsequent end-use performance. In particular, the phenomenon of "billowing" gives a measurable indication of the extent of slippage on the IBM 3800 printer between the undriven roll beyond the fuser and the driven roll above the stacker.
- Such billowing involves a divergence of the paper path from the straight line between the rolls, which is two inches (5 cm) above the base plate, causing registration errors and dropped folds in the stacker. The rate of billowing during steady-state running time is measured as the billowing height in inches (1 inch = 0.025m) above the straight paper path after 600 seconds of running time and multiplied by 10,000.
- Typical alkaline AKD sized fine paper using a size furnish of 2.2 lbs. per ton (1 kg per 0.9 metric ton) of paper shows an unacceptable rate-of-billowing, typically of the order of 20 to 80. Paper handling rates on other high-speed converting machinery, such as the Hamilton-Stevens continuous forms press, or the Winkler & Dunnebier CH envelope folder also provide numerical measures of convertibility.
- Ketene multimers containing more than one beta-lactone ring have also been disclosed as sizing agents for paper in Japanese Kokai 168991/89 and 168992/89. The ketene multimers are said to show improved sizing compared to the ketene dimers previously used. The multimers are prepared from a mixture of mono- and dicarboxylic acids. The advantage of a combination of good sizing and good performance on high speed converting or reprographic equipment is not disclosed. These references also do not disclose the specific multimers claimed in the present invention.
- There is a need for alkaline fine paper that provides improved handling performance in typical converting and reprographic operations. At the same time, the levels of sizing development must be comparable to that obtained with the current furnish levels of AKD or ASA for alkaline fine paper.
- The paper used in this invention is sized with a sizing agent comprising a mixture of 2-oxetanone compounds under alkaline conditions and the 2-oxetanone compounds have the formula in which n is 0 or an integer; R and R", which can be the same or different, are saturated, linear straight chain alkyl groups having 8-24 carbon atoms, preferably 14 or 16 carbon atoms; R' is a saturated, linear alkylene group having 4-40 carbon atoms, preferably 5 or 6 carbon atoms, and in at least 50% by weight of the 2-oxetanone compounds, preferably 60%, n = at least 1, said mixture being the reaction product of a reaction mixture comprising at least one 10-26 carbon linear saturated alkyl monocarboxylic acid and at least one 8-44 carbon linear saturated alkylene dicarboxylic acid wherein the ratio of mono- to di-carboxylic acid is 1.0 to 3.5 and is used in a high speed precision converting or reprographic operation comprising converting continuous forms bond paper to perforated continuous forms paper at a press speed of at least 390 metres per minute, or converting a roll of envelope paper into envelopes at a rate of at least 900 envelopes per minute, or a printer or copier operation at a speed of at least 66.7 metres per minute or at least 58 sheets per minute. The used paper is capable of performing without encountering significant machine-feed problems on high speed converting machines or in reprographic operations.
- According to the invention, the mixture of 2-oxetanone compounds to be used is the reaction product of a reaction mixture comprising at least one 10-26 carbon linear, saturated alkyl monocarboxylic acid and at least one 8-44 carbon linear, saturated alkyl dicarboxylic acid, wherein the mole ratio of mono- to dicarboxylic acids is 1.0 to 3.5, at least 50% by weight of the 2-oxetanone compounds in the mixture having at least two 2-oxetanone rings.
- Preferably, the paper used according to the invention is capable of being formed into a roll of continuous forms bond paper having a basis weight of 30 to 60 lb/3000 ft2 (13.6 to 27.2 kg per 279 m2) and is capable of running on the IBM Model 3800 high speed, continuous-forms laser printer without causing a rate of billowing in inches (1 inch = 0.025 m) of increase per second x 10,000 greater than 5.
- The paper used in this invention can be made into sheets of 8 1/2 x 11 inch (21.6 x 28 cm) reprographic cut paper having a basis weight of 15-24 lb/1300 ft2 (6.8 to 10.9 kg/121 m2) and is capable of running on a high speed laser printer or copier without causing misfeeds or jams at a rate of 5 or less in 10,000.
- The paper used in this invention having a basis weight of 20-24 lb/3000 ft2 (9.1 to 10.9 kg/279 m2) can be converted to a standard perforated continuous form on a continuous forms press at a press speed of 1300 to 2000 feet (390 m to 600 m) per minute. The preferred paper used according to the invention having a basis weight of 20-24 lb/3000 ft2 (9.1 to 10.9 kg/279 m2) is sized at an addition rate of at least 2.2 lb/ton (1 kg/0.9 metric ton) and can be converted to a standard perforated continuous form on the Hamilton-Stevens continuous forms press at a press speed of at least 1775 feet (541 m) per minute, preferably 1900 feet (579 m) per minute.
- Also according to the invention, the paper to be used having a basis weight of 20-24 lb/1300 ft2 (9.1 to 10.9 kg/121 m2) can be converted into at least 900 envelopes per minute, preferably at least 1000 per minute, on a Winkler & Dunnebier CH envelope folder.
- Machine-feed problems on high speed converting machines or during reprographic operations are defined as significant in any specific conversion or reprographic application if they cause misfeeds, poor registration, or jams to a commercially unacceptable degree as will be discussed below, or cause machine speed to be reduced.
- The use according to this invention for making paper under alkaline conditions exhibits levels of sizing comparable to those obtained with current AKD and ASA sizing technology, and gives improved handling performance in typical end-use and converting operations.
- The used 2-oxetanone sizing agents of this invention are a mixture of saturated, linear alkyl ketene dimers and 2-oxetanone multimers of varying molecular weights, at least 50 mole %, preferably 60 mole %, of the compounds in the mixture having at least two 2-oxetanone rings. The sizing agent therefore has more reactive sites for covalently bonding with cellulose fibers than conventional AKD and ASA alkaline sizes. The mole % of compounds having two or more 2-oxetanone rings increases as the mole ratio of mono- to dicarboxylic acids decreases.
- These reactive sizing agents can be prepared using methods disclosed in Japanese Kokai 168992/89 and US-A-4,317,756. In the first step, acid chlorides are formed from a mixture of at least one linear, saturated alkyl monocarboxylic acid and at least one linear, saturated alkylene dicarboxylic acid, using phosphorous trichloride or another conventional chlorinating agent. The mole ratio of mono- to dicarboxylic acids is 1.0 to 3.5, preferably 2.5, and more preferably 2.0. The acid chlorides are then dehydrochlorinated in the presence of triethylamine or another suitable base, in propylene dichloride or another anhydrous, aprotic solvent, to form the mixture of 2-oxetanone compounds. The monocarboxylic acid can be a mixture of C16 and C18 linear, saturated alkyl monocarboxylic acids, for example, Emery 135 fatty acids, available from Henkel-Emery, Cincinnati, Ohio, U.S.A. Stable emulsions of these sizing agents can be prepared in the same way as standard AKD emulsions.
- The linear, saturated alkyl monocarboxylic acids used to prepare the 2-oxetanone compounds of this invention have 10-26 carbon atoms, preferably 14-22 carbon atoms, and most preferably 16-18 carbon atoms. These acids include, for example, stearic, myristic, palmitic, margaric, pentadecanoic, decanoic (capric), undecanoic, dodecanoic (lauric), tridecanoic, nonadecanoic, arachidic, and behenic acids. One or more of these monocarboxylic acids can be used.
- The linear, saturated alkylene dicarboxylic acids used to alkylene prepare the 2-oxetanone multimers of this invention have 8-44 carbon atoms, preferably 9-10, 22 or 36 carbon atoms. Dicarboxylic acids with 9-10 carbon atoms are most preferred. Such dicarboxylic acids include, for example, sebacic, azelaic, dodecanedioic, suberic, brazylic, and docosanedioic acids, and EMPOL 1008 dimer acids (C36), available from Henkel-Emery, Cincinnati, Ohio, U.S.A. One or more of these dicarboxylic acids can be used.
- Preferably, the alkaline fine paper used according to the invention contains a water soluble inorganic salt of an alkali metal, preferably sodium chloride (NaCl), as well as alum and precipitated calcium carbonate. However, the paper used in this invention will often be made without NaCl.
- The sizing agents used in this invention can be applied as internal sizing agents or surface sizing agents. Internal sizing involves adding the size to the paper pulp slurry before sheet formation, while surface sizing involves immersion of the paper in the sizing agent or spraying the sizing agent on the paper, followed by drying at elevated temperatures using know drying techniques.
- The paper used in this invention is generally sized at a size addition rate of at least 0.5 lb (0.23 kg), preferably at least 1.5 lb (0.68 kg), and more preferably at least 2.2 lb/ton (1 kg/0.9 metric tons) or higher. It may be, for example, in the form of continuous forms bond paper, perforated continuous forms paper, adding machine paper, or envelope-making paper, as well as converted products, such as copy paper and enyelopes.
- The paper used in this invention is capable of performing effectively in tests that measure its convertibility on state-of-the-art converting equipment and its performance on high speed end-use machinery. In particular, the paper used in the invention that can be made into a roll of continuous forms bond paper having a basis weight of 30 to 60 lb/3000 ft2 (13.6 to 27.2 kg/279 m2), preferably 40 to 50 lb/3000 ft2 (18 to 22.6 kg/279 m2), is capable of running on a high speed, continuous forms laser printer. When this paper is sized at an addition rate of at least 2.2 lb/ton (1 kg/0.9 metric ton), it is capable of running on the IBM Model 3800 high speed, continuous-forms laser printer without causing a rate of billowing in inches (1 inch = 0.025 m) of increase per second x 10,000 greater than 5 after ten minutes running time, preferably 3 or less.
- Further, the preferred paper used according to the invention, that can be made into sheets of 8 1/2 x 11 inch (21.6 cm x 28 cm) reprographic cut paper having a basis weight of 15-24 lb/1300 ft2 (6.8 to 10.9 kg/121 m2) is capable of running on a high speed laser printer or copier. When the paper is sized at an addition rate of at least 1.5 lb/ton (0.68 kg/0.9 metric ton, preferably at least 2.2 lb/ton (1 kg/0.9 metric ton), it is capable of running on the IBM model 3825 high-speed copier without causing misfeeds or jams at a rate of 5 or less in 10,000, preferably at a rate of 1 or less in 10,000. By comparison, paper sized with standard AKD has a much higher rate of double feeds on the IBM 3825 high speed copier (14 double feeds in 14,250 sheets). In conventional copy-machine operation, 10 double feeds in 10,000 is unacceptable. A machine manufacturer considers 1 double feed in 10,000 sheets to be unacceptable.
- The paper used in this invention in the form of a roll of continuous forms bond paper having a basis weight of 20-24 lb/3000 ft2 (9.1 to 10.9 kg/279 m2) can be converted to a standard perforated continuous form on a continuous forms press at a press speed of 1300 to 2000 feet (390 m to 600 m) per minute. The preferred paper used according to the invention, in the form of a roll of continuous forms bond paper having a basis weight of 20-24 lb/3000 ft2 (9.1 to 10.9 kg/279 m2), and that is sized at an addition rate of at least 2.2 lb/ton (1 kg per 0.9 metric ton) can be converted to a standard perforated continuous form on the Hamilton-Stevens continuous forms press at a press speed of at least 1775 feet (541 m) per minute, preferably at least 1900 feet (579 m) per minute.
- The paper used in this invention can also be made into a roll of envelope paper having a basis weight of 20-24 lb/1300 ft2 (9.1 to 10.9 kg/121 m2) that is sized at an addition rate of at least 2.2 lb/ton (1 kg/0.9 metric ton). The paper can be converted into at least 900 envelopes per minute, preferably at least 1000 per minute on a Winkler & Dunnebier CH envelope folder.
- The paper used in this invention can be run at a speed of at least 58 sheets per minute on a high speed IBM 3825 sheet-fed copier with less than 1 in 10,000 double feeds or jams.
- The paper used in this invention is capable of running on a high speed, continuous-forms laser printer with a rate of billowing at least 10% less, preferably 20% less, than that produced when running on the same printer, a roll of continuous forms bond paper having the same basis weight and sized at the same level with an AKD size made from a mixture of stearic and palmitic acids, after 10 minutes of running time.
- The paper used in this invention is capable of running on a high speed IBM 3825 sheet-fed copier at a speed of 58 sheets per minute with at least 50% fewer, preferably 70% fewer, double feeds or jams than the number of double feeds or jams caused when running on the same copier, sheets of paper having the same basis weight and sized at the same level with an AKD size made from a mixture of stearic and palmitic acids.
- The paper used in this invention is also capable of being converted to a standard perforated continuous form on a continuous forms press at a press speed at least 3% higher, preferably at least 5% higher, than paper having the same basis weight and sized at the same level with an AKD size made from a mixture of stearic and palmitic acids.
- Paper for evaluation on the IBM 3800 was prepared on a pilot paper machine. To make a typical forms bond papermaking stock, the pulp furnish (three parts Southern hardwood kraft pulp and one part Southern softwood kraft pulp) was refined to 425 ml Canadian Standard Freeness (C.S.F.) using a double disk refiner. Prior to the addition of the filler to the pulp furnish (10% medium particle-size precipitated calcium carbonate), the pH (7.8-8.0), alkalinity (150-200 p.p.m.), and hardness (100 p.p.m.) of the papermaking stock were adjusted using the appropriate amounts of NaHCO3, NaOH, and CaCl2.
- The mixture of 2-oxetanone compounds was prepared by methods used conventionally to prepare commercial alkyl ketene dimers, i.e, acid chlorides from a mixture of a linear, saturated fatty acid and a linear, saturated alkylene dicarboxylic acid are formed, using a conventional chlorination agent, and the acid chlorides are dehydrochlorinated in the presence of a suitable base. Emulsions of the mixture of 2-oxetanone compounds were prepared according to the disclosure of U.S. Patent 4,317,756, with particular reference to Example 5 of the patent. Wet-end additions of the 2-oxetanone multimer sizing agent, quaternary-amine-substituted cationic starch (0.75%), alum (0.2%), and retention aid (0.025%) were made. Stock temperature at the headbox and white water tray was controlled at 110°F (43.3°C).
- The wet presses were set at 40 p.s.i. (2.8 kg/cm2) gauge. A dryer profile that gave 1-2% moisture at the size press and 4-6% moisture at the reel was used (77 feet (23.4 m) per minute). Before the size press, the sizing level was measured on a sample of paper torn from the edge of the sheet, using the Hercules Size Test (HST). Approximately 35 lb/ton (15.9 kg/0.9 metric ton) of an oxidized corn starch and 1 lb/ton (0.45 kg/0.9 metric ton) of NaCl were added at the size press (130°F (54.4°C), pH 8). Calender pressure and reel moisture were adjusted to obtain a Sheffield smoothness of 150 flow units at the reel (Column #2, felt side up).
- A 35 minute roll of paper was collected and converted on a commercial forms press to two boxes of standard 8 1/2" x 11" (21.6 x 28 cm) forms. Samples were also collected before and after each 35 minute roll for natural aged size testing basis weight (46 lb/3000 ft2, 20.8 kg/279 m2), and smoothness testing.
- The converted paper was allowed to equilibrate in the printer room for at least one day prior to evaluation. Each box of paper allowed a 10-14 minute (220 feet (66.7 m) per minute) evaluation on the IBM 3800. All samples were tested in duplicate. A standard acid fine paper was run for at least two minutes between each evaluation to reestablish initial machine conditions.
- In order to establish whether a sizing agent contributes to difficulties in converting operations, paper was made on a pilot paper machine, converted into forms, and then printed on an IBM 3800 high speed printer. The runnability on the IBM 3800 was used as a measure of converting performance. Specifically, the height to which the paper billows between two defined rolls on the IBM 3800 was used to quantify converting performance. The faster and higher the sheet billows, the worse the converting performance.
- The Hercules Size Test (HST) is a standard test in the industry for measuring the degree of sizing. This method employs an aqueous dye solution as the penetrant to permit optical detection of the liquid front as it moves through the sheet. The apparatus determines the time required for the reflectance of the sheet surface not in contact with the penetrant to drop to a predetermined percentage of its original reflectance. All HST testing data reported measure the seconds to 80% reflection with 1% formic acid ink mixed with naphthol green B dye unless otherwise noted. The use of formic acid ink is a more severe test than neutral ink and tends to give faster test times. High HST values are better than low values. The amount of sizing desired depends upon the kind of paper being made and the system used to make it.
- This example describes the preparation of a mixture of 2-oxetanone compounds from a blend of stearic and sebacic acids at a molar ratio of 2.5.
- A blend of stearic acid (227.2 g, 0.8 mole) and sebacic acid (64.64 g, 0.32 mole) with a molar ratio of 2.5 was heated to melt at a temperature in the range of 110 to 116°C under a nitrogen atmosphere. The molten acid blend was then poured into a pyrex jacketed vessel equipped with a mechanical stirrer, condenser, nitrogen purge, and thermocouple and preheated to 95°C. When the molten acids in the vessel cooled down to a temperature of 75° to 85°C, PCl3 (130.5 g) was dropped into the reactor all at one time. After 3 hours of chlorination and settling, phosphorous acid was separated from the acid chloride blend. The excess PCl3 was stripped off under a vacuum to recover the acid chloride blend (307.5 g, 1.12 moles) in an almost theoretical yield. The blend of stearic and sebacic chlorides was then added by drops to a reactor containing propylene dichloride as the reaction solvent (650 ml) and triethylamine (160 g, 1.584 moles, 10% molar excess) as the base catalyst at 40 to 45°C. After 2 hours, the triethylamine hydrochloride salt was separated by suction filtration and a stearic/sebacic 2-oxetanone multimer mixture was recovered as a pale-yellow solid (232.78 g). Solvent and excess triethylamine were evaporated to give an overall yield of 90% multimer. The mixture contained 54.7% multimers having 2 or more oxetanone rings.
- This example describes the preparation of a mixture of 2-oxetanone compounds from a blend of palmitic/azelaic acids at a molar ratio of 2.5.
- A blend of palmitic acid (204.8 g, 0.8 mole) and azelaic acid (60.16 g, 0.32 mole) with a molar ratio of 2.5 was heated to melt at a temperature of 80° to 85°C under a nitrogen atmosphere. The molten acid blend was then poured into a pyrex glass jacketed vessel equipped with a mechanical stirrer, condenser, nitrogen purge and thermocouple, and preheated to the chlorination temperature (70±2°C). The chlorinating agent, PCl3 (97.9 g) was added to the vessel all at one time. The vessel temperature dropped 2° to 5°C initially, but eventually stabilized at 70±2°C. After 3 hours of chlorination and settling, phosphorous acids were separated from the acid chloride blend. The excess PCl3 was stripped off under a vacuum to recover 290.0 g of the acid chloride blend in an almost theoretical yield. The blend of palmitic and azelaic chlorides was then added by drops to a reactor containing propylene dichloride (600 ml) as the reaction solvent and triethylamine (160 g, 10% excess) as the base catalyst at 40 to 45°C. After two hours, the triethylamine hydrochloride salts were separated by suction filtration and the 2-oxetanone multimer mixture was recovered as a pale-yellow solid by evaporation of solvent and excess triethylamine. The an overall yield was 96% (240.53 g). The mixture contained 58.2% multimers having 2 or more oxetanone rings.
- In this example a number of sizing agents were tested for their effects on the IBM 3800 runnability of a difficult-to-convert grade of alkaline fine paper. The control was a standard AKD sizing agent made from a mixture of stearic and palmitic acids using the method described in Examples 1 and 2. The mixture of 2-oxetanone compounds used in samples 2-6 was prepared using the method described in Examples 1 and 2, using the following mixtures of mono- and dicarboxylic acids at the mole ratio indicated in the table: Sample 2 - palmitic acid/dodecanedioic acid; Sample 3 - palmitic acid/sebacic acid; Sample 4 - palmitic acid/azelaic acid; Sample 5 - stearic acid/sebacic acid; Sample 6 - stearic acid/EMPOL 1008 C36 dimer acids, available from Henkel-Emery, Cincinnati, Ohio, U.S.A. The percentage of 2-oxetanone compounds containing two or more rings is: Sample 2, 58.2%; Sample 3, 64.7%; Sample 4, 58.2%; Sample 5, 54.7%, and Sample 6, 63.1%.
-
- The data show that the 2-oxetanone sizing agents of this invention gave a better balance of sizing and converting performance (less billowing at the same level of sizing) than the commercial alkene dimer size used as the control. The best balance of sizing and handling performance was obtained with Sample 3. This sizing agent gave a level of sizing comparable to that obtained with the AKD control and gave paper with better runnability on the IBM 3800 than the paper sized with the AKD control.
Claims (9)
- Use of fine paper having been sized under alkaline conditions with a sizing agent comprising a mixture of 2-oxetanone compounds, wherein the 2-oxetanone compounds have the formula in which n is 0 or an integer, R and R" can be the same or different and are saturated, linear alkyl groups having 8-24 carbon atoms; R' is a saturated, linear alkylene group having 4-40 carbon atoms, and n = at least one in at least 50% by weight of the compounds in the mixture, said mixture being the reaction product of a reaction mixture comprising at least one 10-26 carbon linear saturated alkyl monocarboxylic acid and at least one 8-44 carbon linear saturated alkylene dicarboxylic acid wherein the ratio of mono- to di-carboxylic acid is 1.0 to 3.5, and characterised in that the paper is used in a high speed precision converting or reprographic operation comprising converting continuous forms bond paper to perforated continuous forms paper at a press speed of at least 390 metres per minute, or converting a roll of envelope paper into envelopes at a rate of at least 900 envelopes per minute, or a printer or copier operation at a speed of at least 66.7 metres per minute or at least 58 sheets per minute.
- Use of fine paper according to claim 1, wherein the 2-oxetanone compounds have the formula in which n is 0 or an integer, R and R" can be the same or different and are saturated, linear alkyl groups having 14 or 16 carbon atoms; R' is a saturated, linear alkylene group having 5-6 carbon atoms, and n = at least one in at least 50% by weight of the compounds in the mixture, said mixture being the reaction product of a reaction mixture comprising a 16 or 18 carbon linear saturated alkyl monocarboxylic acid and a 9 or 10 carbon linear saturated alkylene dicarboxylic acid wherein the ratio of mono- to di-carboxylic acid is 1.0 to 3.5.
- Use of fine paper as claimed in claim 2 in making perforated continuous paper, adding machine paper or envelopes.
- Use of fine paper as claimed in claim 2 in making photocopies using reprographic cut paper or continuous forms bond paper.
- Use of a mixture of 2-oxetanone compounds wherein the 2-oxetanone compounds have the formula in which n is 0 or an integer, R and R" can be the same or different and are saturated, linear alkyl groups having 8-24 carbon atoms; R' is a saturated, linear alkylene group having 4-40 carbon atoms, and n = at least one in at least 50% by weight of the compounds in the mixture, said mixture being the reaction product of a reaction mixture comprising at least one 10-26 carbon linear saturated alkyl monocarboxylic acid and at least one 8-44 carbon linear saturated alkylene dicarboxylic acid wherein the ratio of mono- to di-carboxylic acid is 1.0 to 3.5, in the treatment of fine paper to prevent handling problems in a high speed precision converting or reprographic operation comprising converting continuous forms bond paper to perforated continuous forms paper at a press speed of at least 390 metres per minute, or converting a roll of envelope paper into envelopes at a rate of at least 900 envelopes per minute, or a printer or copier operation at a speed of at least 66.7 metres per minute or at least 58 sheets per minute.
- Use of a mixture of 2-oxeranone compounds according to claim 5, wherein the 2-oxetanone compounds have the formula in which n is 0 or an integer, R and R" can be the same or different and are saturated, linear alkyl groups having 14 or 16 carbon atoms; R' is a saturated, linear alkylene group having 5-6 carbon atoms, and n = at least one in at least 50% by weight of the compounds in the mixture, said mixture being the reaction product of a reaction mixture comprising a 16 or 18 carbon linear saturated alkyl monocarboxylic acid and a 9 or 10 carbon linear saturated alkylene dicarboxylic acid wherein the ratio of mono- to di-carboxylic acid is 1.0 to 3.5.
- A use accoding to any preceding claims wherein the high speed precision converting a reprographic operation comprises converting continuous forms bond paper to perforated continuous forms paper at a press speed of at least 390 metres per minute.
- A use according to any one of claims 1 to 10 wherein the high speed precision converting or reprographic operation comprises converting a roll of envelope paper into envelopes at a rate of at least 900 envelopes per minute.
- A use according to any one of claims 1 to 10 wherein the high speed precision converting or reprographic operation comprises a printer or copier operation at a speed of at least 66.7 metres per minute or at least 58 sheets per minute.
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GB9311944 | 1993-06-10 | ||
GB939311944A GB9311944D0 (en) | 1993-06-10 | 1993-06-10 | Synthesis of alkyl ketene multimers (akm) and application for precision converting grades of fine paper |
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EP0629741B1 true EP0629741B1 (en) | 2001-08-16 |
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EP (1) | EP0629741B1 (en) |
JP (1) | JPH0797791A (en) |
KR (1) | KR950001019A (en) |
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AU (1) | AU671212C (en) |
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DE (1) | DE69427939T2 (en) |
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PT (1) | PT629741E (en) |
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1993
- 1993-06-10 GB GB939311944A patent/GB9311944D0/en active Pending
-
1994
- 1994-06-07 FI FI942685A patent/FI942685A/en unknown
- 1994-06-08 EP EP94304136A patent/EP0629741B1/en not_active Expired - Lifetime
- 1994-06-08 PT PT94304136T patent/PT629741E/en unknown
- 1994-06-08 DE DE69427939T patent/DE69427939T2/en not_active Expired - Fee Related
- 1994-06-08 ES ES94304136T patent/ES2160112T3/en not_active Expired - Lifetime
- 1994-06-08 AT AT94304136T patent/ATE204347T1/en not_active IP Right Cessation
- 1994-06-09 CA CA002117318A patent/CA2117318C/en not_active Expired - Fee Related
- 1994-06-09 AU AU64650/94A patent/AU671212C/en not_active Ceased
- 1994-06-10 BR BR9402372A patent/BR9402372A/en not_active IP Right Cessation
- 1994-06-10 KR KR1019940013070A patent/KR950001019A/en not_active Application Discontinuation
- 1994-06-10 ZA ZA944111A patent/ZA944111B/en unknown
- 1994-06-10 JP JP6129122A patent/JPH0797791A/en active Pending
- 1994-06-16 TW TW083105460A patent/TW279913B/zh active
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Technical Bulletin 145S, "Specifications and Characteristics of Emery Oleochemicals", Henkel Corporation, Emery Group, May 1993 * |
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Also Published As
Publication number | Publication date |
---|---|
BR9402372A (en) | 1995-03-14 |
CA2117318C (en) | 2001-06-05 |
DE69427939T2 (en) | 2001-11-29 |
TW279913B (en) | 1996-07-01 |
ATE204347T1 (en) | 2001-09-15 |
ZA944111B (en) | 1995-02-02 |
JPH0797791A (en) | 1995-04-11 |
AU671212C (en) | 2001-07-19 |
FI942685A (en) | 1994-12-11 |
PT629741E (en) | 2002-02-28 |
DE69427939D1 (en) | 2001-09-20 |
GB9311944D0 (en) | 1993-07-28 |
AU6465094A (en) | 1994-12-15 |
ES2160112T3 (en) | 2001-11-01 |
EP0629741A1 (en) | 1994-12-21 |
AU671212B2 (en) | 1996-08-15 |
CA2117318A1 (en) | 1994-12-11 |
KR950001019A (en) | 1995-01-03 |
FI942685A0 (en) | 1994-06-07 |
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