WO1995024526A1 - Method of agglomerating printing ink and formulations for use therein - Google Patents
Method of agglomerating printing ink and formulations for use therein Download PDFInfo
- Publication number
- WO1995024526A1 WO1995024526A1 PCT/US1995/002670 US9502670W WO9524526A1 WO 1995024526 A1 WO1995024526 A1 WO 1995024526A1 US 9502670 W US9502670 W US 9502670W WO 9524526 A1 WO9524526 A1 WO 9524526A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ink
- formula
- formulation
- ethylene oxide
- propylene oxide
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 238000009472 formulation Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000007639 printing Methods 0.000 title description 8
- 239000002245 particle Substances 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 239000000835 fiber Substances 0.000 claims abstract description 29
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 23
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003209 petroleum derivative Substances 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims description 24
- 230000000996 additive effect Effects 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 9
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 5
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 5
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 101000666896 Homo sapiens V-type immunoglobulin domain-containing suppressor of T-cell activation Proteins 0.000 claims 1
- 102100038282 V-type immunoglobulin domain-containing suppressor of T-cell activation Human genes 0.000 claims 1
- IJJVMEJXYNJXOJ-UHFFFAOYSA-N fluquinconazole Chemical group C=1C=C(Cl)C=C(Cl)C=1N1C(=O)C2=CC(F)=CC=C2N=C1N1C=NC=N1 IJJVMEJXYNJXOJ-UHFFFAOYSA-N 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000000976 ink Substances 0.000 description 35
- 239000002002 slurry Substances 0.000 description 9
- 238000004537 pulping Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 150000004665 fatty acids Chemical group 0.000 description 3
- -1 poly(ethylene oxide) Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000013055 pulp slurry Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 238000007648 laser printing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/02—Working-up waste paper
- D21C5/025—De-inking
- D21C5/027—Chemicals therefor
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
Definitions
- This invention relates to methods and formulations to de-ink paper containing printed matter that has been applied by non-impact printing methods. More specifically, the invention relates to methods and formulations which separate the ink from paper and agglomerate the separated ink to form particles of a size sufficient that they can be efficiently removed from the paper.
- U.S. Patent Nos . 4,820,379 and 5,102,500 disclose agglomerating reprographic inks with alkoxy-capped poly(ethylene oxide) additives in the presence of a polymeric material and, optionally, a chelating agent.
- U.S. Patent No. 5,141,598 discloses de-inking electrostatically printed paper using a mixture of an aliphatic petroleum distillate, an alkylphenoxy (ethyleneoxy) ethanol and an ethoxylated polyoxypropylene glycol . The mixture has a combined HLB less than 10 and a weight ratio of 6:1:3.
- this invention provides a de-inking method where reprographic or non-impact inks are separated from repulped paper fibers and agglomerated to a size sufficient to permit their removal from those fibers.
- the method comprises the step of contacting repulped fibers containing non-impact printed subject matter with an additive formulation for a time and at a temperature sufficient to separate the ink from the repulped paper fibers and to agglomerate the separated ink into particles of a size sufficient to permit their removal from the fibers.
- the additive formulation comprises (1) 85 to 10% by weight of at least one petroleum distillate and (2) 15 to 90% by weight of at least one derivatized ethylene oxide/propylene oxide polymer having the structural formula I :
- R is a linear or branched, saturated or unsaturated hydrocarbon chain having 1 to 20 carbon atoms.
- the invention also provides a formulation useful for carrying out the method. That formulation comprises
- Additives commonly used in de-inking operations include surfactants, bleaches, brighteners, softeners, defoamers, dispersants, and chelants.
- Conventionally used repulping de-inking agents such as ethoxylated alcohols and phenol ethoxylates can also be present. Phenol ethoxylates are particularly useful when the pulp contains a mixture of non-impact printed paper along with conventional, impact printed paper.
- These additives and the additive formulations can be added to the hydropulps at any time before, during, or after repulping. Since the pulping per se takes only a very short time, the additives are usually added to the hydropulper at the beginning of the pulping operation.
- R is a linear or branched, saturated or unsaturated hydrocarbon chain having 1 to 20 carbon atoms.
- R represents an aliphatic acid residue (b)
- R is preferably a linear radical having 5 to 10 and more preferably 8 to 12 carbon atoms.
- R in this case, will be saturated or contain no more than 1 carbon-carbon double bond.
- the aliphatic acid residue (b) is a fatty acid residue.
- Preferred fatty acid residues include oleic and linoleic fatty acids.
- R represents a phenol residue (c)
- the phenol residue may be derived from an ortho, meta-, or para-phenol, preferably a para-phenol.
- R. is preferably a linear saturated aliphatic radical having 1 to 30 and, more preferably, 8 to 14 carbon atoms.
- an aqueous pulp slurry is contacted with the additive formulation at a concentration and for a time and at a temperature sufficient to remove ink from the paper fibers and to cause the removed ink to agglomerate into particles sufficiently large to permit their removal from the paper fibers by means known in the art, preferably screening or centrifuging.
- the additive formulation may be employed at a level of about 5 to 30 pounds, preferably about 10 to 20 pounds, per ton of fiber, dry weight.
- additives commonly used in de-inking operations may also be added with or as a part of the additive formulation according to the invention.
- One of ordinary skill would know the amount of additives commonly used in de-inking operations.
- the paper to be de-inked may be treated in a hydropulper or other de-inking apparatus with an additive formulation according to the invention to produce an aqueous slurry of about 3 to 20, preferably about 4 to 8, weight percent dry fiber based on the total weight of the slurry.
- the pulp is preferably contacted with the additive formulation at a temperature above the softening point of the ink, preferably where the ink becomes tacky and agglomeration occurs.
- the temperature should be about 40 to 100°C, preferably about 65 to 80°C and most preferably about 70°C.
- the pulp is preferably contacted with the additive formulation at a pH of about 6 to 13, preferably at pH 8 to 11, and most preferably at about pH 11.
- these conditions may be varied depending upon the particular composition of the ink, or inks, involved in a given de-inking operation.
- the ink may be separated from the pulped fibers and agglomerated into particles for removal in a stepwise manner or essentially simultaneously. Again, simultaneous separation and agglomeration is preferred. Generally, at these conditions, about 5 to 60 minutes time is required for pulping to be complete and for the ink to be removed from the paper.
- the ink formulations (frequently referred to as "toners") used in non-impact printing are generally comprised of low molecular weight thermoplastic polymers and pigments, typically carbon black, although colored pigments are also frequently employed.
- the polymers used are usually low molecular weight polystyrenes, styrene/methacrylate co- polymers, butadienes, and polyesters, by way of example. Waxes are sometimes blended into the inks to improve their fixing efficiency.
- these polymers In general, the major requirements for these polymers are: (1) they must have a melting point between 120 and 200°C; (2) they must be stable at temperatures up to about 54°C; (3) they must fuse on paper at about 150°C; and (4) they should have a glass transition temperature (softening point) between about 65 and 75°C.
- the pulp is contacted with an additive formulation according to the invention at the temperature where the thermoplastic ink binder becomes tacky and the ink particles more readily agglomerate into tacky particles.
- the agglomerated particles are preferably at least about 175 microns in diameter and more preferably at least about 200 microns.
- the temperature of the pulp is preferably lowered to a temperature below the softening point of the polymer, preferably to about 55°C or lower.
- the agglomerated resin particles harden to a more rigid, non- tacky state which permits ready removal from the pulp by means known in the art. This removal is preferably accomplished by screening or centrifuging.
- the cooling temperature is not critical, but should be sufficiently low to permit the thermoplastic binder to harden to a sufficient non-tacky state.
- Xerographically printed paper was de-inked using additive formulae according to this invention.
- Each formulation was made up of 25% of petroleum distillate and 75% by weight of derivatized ethylene oxide/propylene oxide polymer according to the following list.
- a slurry of 4% by weight xerographically printed paper was prepared in aqueous alkali at pH 11.0 at 70°C.
- Each formulation A-E was added to a separate slurry at a concentration of about 20 pounds per ton of slurry. Pulping/ de-inking was carried out for 30 minutes at 70°C, after which the temperature was lowered to 40°C to harden the agglomerated ink/resin particles. Controls with no additive formulation and with petroleum distillate only were run simultaneously with the test run.
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Paper (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
A method of de-inking non-impact printed paper comprises contacting repulped paper with a formulation comprised of a derivatized ethylene oxide/propylene oxide polymer and a petroleum hydrocarbon distillate. The process separates the ink from the paper and agglomerates the separated ink into particles of a size sufficient that they can be efficiently removed from the paper fibers.
Description
Description METHOD OF AGGLOMERATING PRINTING INK AND FORMULATIONS FOR USE THEREIN
Technical Field
This invention relates to methods and formulations to de-ink paper containing printed matter that has been applied by non-impact printing methods. More specifically, the invention relates to methods and formulations which separate the ink from paper and agglomerate the separated ink to form particles of a size sufficient that they can be efficiently removed from the paper. Background Art
In recent years, the growth of environmental consciousness has spurred the increasing use of recycled paper. At the same time, the increased use of non-impact, reprographic printing processes such as electrographic photocopying (e.g. xerography) , laser printing, or ink-jet printing has greatly increased the difficulty encountered in the paper recycling process.
For printed paper to be recycled, the ink must be substantially, or preferably completely, removed to permit the manufacture of high quality paper with the recycled or secondary fibers. Conventional de-inking procedures remove conventional water or oil based inks by mechanically repulping the printed paper and then contacting the repulped paper with an aqueous medium containing a surfactant to separate the ink from the pulped fibers. The separated ink is then removed by washing or flotation.
Conventional de-inking techniques, however, cannot be used to satisfactorily recycle paper printed with non-impact printing inks. This deficiency arises from the composition of non-impact printing inks. Generally speaking, non-impact printing inks are formulated with a thermoplastic binder which, during conventional pulping and de-inking, forms particles that are too large to be removed by washing or
flotation but too small to be removed satisfactorily by screening or centrifuging.
Several techniques have been tried to agglomerate these polymer-based inks into larger, denser particles that can be removed by screening or centrifuging. For example, U.S. Patent Nos . 4,820,379 and 5,102,500 disclose agglomerating reprographic inks with alkoxy-capped poly(ethylene oxide) additives in the presence of a polymeric material and, optionally, a chelating agent. U.S. Patent No. 5,141,598 discloses de-inking electrostatically printed paper using a mixture of an aliphatic petroleum distillate, an alkylphenoxy (ethyleneoxy) ethanol and an ethoxylated polyoxypropylene glycol . The mixture has a combined HLB less than 10 and a weight ratio of 6:1:3.
Disclosure of the Invention
Accordingly, the present invention is directed to a method of de-inking non-impact printed paper that substantially obviates one or more of the problems due to limitations and disadvantages of currently used de-inking methods. In one aspect, this invention provides a de-inking method where reprographic or non-impact inks are separated from repulped paper fibers and agglomerated to a size sufficient to permit their removal from those fibers. The method comprises the step of contacting repulped fibers containing non-impact printed subject matter with an additive formulation for a time and at a temperature sufficient to separate the ink from the repulped paper fibers and to agglomerate the separated ink into particles of a size sufficient to permit their removal from the fibers. The additive formulation comprises (1) 85 to 10% by weight of at least one petroleum distillate and (2) 15 to 90% by weight of at least one derivatized ethylene oxide/propylene oxide polymer having the structural formula I :
R(CH2CH2-0)x(CHCH2-0)yH (I)
CH3
wherein x and y are each integers from 1 to 20 and R is the derivatizing radical selected from
(a) an aliphatic alcohol residue having the formula: R2-CH2-0-;
(b) an aliphatic acid residue of the formula:
O
// Ri-C
\ 0-;
(c) a phenol residue of the formula:
wherein R is a linear or branched, saturated or unsaturated hydrocarbon chain having 1 to 20 carbon atoms.
The invention also provides a formulation useful for carrying out the method. That formulation comprises
(1) 85 to 10% by weight of at least one petroleum distillate; and
(2) 15 to 90% by weight of at least one derivatized ethylene oxide/polypropylene oxide polymer of the formula I :
R- (CH2CH2-0-)x- (CH-CH2-0-)y-H (I)
CH3 wherein x and y are integers from 1 to 20 and R is the derivatizing radical selected from
(a) an aliphatic alcohol residue having the formula:
R1-CH2-0-;
(b) an aliphatic acid residue of the formula:
O
// R-L-C \ 0-;
(c) a phenol residue of the formula:
--® -0-;
wherein R is a linear or branched, saturated or unsaturated hydrocarbon chain having 1 to 20 carbon atoms.
DETAILED DESCRIPTION OF THE INVENTION
Typically when de-inking waste paper containing non¬ impact printed subject matter, the paper is treated in a hydropulper to produce an aqueous slurry of repulped paper fibers. Pulp slurries usually comprise about 3 to 20 and, often, about 4 to 8 weight percent repulped paper fiber based on the total weight of slurry.
Additives commonly used in de-inking operations include surfactants, bleaches, brighteners, softeners, defoamers, dispersants, and chelants. Conventionally used repulping de-inking agents such as ethoxylated alcohols and phenol ethoxylates can also be present. Phenol ethoxylates are particularly useful when the pulp contains a mixture of non-impact printed paper along with conventional, impact printed paper. These additives and the additive formulations can be added to the hydropulps at any time before, during, or after repulping. Since the pulping per se takes only a very short time, the additives are usually added to the hydropulper at the beginning of the pulping operation.
To remove ink from non-impact printed paper according to the present invention, repulped paper fibers are contacted with a formulation comprising at least one petroleum distillate and at least one polymer of formula I, shown below. The formulation comprises, typically, 10 to 85% by weight of a petroleum distillate, preferably 15 to 40%, and 15 to 90% by weight of a derivatized ethylene oxide/ propylene oxide polymer of formula I, preferably 60 to 85%, more preferably 65 to 80%. A preferred formulation comprises about 25% petroleum distillate and 75% polymer.
The petroleum distillate is preferably a relatively high boiling hydrocarbon fraction, having a boiling point between about 185° and 275°C. Such a fraction typically contains a mixture of aliphatic and naphthenic hydrocarbons with a low level of aromatics. Petroleum distillates having these characteristics are available commercially, e.g., under the trade names Vista LPA-140 (CAS #64742-47-8) , boiling
range 187-232°C, Vista LPA-210 (CAS #64742-47-8) , boiling range 203-278°C, both sold by Vista Chemical Company, and ArcoPrime 55 (CAS #8042-47-5) , sold by Lyondell Petrochemical Company.
The polymers employed in the de-inking method of the invention are derivatized ethylene oxide/propylene oxide polymers. These polymers, which may be random or block copolymers, are represented by the following formula I:
R- (CH2CH2-0-)x- (CH-CH2-0-)y-H (I)
CH3
Commercially available polymers of formula I are sold by Chemax, Inc. under the trade names Chemal DA-5P8, by PPG Industries, Inc. under the trade names of Macol LF110 and Macol LF120, and by BASF as Afranilf.
Within the polymer, the ratio of ethylene oxide units to propylene oxide units, x:y, can vary from about 1 to 20 to 20 to 1. Preferably, this ratio will be no greater than about 1 to 1 and, more preferably less than about 1 to 1, i.e., the propylene oxide units will preponderate. The ethylene oxide and propylene oxide units can be distributed in random or block configuration within the polymer structure.
As shown in formula I, R, the derivatizing radical, is derived from (a) a linear or branched, saturated or unsaturated, aliphatic alcohol, (b) a saturated or unsaturated aliphatic carboxylic acid or (c) a phenol residue.
The aliphatic alcohol residue (a) has the formula:
Rl-CH2-0-;
The aliphatic acid residue, (b) , the formula:
O // R-L-C \ O- ; and
The phenol res formula:
In each formula (a) , (b) , and (c) , R is a linear or branched, saturated or unsaturated hydrocarbon chain having 1 to 20 carbon atoms.
When the derivatizing radical, R, represents an aliphatic alcohol residue (a) , the radical R preferably is a saturated radical having 1 to 20 and more preferably 8 to 14 carbon atoms, either in a linear or branched chain. If the residue is branched, it is preferred that it have about 5 to 10 carbon atoms in the longest chain.
When the derivatizing radical, R, represents an aliphatic acid residue (b) , R is preferably a linear radical having 5 to 10 and more preferably 8 to 12 carbon atoms. Preferably R , in this case, will be saturated or contain no more than 1 carbon-carbon double bond. In a further preferred embodiment, the aliphatic acid residue (b) is a fatty acid residue. Preferred fatty acid residues include oleic and linoleic fatty acids.
When the derivatizing radical, R, represents a phenol residue (c) , the phenol residue may be derived from an ortho, meta-, or para-phenol, preferably a para-phenol. R. is preferably a linear saturated aliphatic radical having 1 to 30 and, more preferably, 8 to 14 carbon atoms.
The molecular weight of the polymer of Formula I, including the derivatizing radical, can be between about 400 and 8000. Preferably, the molecular weight is between 400 and 2000 and most preferably, between about 600 and 1400.
In the de-inking method according to the invention, an aqueous pulp slurry is contacted with the additive formulation at a concentration and for a time and at a temperature sufficient to remove ink from the paper fibers and to cause the removed ink to agglomerate into particles sufficiently large to permit their removal from the paper fibers by means known in the art, preferably screening or
centrifuging. The additive formulation may be employed at a level of about 5 to 30 pounds, preferably about 10 to 20 pounds, per ton of fiber, dry weight.
Other additives commonly used in de-inking operations, discussed above, may also be added with or as a part of the additive formulation according to the invention. One of ordinary skill would know the amount of additives commonly used in de-inking operations.
In the de-inking method according to the invention, the paper may first be repulped and then contacted with the additive formulation or the repulping and de-inking may occur simultaneously. A simultaneous method is preferred. In either a sequential or simultaneous method, the pulp slurry may be formed by means known in the art.
The paper to be de-inked may be treated in a hydropulper or other de-inking apparatus with an additive formulation according to the invention to produce an aqueous slurry of about 3 to 20, preferably about 4 to 8, weight percent dry fiber based on the total weight of the slurry. The pulp is preferably contacted with the additive formulation at a temperature above the softening point of the ink, preferably where the ink becomes tacky and agglomeration occurs. For example, the temperature should be about 40 to 100°C, preferably about 65 to 80°C and most preferably about 70°C. The pulp is preferably contacted with the additive formulation at a pH of about 6 to 13, preferably at pH 8 to 11, and most preferably at about pH 11. One of ordinary skill would understand that these conditions may be varied depending upon the particular composition of the ink, or inks, involved in a given de-inking operation.
The ink may be separated from the pulped fibers and agglomerated into particles for removal in a stepwise manner or essentially simultaneously. Again, simultaneous separation and agglomeration is preferred. Generally, at these conditions, about 5 to 60 minutes time is required for
pulping to be complete and for the ink to be removed from the paper.
The ink formulations (frequently referred to as "toners") used in non-impact printing are generally comprised of low molecular weight thermoplastic polymers and pigments, typically carbon black, although colored pigments are also frequently employed. The polymers used are usually low molecular weight polystyrenes, styrene/methacrylate co- polymers, butadienes, and polyesters, by way of example. Waxes are sometimes blended into the inks to improve their fixing efficiency. In general, the major requirements for these polymers are: (1) they must have a melting point between 120 and 200°C; (2) they must be stable at temperatures up to about 54°C; (3) they must fuse on paper at about 150°C; and (4) they should have a glass transition temperature (softening point) between about 65 and 75°C.
Preferably, therefore, the pulp is contacted with an additive formulation according to the invention at the temperature where the thermoplastic ink binder becomes tacky and the ink particles more readily agglomerate into tacky particles. The agglomerated particles are preferably at least about 175 microns in diameter and more preferably at least about 200 microns.
After pulping and particle agglomeration are complete, the temperature of the pulp is preferably lowered to a temperature below the softening point of the polymer, preferably to about 55°C or lower. At this point, the agglomerated resin particles harden to a more rigid, non- tacky state which permits ready removal from the pulp by means known in the art. This removal is preferably accomplished by screening or centrifuging. The cooling temperature is not critical, but should be sufficiently low to permit the thermoplastic binder to harden to a sufficient non-tacky state.
The invention will be demonstrated by the following examples. The examples illustrate but do not limit the present invention.
Example 1
Xerographically printed paper was de-inked using additive formulae according to this invention. Each formulation was made up of 25% of petroleum distillate and 75% by weight of derivatized ethylene oxide/propylene oxide polymer according to the following list. Formulation A
- Petroleum distillate: Vista LPA-140 product
- Derivatized Ethylene Oxide/Propylene Oxide Polymer:
Random CH3CH(CH2) (g-n) -0- (CH2CH2-0) 2- (CH-CH2-0) 6-H CH3 CH3
Formulation B
- Petroleum distillate: Vista LPA-140 product
- Derivatized Ethylene Oxide/Propylene Oxide Polymer:
Block CH3CH(CH2)7-0- (CH2CH20) 5 (CH-CH2-0) 8-H CH3 "CH3
Formulation C
- Petroleum distillate: Vista LPA-140 product
- Derivatized Ethylene Oxide/Propylene Oxide Polymer:
Block CH3(CH2) (11_13)-0-(CH2CH2-0)5-(CH-CH2-0)8-H
CH3 Formulation D
- Petroleum distillate: Vista LPA-140 product
- Derivatized Ethylene Oxide/Propylene Oxide Polymer:
O // Block CH3 (CH2) 7-CH=CH- (CH2) 7-C-O- (CH2CH2-0) 5- (CH-CH2-0) 8-H
CH3
Formulation E
- Petroleum distillate: Vista LPA-140 product
- Derivatized Ethylene Oxide/Propylene Oxide Polymer:
Block CH3- (CH) - (CH2) 5-C6H4-0- (CH2-CH2-0) 5- (CH-CH2-0) 8-H
CH3 CH3
A slurry of 4% by weight xerographically printed paper was prepared in aqueous alkali at pH 11.0 at 70°C.
Each formulation A-E was added to a separate slurry at a concentration of about 20 pounds per ton of slurry. Pulping/ de-inking was carried out for 30 minutes at 70°C, after which the temperature was lowered to 40°C to harden the agglomerated ink/resin particles. Controls with no additive formulation and with petroleum distillate only were run simultaneously with the test run.
The fibers were then washed at 0.5% slurry consistency in the water through a 5 mesh screen, then through a 10 mesh screen, and finally through a 20 mesh screen to remove the agglomerated ink particles.
Resin particle size was measured for all runs by a Thomas Optical Image analyzer. It was found that, when using a formulation of this invention, particle size greater than 200 microns was consistently realized, allowing the particles to be removed easily by screening. By contrast, when a formulation according to the invention was not used, a substantial number of particles of less than 200 microns were produced, and could not be removed by screening. These results are set forth in Table I .
Table I
Median Particle Minimum Particle Particle Size
Formulation Size Size Ranαe A 1300 microns 250 microns 250-2100
B 1200 275 275-1700
C 1400 220 220-2300
D 1200 320 320-1900
E 1400 280 280-1650
Pet. Distill.
Only <100 <50 <50-350
Control <100 <50 <50-350
Each batch of recycled fibers recovered in this example was made into hand sheets using conventional paper laboratory methods. Brightness was determined on each sheet using a General Electric Brightness Meter, as a quality evaluation.
Each of specimens A through E exhibited paper brightness between 80 and 83 indicating that little or no ink remained in this paper. By contrast, the control run, in which none of the additive formulations of this invention was employed, had a brightness value of 76.3, indicating that significantly more ink remained in this paper than in specimens A through E. The formulation containing petroleum distillate only had a brightness value of 76.5. The brightness of the initial paper in its original state was 84.5. Thus, the present invention successfully recycled the xerographic paper to a state closest to its original brightness by removing the greatest amount of ink.
Example II
Using the same procedures and additive formulations as in Example 1, a batch of laser-printed paper was de-inked.
The ink/resin particles were removed by screening and their particle size was measured. The results are recorded in Table II.
Table II
Median Particle Minimum Particle Particle Size
Formulation Size (Microns) Size (Microns) Range (Microns) A 1000 230 230-2200
B 900 270 270-1500
C 1100 240 240-1900
D 1000 250 250-1700
E 800 240 240-1200
Pet. Distill.
Only <100 <50 <50-350
Control <100 <50 <50-350
Handsheet brightness for fibers de-inked according to the invention ranged from about 77.8 to 80.1. This compares to a brightness of 75.4 for the control, 84.5 for the initial paper in its original state, 76.5 for the formulation using only petroleum distillate.
Claims
1. A de-inking method for removing ink from non¬ impact printed paper, the method comprising the step of contacting repulped paper fibers containing non-impact printed subject matter with an additive formulation for a time and at a temperature sufficient to separate the ink from the repulped paper fibers and to agglomerate the separated ink into particles of a size sufficient to permit their removal from the fibers, the formulation comprising:
(1) 85 to 10% by weight of at least one petroleum distillate, and
(2) 15 to 90% by weight of at least one derivatized ethylene oxide/propylene oxide polymer of formula I :
R- (CH2CH2-0)x- (CH-CH2-0-)y-H (I)
CH3 wherein x and y are each integers from 1 to 20 and R is the derivatizing radical selected from
(a) an aliphatic alcohol residue having the formula:
R-L-CH2-0-; '
(b) an aliphatic acid residue of the formula:
O
// Ri-C \ 0-;
(c ) a phenol -residue of the formula :
wherein R is a linear or branched, saturated or unsaturated hydrocarbon chain having 1 to 20 carbon atoms.
2. A method according to claim 1, further comprising the steps of lowering the temperature to render the agglomerated ink particles solid and non-tacky and removing the agglomerated ink particles from said fibers.
3. A method according to claim 2, wherein the contacting step comprises a first step of separating the ink from the fiber followed by a second step of agglomerating the separated ink into particles of a size to permit their removal for the fibers.
4. A method according to claim 2, wherein the contacting step essentially simultaneously separates the ink from the fibers and agglomerates the separated ink into particles of a size to permit their removal from the fibers.
5. A method according to claim 2, wherein the agglomerated ink is removed by screening.
6. A method according to claim 2, wherein the agglomerated ink is removed by centrifuging.
7. A method according to claim 2 wherein the ratio of ethylene oxide to propylene oxide units in formula I is less than 1 to 1.
8. A method according to claim 2, wherein the contacting step is carried out at a temperature ranging from 65° to 80°C.
9. A method according to claim 8, wherein the ratio of ethylene oxide units to propylene oxide units in formula I is less than 1 to 1.
10. A method according to claim 9, wherein the additive formulation is employed at a level of about 5 to 30 pounds per ton of fiber, dry weight.
11. A method according to claim 2, wherein the additive formulation is employed at a level of about 5 to 30 pounds per ton of fiber, dry weight.
12. A method according to claim 11, wherein the agglomerated ink particles are removed by screening.
13. A method according to claim 11, wherein the agglomerated ink particles are removed by centrifuging.
14. A formulation for use in de-inking paper containing non-impact printed subject matter comprising: (1) 85 to 10% by weight of at least one petroleum distillate, and
(2) 15 to 90% by weight of at least one derivatized ethylene oxide/propylene oxide polymer of formula I :
R- (CH2CH2-0)x- (CH-CH2-0-)y-H (I)
CH3 wherein x and y are each integers from 1 to 20 and R is the derivatizing radical selected from
(a) an aliphatic alcohol residue having the formula:
R -CH2-0-;
(b) an aliphatic acid residue of the formula:
O
// Rχ-C \ 0-;
(c) a phenol residue of the formula:
wherein R is a linear or branched, saturated or unsaturated hydrocarbon chain having 1 to 20 carbon atoms.
15. A formulation according to claim 14, wherein the ratio of ethylene oxide to propylene oxide in the polymer is less than 1 to 1.
16. A formulation according to claim 14, wherein the petroleum distillate is a mixture of aliphatic and naphthenic hydrocarbons having a boiling point between about 185 and 275°C.
17. A formulation according to claim 16, wherein the petroleum distillate is VISTA LPA-140 product.
18. A formulation according to claim 16, wherein the derivatized ethylene oxide/propylene oxide polymer is
Random CH3CH(CH2) (g-n) -O- (CH2CH2-0) 2- (CH-CH2-0) 6-H.
CH3 CH3
19. A formulation according to claim 16, wherein the derivatized ethylene oxide/propylene oxide polymer is
Block CH3CH(CH2)7-0- (CH2CH20) 5 (CH-CH2-0) 8-H.
CH3 CH3
20. A formulation according to claim 16, wherein the derivatized ethylene oxide/propylene oxide polymer is
Block CH3 (CH2) (ιi-i3) -O- (CH2CH2-0) 5- (CH3CH-CH2-0) 8-H.
CH3
21. A formulation according to claim 16, wherein the derivatized ethylene oxide/propylene oxide polymer is
0
// Block CH3 (CH2) 7-CH=CH- (CH2) 7-C-0- (CH2CH2-0) 5- (CH-CH2-0) 8-H.
CH3
22. A formulation according to claim 16, wherein the derivatized ethylene oxide/propylene oxide polymer is
Block CH3- (CH) - (CH2) 5-C6H -0- (CH2-CH2-0) 5- (CH-CH2-0) 8-H.
CH3 CH3
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SK1130-96A SK113096A3 (en) | 1994-03-08 | 1995-03-08 | Agent for deinking printing ink and a method of deinking |
| NZ282606A NZ282606A (en) | 1994-03-08 | 1995-03-08 | Deinking recycled waste paper using a petroleum distillate and an ethylene/propylene oxide polymer |
| MX9603814A MX9603814A (en) | 1994-03-08 | 1995-03-08 | Method of agglomerating printing ink and formulations for use therein. |
| EP19950912711 EP0749506A1 (en) | 1994-03-08 | 1995-03-08 | Method of agglomerating printing ink and formulations for use therein |
| AU31048/95A AU3104895A (en) | 1994-03-08 | 1995-03-08 | method of agglomerating printing ink and formulations for use therein |
| JP52354095A JPH10500739A (en) | 1994-03-08 | 1995-03-08 | Method for aggregating printing ink and composition for use in the method |
| BR9507406A BR9507406A (en) | 1994-03-08 | 1995-03-08 | Formulation for use in deinking paper containing non-impact printed matter and deinking method |
| FI963483A FI963483A0 (en) | 1994-03-08 | 1996-09-05 | Process for agglomerating inks and formulations used therein |
| NO963747A NO963747L (en) | 1994-03-08 | 1996-09-06 | Process for agglomerating ink, and formulation for use in the process |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US20742394A | 1994-03-08 | 1994-03-08 | |
| US08/207,423 | 1994-03-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1995024526A1 true WO1995024526A1 (en) | 1995-09-14 |
Family
ID=22770491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1995/002670 WO1995024526A1 (en) | 1994-03-08 | 1995-03-08 | Method of agglomerating printing ink and formulations for use therein |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0749506A1 (en) |
| JP (1) | JPH10500739A (en) |
| CN (1) | CN1143399A (en) |
| AU (1) | AU3104895A (en) |
| BR (1) | BR9507406A (en) |
| CA (1) | CA2185007A1 (en) |
| CZ (1) | CZ260396A3 (en) |
| FI (1) | FI963483A0 (en) |
| MX (1) | MX9603814A (en) |
| NO (1) | NO963747L (en) |
| NZ (1) | NZ282606A (en) |
| SK (1) | SK113096A3 (en) |
| WO (1) | WO1995024526A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532981A (en) * | 2012-02-10 | 2012-07-04 | 南京博超科技有限责任公司 | Polyether waste paper deinking agent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3501373A (en) * | 1966-11-04 | 1970-03-17 | Garden State Paper Co Inc | De-inking waste printed cellulosic stock |
| GB2063326A (en) * | 1979-11-13 | 1981-06-03 | Economics Lab | Methods of deinking secondary fiber |
| DE3401444A1 (en) * | 1983-01-17 | 1984-07-19 | Kao Corp., Tokio/Tokyo | Process for de-inking decolorising and regenerating wastepaper |
| EP0510954A1 (en) * | 1991-04-25 | 1992-10-28 | Betz Europe, Inc. | Process and composition for deinking dry toner electrostatic printed wastepaper |
-
1995
- 1995-03-08 CN CN95191972A patent/CN1143399A/en active Pending
- 1995-03-08 JP JP52354095A patent/JPH10500739A/en active Pending
- 1995-03-08 NZ NZ282606A patent/NZ282606A/en unknown
- 1995-03-08 SK SK1130-96A patent/SK113096A3/en unknown
- 1995-03-08 CZ CZ962603A patent/CZ260396A3/en unknown
- 1995-03-08 EP EP19950912711 patent/EP0749506A1/en not_active Withdrawn
- 1995-03-08 WO PCT/US1995/002670 patent/WO1995024526A1/en not_active Application Discontinuation
- 1995-03-08 MX MX9603814A patent/MX9603814A/en unknown
- 1995-03-08 CA CA 2185007 patent/CA2185007A1/en not_active Abandoned
- 1995-03-08 BR BR9507406A patent/BR9507406A/en not_active Application Discontinuation
- 1995-03-08 AU AU31048/95A patent/AU3104895A/en not_active Abandoned
-
1996
- 1996-09-05 FI FI963483A patent/FI963483A0/en unknown
- 1996-09-06 NO NO963747A patent/NO963747L/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3501373A (en) * | 1966-11-04 | 1970-03-17 | Garden State Paper Co Inc | De-inking waste printed cellulosic stock |
| GB2063326A (en) * | 1979-11-13 | 1981-06-03 | Economics Lab | Methods of deinking secondary fiber |
| DE3401444A1 (en) * | 1983-01-17 | 1984-07-19 | Kao Corp., Tokio/Tokyo | Process for de-inking decolorising and regenerating wastepaper |
| EP0510954A1 (en) * | 1991-04-25 | 1992-10-28 | Betz Europe, Inc. | Process and composition for deinking dry toner electrostatic printed wastepaper |
Also Published As
| Publication number | Publication date |
|---|---|
| FI963483A (en) | 1996-09-05 |
| NO963747D0 (en) | 1996-09-06 |
| JPH10500739A (en) | 1998-01-20 |
| AU3104895A (en) | 1995-09-25 |
| SK113096A3 (en) | 1997-02-05 |
| CN1143399A (en) | 1997-02-19 |
| EP0749506A1 (en) | 1996-12-27 |
| CA2185007A1 (en) | 1995-09-14 |
| NO963747L (en) | 1996-09-06 |
| BR9507406A (en) | 1997-09-02 |
| MX9603814A (en) | 1997-03-29 |
| NZ282606A (en) | 1998-09-24 |
| FI963483A0 (en) | 1996-09-05 |
| CZ260396A3 (en) | 1997-02-12 |
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