CA1239491A - Calcium control system - Google Patents
Calcium control systemInfo
- Publication number
- CA1239491A CA1239491A CA000489231A CA489231A CA1239491A CA 1239491 A CA1239491 A CA 1239491A CA 000489231 A CA000489231 A CA 000489231A CA 489231 A CA489231 A CA 489231A CA 1239491 A CA1239491 A CA 1239491A
- Authority
- CA
- Canada
- Prior art keywords
- guar
- salt
- mixture
- hydrocolloid
- calcium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B65/00—Compositions containing mordants
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/001—Special chemical aspects of printing textile materials
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/163—Sugars; Polysaccharides
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/40—Feeding-stuffs specially adapted for particular animals for carnivorous animals, e.g. cats or dogs
- A23K50/48—Moist feed
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
- A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L9/00—Puddings; Cream substitutes; Preparation or treatment thereof
- A23L9/10—Puddings; Dry powder puddings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/04—Alginic acid; Derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
- D06P1/48—Derivatives of carbohydrates
Abstract
ABSTRACT
CALCIUM CONTROL SYSTEM
Hydrocolloid/salt blends are prepared which controllably release ions into solution. The blends are especially useful in alginate print paste compositions.
CALCIUM CONTROL SYSTEM
Hydrocolloid/salt blends are prepared which controllably release ions into solution. The blends are especially useful in alginate print paste compositions.
Description
I
C:ALCIUhl CONTROL SIESTA
It is well known that the introduction of diva lent ions into soluble alienate solutions rapidly causes gelatin through the formation of mixed algina~e salts. Where it is desirable to control the speed ox this julienne, various methods have been proposed to delay the rate of release of the dip 5 valet ions. An example of this has been the use of a sparingly soluble salter calcium citrate, in combination with the soluble alienate, eye., sodium allegiant. The calcium ions are released over time and thus complete gelatin is not instantaneous.
It has now been found that if the jelling salt is first mixed with 10 certain hydrocolloids prior to incorporation into the soluble alienate solution, there is a more uniform release of diva lent cation. This minimizes localized golfing and thus allows lower concentrations of allegiant to be used to generate a given viscosity. This controlled release of ion also minimizes the amount of insoluble due to incomplete hydration, i.e., a 15 smoother gel is produced. Further, more rapid and complete dissolution is observed when hard water is used in the make-up of the soluble allegiant solution.
In the compositions of this invention, the preferred hydrocolloid is guar. Guard is a commercially available gum derived from the seed of the
C:ALCIUhl CONTROL SIESTA
It is well known that the introduction of diva lent ions into soluble alienate solutions rapidly causes gelatin through the formation of mixed algina~e salts. Where it is desirable to control the speed ox this julienne, various methods have been proposed to delay the rate of release of the dip 5 valet ions. An example of this has been the use of a sparingly soluble salter calcium citrate, in combination with the soluble alienate, eye., sodium allegiant. The calcium ions are released over time and thus complete gelatin is not instantaneous.
It has now been found that if the jelling salt is first mixed with 10 certain hydrocolloids prior to incorporation into the soluble alienate solution, there is a more uniform release of diva lent cation. This minimizes localized golfing and thus allows lower concentrations of allegiant to be used to generate a given viscosity. This controlled release of ion also minimizes the amount of insoluble due to incomplete hydration, i.e., a 15 smoother gel is produced. Further, more rapid and complete dissolution is observed when hard water is used in the make-up of the soluble allegiant solution.
In the compositions of this invention, the preferred hydrocolloid is guar. Guard is a commercially available gum derived from the seed of the
2 guard plant, yo-yo bus. It addition to guard gum other hydrocolloids usable in this invention include guard derivatives such as oxidized guard carboxymethyl guard de-polymerized guard and hydroxyalkyl guard such as hydroxyethyl- and hydroxypropyl-~uar, polyvinyl alcohol, carboxymethyl cellulose (CMC), xenon gum, cold water soluble locus bean 25 sum, cold water soluble starch, and starch derivatives such as hydroxyethylated and hydroxypropylated starch.
The alginates to be used are the soluble salts of alginic acid Alginic acid derived primarily from kelp, is a commercially available product, as are the alginates. Especially preferred algin~tes are the sodium, potassium and ammonlum salts. ,,~
The diva lent salts which can be used in this invention are preferably those ox calcium, barium, and strontium. The salts include a range of different solubilities from the least soluble like calcium citrate tart rate, sulfite, and phosphate Jo the very soluble like calcium chloride. Thus, the 5 salts include the acetate, bromide, carbonate, fluoride, fumarate, d gluconate, glycerophosphate, hydroxide, iodide, lactate, dl-malate, d-rnalate, Malta, malonate, nitrate, nitrite, owlet, primary-, secondary-, and tertiary-orthophosphate, proprionate, soullessly lo, and d-tartrate salts.
However, the exact amount and type of each salt and hydrocolloid would 10 depend on the level of ion control required by each application. The in-valet salts, such as those of aluminum, may also be used.
The blends of the hydrocolloids and diva lent salts are prepared by dry mixing the two ingredients and then slowly adding water under agitation Jo form a paste or dough. If insufficient water is used (as evidenced by a 15 lack of pasting), the hydrocolloid is not properly hydrated and an unacceptable product is produced. If an excess of water is used such that the hydrocolloid is mostly dissolved) an acceptable product can be produced but the drying step becomes time-consuming and expensive. The ratio of dip valet salt to hydrocolloid ranges from loll to 1:20 (based on total dry 20 weights). Preferably the range is 5:1 to 1:5. Mixing of the dry ingredients and pasting are easily accomplished, e.g., in a Z-blade or paddle-type dough mixer, although other apparatuses are suitable. To assure proper mixing, the dry ingredients are mixed for about 5 minutes, the water is added for 5-lo minutes, and the paste is mixed for an additional 30 minutes. Following pasting, the dough is crumbled and dried to about 90% solids, e.g., 60-70 C
in a tray drier. l he dried product is milled and classified through 850 micron on ion micron sieves. These blends therefore are not mere n mixtures of hydrocolloid and salt. Rather, the salts are intimately blended with the hydrocolloid. Advantageously, this allows for the controlled release of the salt into solution as described above. Further dry mixtures of these blends with alginates are non-segre~ating, i.e., the distribution of diva lent salt in the dry mixtures remains essentially unchanged over time. This assures the end user that there will be a homogeneous distribution of diva lent cations available for geJation when the jelled aqueous solutions are prepared.
These hydrocolloid/di-valent salt blends are usable wherever it is desirable to controllable gel aqueous alienate solutions. Examples of such I
The alginates to be used are the soluble salts of alginic acid Alginic acid derived primarily from kelp, is a commercially available product, as are the alginates. Especially preferred algin~tes are the sodium, potassium and ammonlum salts. ,,~
The diva lent salts which can be used in this invention are preferably those ox calcium, barium, and strontium. The salts include a range of different solubilities from the least soluble like calcium citrate tart rate, sulfite, and phosphate Jo the very soluble like calcium chloride. Thus, the 5 salts include the acetate, bromide, carbonate, fluoride, fumarate, d gluconate, glycerophosphate, hydroxide, iodide, lactate, dl-malate, d-rnalate, Malta, malonate, nitrate, nitrite, owlet, primary-, secondary-, and tertiary-orthophosphate, proprionate, soullessly lo, and d-tartrate salts.
However, the exact amount and type of each salt and hydrocolloid would 10 depend on the level of ion control required by each application. The in-valet salts, such as those of aluminum, may also be used.
The blends of the hydrocolloids and diva lent salts are prepared by dry mixing the two ingredients and then slowly adding water under agitation Jo form a paste or dough. If insufficient water is used (as evidenced by a 15 lack of pasting), the hydrocolloid is not properly hydrated and an unacceptable product is produced. If an excess of water is used such that the hydrocolloid is mostly dissolved) an acceptable product can be produced but the drying step becomes time-consuming and expensive. The ratio of dip valet salt to hydrocolloid ranges from loll to 1:20 (based on total dry 20 weights). Preferably the range is 5:1 to 1:5. Mixing of the dry ingredients and pasting are easily accomplished, e.g., in a Z-blade or paddle-type dough mixer, although other apparatuses are suitable. To assure proper mixing, the dry ingredients are mixed for about 5 minutes, the water is added for 5-lo minutes, and the paste is mixed for an additional 30 minutes. Following pasting, the dough is crumbled and dried to about 90% solids, e.g., 60-70 C
in a tray drier. l he dried product is milled and classified through 850 micron on ion micron sieves. These blends therefore are not mere n mixtures of hydrocolloid and salt. Rather, the salts are intimately blended with the hydrocolloid. Advantageously, this allows for the controlled release of the salt into solution as described above. Further dry mixtures of these blends with alginates are non-segre~ating, i.e., the distribution of diva lent salt in the dry mixtures remains essentially unchanged over time. This assures the end user that there will be a homogeneous distribution of diva lent cations available for geJation when the jelled aqueous solutions are prepared.
These hydrocolloid/di-valent salt blends are usable wherever it is desirable to controllable gel aqueous alienate solutions. Examples of such I
3 A-1003 applications include golfed foods such as pet foods, sauces, gravies, bakery fillings, and structured foods such as structured pimento strips for olives.
As stated above, there is a range of usable hydrocolloid:saJt ratios.
Likewise, there is a variety of specific salts, with varying volubility rates.
The combination of these will determine the rate of viscosity build-up, which is dependent on the needs of the individual practitioner.
This blend is especially useful in allegiant dye printing systems. Thy combination of aligns and calcium salts has been disclosed in US. Patent
As stated above, there is a range of usable hydrocolloid:saJt ratios.
Likewise, there is a variety of specific salts, with varying volubility rates.
The combination of these will determine the rate of viscosity build-up, which is dependent on the needs of the individual practitioner.
This blend is especially useful in allegiant dye printing systems. Thy combination of aligns and calcium salts has been disclosed in US. Patent
4,2~2,740 as a means of forming dye resist areas on textiles. As taught therein, golfed regions are formed by separately applying a getable talginate) composition and a julienne (calcium) agent composition to a textile and then overweighing the material, the golfed regions serving as dye resist areas.
US 8300635 ODE 3300705 Al) teaches that when very low levels of a golfing agent are used to pretreat a substrate followed by printing with an alginate-con~aining print paste, the dye usage for equal color yield is reduced, accompanied by improved print definition.
The use of a mixed divalen~/monovalent (such as calcium/sodium) salt of alginic acid in the print paste effects a reduction in dye usage for equivalent color yield when compared Jo a print paste using sodium allegiant or other conventional thickener. The reduction in dye usage is accomplished without the necessity of pretreating the substrate. Thus, the use of the mixed calcium/sodium allegiant advantageously eliminates one of the process steps required by US. Patent 4,2229740 and US 8300635 pushed Fern , 1984 Nile producitlg a savings ill usage.
In a mixed alienate print paste as describe above, the calcium (i.e., diva lent ion) can conveniently be provided by the hydrocolloid/salt blends of this invention. This invention, therefore, comprises a mixture of blend of hydrocolloid and salt as herein before described and a soluble allegiant, said mixture being especially useful in print paste compositions.
I The specific amount and type of allegiant used in any particular application will, of course, be dependent on the other materiels in the print paste, ego oxidizing agents buffers, etc. These can be determined by the individual practitioner depending on his particular formula~is)n. However, usage levels of to mixture of blend and algina~e in the range 10 to I by weight are recommended, preferably 40 to 60%. The viscosity of the print pastes should be owe to 30,000 cup (RYE or RVF, Brook field Viscometer at .
" .
1~3~
20 rum, spindle 6, 20 "C) immediately before printing, preferably between l 2,000 - l 8,000 cup. Optionally, thickening agents such as guard carboxymethyl guard de-polymerized guard locust bean gum, COCK suitable synthetic puller ens, cellulose derivatives such as sodium-carboxymethyl cellulose, and starch derivatives such as starch ether or combinations of said agents may be included Jo provide some of the viscosity and flow character it its.
The ~i-valent ion level is defined as the amount theoretically necessary to convert 16 ^ 60% of the soluble allegiant, preferably 25 - 50%, to the desired mixed allegiant salt.
The print pastes of this invention are those prepared using pigments or dyes such as disperse dyes, reactive dyes, combinations of disperse and rocketry dyes, and acid dyes, i.e., alp anionic or non-ionic dyes but not cat ionic dyes. Reactive dyes are difficult Jo use because fixation, as with 1.5% sodium carbonate, is deleterious to the Cay Noah ratio in the allegiant.
For brevity's sake, as used herein, the term "dye" is intended to also include "pigment". The invention is most effective with disperse dyes. In addition to the allegiant and dye, these print pastes comprise a variety of well known compounds such as buffers, oxidizing agents, etc. The preparation of such pasts is known in the art.
The substrates to be treated include, for example, polyesters, cellulosics, cottons, blends of these such as polyester/cottons, nylons, and polyamides. The substrates can be any material which can be printed with the appropriate dyes.
In the process of this invention the print paste composition con be applied by any conventional printing or dye method such as flat or rotary screen printing, block or raised relief printing, jet printing stencil printing,engraved cylinder printing, Teak dying, Juster dying, dip squeeze application, or hand application.
When a substrate it treated according to this invention, the print paste pick-up can be Z5% less when compared to pastes using comentional thickeners. The dye actually consumed can be reduced by up to 15 - 25~6 typically but awaken into account shade strength and different dye colors, the range of dye reductions falls within 5 - 40%.
I Following application of the print paste the substrate is treated as necessary to fix any dyes, then washed, dried and otherwise treated by conventional methods to produce the desired end product.
~.-1003 The invention is further defined by reference to the following examples, which are intended Jo be illustrative and not Lyman.
EXAMPLE I
Hydrocolloid/Salt Blend (One-Step Process) Wt. keg }lydroxyethyl-guar gum (disperse dye printing grade) 250 Tricalcium saturate (Pi% through 250 micron sieve;
45% through 40 micron) 90 Tap water 308 250 Kg guard and 90 kg calcium citrate were mixed in a paddle-~ype dough mixer for five minutes. 308 Kg water were added over 5 - 10 minutes and mixing continued for a further 30 minutes. The dough was discharged, disintegrated, and dried to approximately 90% dry matter, at 60 - 70 C in a tray drier. The product was milled and classified through 15 850 micron on 106 micron.
HydrocolloidlSalt Eland (Two-Step Process) Wt. (or?
Hydroxyethyl guard (disperse dye printing grade) 250 Tricalcium saturate (87% through 250 micron sieve;
45% through 40 micron) 67.3 Tap water 154 125 Kg guard and 67.3 kg of calcium citrate were mixed in a paddle-type dough mixer for five minutes. 154 I water were added over 5 - 10 25 minutes and mixing continued for a further 30 minutes. The mixer was stopped and a further 125 I guard added. Mixing resumed for 3 - 4 minutes.
gL~3g39~
Then the dough was crumbled dried, milled, and classified as in Example i.
In the following examples, evaluation of the results was done by visual and instrumental observation of the completely processed substrate.
Percentages are by weight unless otherwise stated.
Where fixation and washing is indicated in the examples, the following procedures were used :-The dye was fixed on the printed material by high temperature (HUT.) steam at 175 US followed by: a wash procedure consisting of:
(i) Washing in running tap water;
10 (ii) Reduction - clear by treating fabric 10 - 20 minutes at 50 C in a solution containing 0.2% detergent + 0.2% sodium hydroxide + 0.2%
sodium hydrosulphite;
(iii) Rinsing in tap water;
(iv) Reduction - clear as above;
15 (v) Rinsing in tap water;
(vi) Treating for 5 - lo minutes at 70 C in a solution containing 0.296 detergent;
(vii) Rinsing in tap water and drying.
Guar/Salt/Al~inate Thickener Polyester knitted fabric was printed with two print pastes constituted as follows:
Test Conventional Recipe US Recipe (%) 25 Palanil brilliant Blue P-BGF liquid (non-ionic disperse dye) 4.Q 4.8 Monosodium orthophosphate 0.1 0.1 SilcQlapse 5006 (anti-30 foam agent based on silicon fluid emulsion) 0.1 0.1 7 Aye Prisulon SPECK (thickener based on ~uar/starch derivative) - 3-75 Thickener 3.5 Water 92.3 91.25 The dye was then fixed and washed.
foe prints showed equal color intensity, although 20% less dye was used in the test recipe.
10 The thickener was prepared by dry mixing the following ingredients:
Amt. (White) Sodium allegiant (Monocled, Colloquial International Ltd.) 34 15 Starch ether (Salivates C5, Tunnel Avebe Starches Ltd.) 38 Hydrocolloid/salt blend of Example 1 28 The calcium convent of the thickener was I based on the amount of 20 sodium allegiant.
Guar/Salt/Al~inate Thickener Polyester knitted fabric was printed with two print pastes constituted as follows:
Test Conventional Recipe (%) Recipe I%) Dispersal Ruben C-13 liquid (anionic disperse dye) 4.0 4.8 ~.~23g~
Monosodium orthophosphate 0.1 0.1 Matexil PA-L (sodium m-nitrobenzene sulphonate) It It Manutex US (high viscosity sodium alienate with 0.6 percent Cay+ on alienate) - 2.25 Thickener 3.6 Calgon (sodium-hexa-m-phosphate) - 0.55 Waxer 91.3 Al 3 10 100 loo The dye was then fixed and washed.
The prints showed equal color intensity although 20 percent less dye was used in the test recipe.
The thickener was the same as in Example 3.
~;uar/Calcium Citrate/Al~inate Thickener Polyester knitted fabric was printed with two print pastes constituted as follows:
Test Conventional recipe (96) Recipe (%) Dispersal Ruben C-B liquid (anionic disperse dye) 4.0 4.8 Monosodium orthophosphate Al 0.1 Matexil PA-L (sodium m-nitrobenzene sulphonate) 1.0 It Monocled (medium viscosity sodium alienate with 0.296 KIWI on alienate) - 3.2 ~Z3~
9 Aye Thickener 3.6 Calgon (sodium hexa-m-phosphate) - 0.8 Water 91.3 90.1 The dye was then fixed and washed.
The color intensity on the prints corresponded to a dye saving of 20% when the test recipe was used The amount of algina~e (Monocle DO) in the test recipe was 1.2% V5. 3.2% in the conventional recipe.
The thickener was the same as in Example 3.
CMC/Salt/Al~inate Thickener Following the procedure of Example I but using carboxymethyl cellulose instead of guard a blend was prepared which was then used to prepare a 34/38/28 thickener as in Example 3.
Polyester knitted fabric was printed with two print pastes constituted as follows:
Test Conventional Recipe (%) Recipe (%) Palanil Brilliant Blue BGF liquid (anionic disperse dye) 4.0 4.6 Monosodium or~hophosphate 0.1 0.1 Silcolapse 5006 (anti-foam agent based on silicon fluid emulsion 0.1 0.1 Prisulon SPECK (thickener based on ~uar/starch derivatives) - 3.75 I
~-1003 Thickener 4.7 Waxer 9 9~-4 The dye was then fixed and washed.
the print showed equal color intensity although 13% less dye was used in the test recipe.
Guar/Salt!Al~inate Thickener Polyester knitted fabric was printed with two print pastes constituted assay follows:
Test Conventional ape (%) Recipe (%) Palanil Brilliant Blue BGlF liquid 3.6 4.8 15 I,uprintan HDF, fixation accelerator (8ASF) 1.5 1.5 Monosodium orthophosphate I 0.2 Silcolapse 5006 0.1 0.1 Prisulon SPECK - 3.75 20 Thickener 2.7 Water 91.9 89.65 The dye was then fixed and washed. The color intensity on the print correspondcnd to a dye saving of 25%.
Thea thickener was prepared by dry mixing the following ingredients:
Amt. (Wt. 96 Sodium alienate (Monocled) 51 Citric acid Andy. 8 Hydrocolloid/salt blend of Example 1 41 Gua!/Salt/Alginate Thickener Knitted polyester was printed with two print pastes constituted as 10 hollows:
Test Conventional Recipe (%) Recipe (%) Palanil Dark glue 3 RUT liquid 15 (anionic disperse dye) 4.2 6.Q
Luprintan HDF (non-ionic fixation accelerator based on fatty acid derivative) 1.5 1.5 Monosodium or orthophosphate 0.2 0.2 20 5ilcolapse 5006 0.1 0.1 Prisulon SPECK - 3.75 Thickener 3.6 .
Water 90.4 88.45 100 1~0 25. The dye was then fixed and itched.
I
12 Aye The prints showed equal color intensity although 30% less dye was used in the test recipe The thickener was the same as in Example 3.
sealability vs. Water Hardness -The following table demonstrates the improved volubility of alginates in hard waxer when mixed with the hydrocolloid/salt blends of this invention as compared to the volubility of alginates when merely mixed with the same salts. In the table the first two samples are dry blends of sodium allegiant 10 and calcium citrate (sufficient to give 45% calcium conversion. The riskiest readings are actual. The third sample was of the same composition as the thickener in Example 3. In the fourth sample, the thickener was of similar composition Jo that of Example 3 except that the hydrocolloid/salt blend was 7496 xanthan gum and 26% calcium saturate.
15 The viscosity readings shown for samples 3 and 4 were obtained from a plot of viscosity vs. water hardness.
Cousteau/ vs. Water hardness RUT Brook field Visa., cup, 20 C, 18hr simply Alvin 50ppm Cook Hardness 350ppm Cook hardness on 1.71 42,800 24,400 2 1.81 42,600 27,400 3 1.75 38,500 701300 4 2.087,000 76,000 Pet Food Formulation A golfed pet food was prepared using as the thickener sodium allegiant and a hydrocolloid/salt blend of this invention comprising guard and calcium sulfate. The composition of the pet food was:
I
Wt. %
Sodium allegiant (ManugelU3J GOB) 5.0 Tetrasodium pyrophosphate 0.5 Water (Do) 249 Gorky So Blend 12.5 Chopped meat 250 Gel strength was measured for one hour and the following data obtained.
Setting time (min.) Gel Strength (ems) * Stevens - LFRA Texture Analyzer, 1 " (2.54 cam plunger, 4 rum penetration.
EXAMPLE I I
Bakery Custard Formulations A custard was prepared of the following compositions:
Wt. (96) Lac~icol~F 336 (dairy grade sodium allegiant blend) 2.5 uric SO blend 1.0 Puzzle EKE, pre-gelatinized potato starch 20 Full cream milk powder 30 Caster sugar 50 Deionized water 250 I The gel strength of the custard was 117 gym at 30 miss and 332 gym at 18 ho, measured on a Stevens LFRA Texture Analyzer.
~4~1~
14 ~-1003 Viscosity vs._Water Hardness Hydrocolloid/salt blends in the ratios 14.3:85.7 and 85.7:14.3 were prepared following the procedure of Example 1. These blends were mixed
US 8300635 ODE 3300705 Al) teaches that when very low levels of a golfing agent are used to pretreat a substrate followed by printing with an alginate-con~aining print paste, the dye usage for equal color yield is reduced, accompanied by improved print definition.
The use of a mixed divalen~/monovalent (such as calcium/sodium) salt of alginic acid in the print paste effects a reduction in dye usage for equivalent color yield when compared Jo a print paste using sodium allegiant or other conventional thickener. The reduction in dye usage is accomplished without the necessity of pretreating the substrate. Thus, the use of the mixed calcium/sodium allegiant advantageously eliminates one of the process steps required by US. Patent 4,2229740 and US 8300635 pushed Fern , 1984 Nile producitlg a savings ill usage.
In a mixed alienate print paste as describe above, the calcium (i.e., diva lent ion) can conveniently be provided by the hydrocolloid/salt blends of this invention. This invention, therefore, comprises a mixture of blend of hydrocolloid and salt as herein before described and a soluble allegiant, said mixture being especially useful in print paste compositions.
I The specific amount and type of allegiant used in any particular application will, of course, be dependent on the other materiels in the print paste, ego oxidizing agents buffers, etc. These can be determined by the individual practitioner depending on his particular formula~is)n. However, usage levels of to mixture of blend and algina~e in the range 10 to I by weight are recommended, preferably 40 to 60%. The viscosity of the print pastes should be owe to 30,000 cup (RYE or RVF, Brook field Viscometer at .
" .
1~3~
20 rum, spindle 6, 20 "C) immediately before printing, preferably between l 2,000 - l 8,000 cup. Optionally, thickening agents such as guard carboxymethyl guard de-polymerized guard locust bean gum, COCK suitable synthetic puller ens, cellulose derivatives such as sodium-carboxymethyl cellulose, and starch derivatives such as starch ether or combinations of said agents may be included Jo provide some of the viscosity and flow character it its.
The ~i-valent ion level is defined as the amount theoretically necessary to convert 16 ^ 60% of the soluble allegiant, preferably 25 - 50%, to the desired mixed allegiant salt.
The print pastes of this invention are those prepared using pigments or dyes such as disperse dyes, reactive dyes, combinations of disperse and rocketry dyes, and acid dyes, i.e., alp anionic or non-ionic dyes but not cat ionic dyes. Reactive dyes are difficult Jo use because fixation, as with 1.5% sodium carbonate, is deleterious to the Cay Noah ratio in the allegiant.
For brevity's sake, as used herein, the term "dye" is intended to also include "pigment". The invention is most effective with disperse dyes. In addition to the allegiant and dye, these print pastes comprise a variety of well known compounds such as buffers, oxidizing agents, etc. The preparation of such pasts is known in the art.
The substrates to be treated include, for example, polyesters, cellulosics, cottons, blends of these such as polyester/cottons, nylons, and polyamides. The substrates can be any material which can be printed with the appropriate dyes.
In the process of this invention the print paste composition con be applied by any conventional printing or dye method such as flat or rotary screen printing, block or raised relief printing, jet printing stencil printing,engraved cylinder printing, Teak dying, Juster dying, dip squeeze application, or hand application.
When a substrate it treated according to this invention, the print paste pick-up can be Z5% less when compared to pastes using comentional thickeners. The dye actually consumed can be reduced by up to 15 - 25~6 typically but awaken into account shade strength and different dye colors, the range of dye reductions falls within 5 - 40%.
I Following application of the print paste the substrate is treated as necessary to fix any dyes, then washed, dried and otherwise treated by conventional methods to produce the desired end product.
~.-1003 The invention is further defined by reference to the following examples, which are intended Jo be illustrative and not Lyman.
EXAMPLE I
Hydrocolloid/Salt Blend (One-Step Process) Wt. keg }lydroxyethyl-guar gum (disperse dye printing grade) 250 Tricalcium saturate (Pi% through 250 micron sieve;
45% through 40 micron) 90 Tap water 308 250 Kg guard and 90 kg calcium citrate were mixed in a paddle-~ype dough mixer for five minutes. 308 Kg water were added over 5 - 10 minutes and mixing continued for a further 30 minutes. The dough was discharged, disintegrated, and dried to approximately 90% dry matter, at 60 - 70 C in a tray drier. The product was milled and classified through 15 850 micron on 106 micron.
HydrocolloidlSalt Eland (Two-Step Process) Wt. (or?
Hydroxyethyl guard (disperse dye printing grade) 250 Tricalcium saturate (87% through 250 micron sieve;
45% through 40 micron) 67.3 Tap water 154 125 Kg guard and 67.3 kg of calcium citrate were mixed in a paddle-type dough mixer for five minutes. 154 I water were added over 5 - 10 25 minutes and mixing continued for a further 30 minutes. The mixer was stopped and a further 125 I guard added. Mixing resumed for 3 - 4 minutes.
gL~3g39~
Then the dough was crumbled dried, milled, and classified as in Example i.
In the following examples, evaluation of the results was done by visual and instrumental observation of the completely processed substrate.
Percentages are by weight unless otherwise stated.
Where fixation and washing is indicated in the examples, the following procedures were used :-The dye was fixed on the printed material by high temperature (HUT.) steam at 175 US followed by: a wash procedure consisting of:
(i) Washing in running tap water;
10 (ii) Reduction - clear by treating fabric 10 - 20 minutes at 50 C in a solution containing 0.2% detergent + 0.2% sodium hydroxide + 0.2%
sodium hydrosulphite;
(iii) Rinsing in tap water;
(iv) Reduction - clear as above;
15 (v) Rinsing in tap water;
(vi) Treating for 5 - lo minutes at 70 C in a solution containing 0.296 detergent;
(vii) Rinsing in tap water and drying.
Guar/Salt/Al~inate Thickener Polyester knitted fabric was printed with two print pastes constituted as follows:
Test Conventional Recipe US Recipe (%) 25 Palanil brilliant Blue P-BGF liquid (non-ionic disperse dye) 4.Q 4.8 Monosodium orthophosphate 0.1 0.1 SilcQlapse 5006 (anti-30 foam agent based on silicon fluid emulsion) 0.1 0.1 7 Aye Prisulon SPECK (thickener based on ~uar/starch derivative) - 3-75 Thickener 3.5 Water 92.3 91.25 The dye was then fixed and washed.
foe prints showed equal color intensity, although 20% less dye was used in the test recipe.
10 The thickener was prepared by dry mixing the following ingredients:
Amt. (White) Sodium allegiant (Monocled, Colloquial International Ltd.) 34 15 Starch ether (Salivates C5, Tunnel Avebe Starches Ltd.) 38 Hydrocolloid/salt blend of Example 1 28 The calcium convent of the thickener was I based on the amount of 20 sodium allegiant.
Guar/Salt/Al~inate Thickener Polyester knitted fabric was printed with two print pastes constituted as follows:
Test Conventional Recipe (%) Recipe I%) Dispersal Ruben C-13 liquid (anionic disperse dye) 4.0 4.8 ~.~23g~
Monosodium orthophosphate 0.1 0.1 Matexil PA-L (sodium m-nitrobenzene sulphonate) It It Manutex US (high viscosity sodium alienate with 0.6 percent Cay+ on alienate) - 2.25 Thickener 3.6 Calgon (sodium-hexa-m-phosphate) - 0.55 Waxer 91.3 Al 3 10 100 loo The dye was then fixed and washed.
The prints showed equal color intensity although 20 percent less dye was used in the test recipe.
The thickener was the same as in Example 3.
~;uar/Calcium Citrate/Al~inate Thickener Polyester knitted fabric was printed with two print pastes constituted as follows:
Test Conventional recipe (96) Recipe (%) Dispersal Ruben C-B liquid (anionic disperse dye) 4.0 4.8 Monosodium orthophosphate Al 0.1 Matexil PA-L (sodium m-nitrobenzene sulphonate) 1.0 It Monocled (medium viscosity sodium alienate with 0.296 KIWI on alienate) - 3.2 ~Z3~
9 Aye Thickener 3.6 Calgon (sodium hexa-m-phosphate) - 0.8 Water 91.3 90.1 The dye was then fixed and washed.
The color intensity on the prints corresponded to a dye saving of 20% when the test recipe was used The amount of algina~e (Monocle DO) in the test recipe was 1.2% V5. 3.2% in the conventional recipe.
The thickener was the same as in Example 3.
CMC/Salt/Al~inate Thickener Following the procedure of Example I but using carboxymethyl cellulose instead of guard a blend was prepared which was then used to prepare a 34/38/28 thickener as in Example 3.
Polyester knitted fabric was printed with two print pastes constituted as follows:
Test Conventional Recipe (%) Recipe (%) Palanil Brilliant Blue BGF liquid (anionic disperse dye) 4.0 4.6 Monosodium or~hophosphate 0.1 0.1 Silcolapse 5006 (anti-foam agent based on silicon fluid emulsion 0.1 0.1 Prisulon SPECK (thickener based on ~uar/starch derivatives) - 3.75 I
~-1003 Thickener 4.7 Waxer 9 9~-4 The dye was then fixed and washed.
the print showed equal color intensity although 13% less dye was used in the test recipe.
Guar/Salt!Al~inate Thickener Polyester knitted fabric was printed with two print pastes constituted assay follows:
Test Conventional ape (%) Recipe (%) Palanil Brilliant Blue BGlF liquid 3.6 4.8 15 I,uprintan HDF, fixation accelerator (8ASF) 1.5 1.5 Monosodium orthophosphate I 0.2 Silcolapse 5006 0.1 0.1 Prisulon SPECK - 3.75 20 Thickener 2.7 Water 91.9 89.65 The dye was then fixed and washed. The color intensity on the print correspondcnd to a dye saving of 25%.
Thea thickener was prepared by dry mixing the following ingredients:
Amt. (Wt. 96 Sodium alienate (Monocled) 51 Citric acid Andy. 8 Hydrocolloid/salt blend of Example 1 41 Gua!/Salt/Alginate Thickener Knitted polyester was printed with two print pastes constituted as 10 hollows:
Test Conventional Recipe (%) Recipe (%) Palanil Dark glue 3 RUT liquid 15 (anionic disperse dye) 4.2 6.Q
Luprintan HDF (non-ionic fixation accelerator based on fatty acid derivative) 1.5 1.5 Monosodium or orthophosphate 0.2 0.2 20 5ilcolapse 5006 0.1 0.1 Prisulon SPECK - 3.75 Thickener 3.6 .
Water 90.4 88.45 100 1~0 25. The dye was then fixed and itched.
I
12 Aye The prints showed equal color intensity although 30% less dye was used in the test recipe The thickener was the same as in Example 3.
sealability vs. Water Hardness -The following table demonstrates the improved volubility of alginates in hard waxer when mixed with the hydrocolloid/salt blends of this invention as compared to the volubility of alginates when merely mixed with the same salts. In the table the first two samples are dry blends of sodium allegiant 10 and calcium citrate (sufficient to give 45% calcium conversion. The riskiest readings are actual. The third sample was of the same composition as the thickener in Example 3. In the fourth sample, the thickener was of similar composition Jo that of Example 3 except that the hydrocolloid/salt blend was 7496 xanthan gum and 26% calcium saturate.
15 The viscosity readings shown for samples 3 and 4 were obtained from a plot of viscosity vs. water hardness.
Cousteau/ vs. Water hardness RUT Brook field Visa., cup, 20 C, 18hr simply Alvin 50ppm Cook Hardness 350ppm Cook hardness on 1.71 42,800 24,400 2 1.81 42,600 27,400 3 1.75 38,500 701300 4 2.087,000 76,000 Pet Food Formulation A golfed pet food was prepared using as the thickener sodium allegiant and a hydrocolloid/salt blend of this invention comprising guard and calcium sulfate. The composition of the pet food was:
I
Wt. %
Sodium allegiant (ManugelU3J GOB) 5.0 Tetrasodium pyrophosphate 0.5 Water (Do) 249 Gorky So Blend 12.5 Chopped meat 250 Gel strength was measured for one hour and the following data obtained.
Setting time (min.) Gel Strength (ems) * Stevens - LFRA Texture Analyzer, 1 " (2.54 cam plunger, 4 rum penetration.
EXAMPLE I I
Bakery Custard Formulations A custard was prepared of the following compositions:
Wt. (96) Lac~icol~F 336 (dairy grade sodium allegiant blend) 2.5 uric SO blend 1.0 Puzzle EKE, pre-gelatinized potato starch 20 Full cream milk powder 30 Caster sugar 50 Deionized water 250 I The gel strength of the custard was 117 gym at 30 miss and 332 gym at 18 ho, measured on a Stevens LFRA Texture Analyzer.
~4~1~
14 ~-1003 Viscosity vs._Water Hardness Hydrocolloid/salt blends in the ratios 14.3:85.7 and 85.7:14.3 were prepared following the procedure of Example 1. These blends were mixed
5 with sodium allegiant to form thickeners, which were dissolved in water of varying hardness. The following volubility data were obtained:
Viscosity vs. Water Hardness Thickener Align Hydro./Salt Viscosity* (cP3 (Ihr/18hr~
10 Cone (%) Cone (%) Blend 50ppm Cook eye 5.78 2.014.3: 85.7 37,400/75,700 30,303/67,600 5.78 2.085.7: 14.3 63,400/66,800 115,800/105,400 * RUT Brook field viscometer, 20C
Viscosity vs. Water Hardness Thickener Align Hydro./Salt Viscosity* (cP3 (Ihr/18hr~
10 Cone (%) Cone (%) Blend 50ppm Cook eye 5.78 2.014.3: 85.7 37,400/75,700 30,303/67,600 5.78 2.085.7: 14.3 63,400/66,800 115,800/105,400 * RUT Brook field viscometer, 20C
Claims (9)
1. A mixture of (A) a blend of (1) a hydrocolloid selected from the group consisting of guar, oxidized guar, carboxymethyl guar, de-polymerized guar, hydroxyalkyl guar, polyvinyl alcohol, carboxymethyl cellulose, xanthan gum, cold water soluble locust bean gum, cold water soluble starch, hydroxyethylated starch, and hydroxypropylated starch and (2) a calcium, barium, or strontium salt wherein the ratio of salt to hydrocolloid ranges from 10:1 to 1:20 and (B) a soluble alginate wherein the ratio (A):(B) is such that the divalent cation level is the amount theoretically necessary to convert 16-60% of the soluble alginate.
2. A mixture of Claim 1 wherein the ratio (A):(B) is such that the divalent cation level is the amount theoretically necessary to convert 25-50 of the soluble alginate.
3. A mixture of Claim 1 wherein the hydrocolloid is guar, a guar derivative, carboxymethylcellulose, or xanthan gum, the salt is a calcium salt, and the alginate is sodium alginate.
4. A mixture of Claim 3 wherein the guar is hydroxyethyl guar and the salt is calcium citrate.
5. A mixture of Claim 1 wherein (A) is prepared by a process which comprises aqueously mixing a hydrocolloid and a salt to form a paste, drying said paste to about 90% solids, and then milling said dried paste.
6. A print paste composition comprising (1) a pigment, anionic dye, or non-ionic dye, and (2) 10 to 90% by weight of a mixture of Claim 1.
7. A print paste composition of Claim 6 wherein the salt in the blend is calcium citrate, the soluble alginate is sodium alginate, and the calcium level ranges from 25 to 50% of the amount theoretically necessary to convert the soluble alginate, further comprising a thickening agent which is one or a combination of guar, guar derivative, locust bean gum, CMC, synthetic polymer, cellulose derivative, or starch derivative.
8. A gelled or structured pet food, sauce gravy, bakery filling, or pimento strip comprising an effective amount of a mixture of Claim 1.
9. A process for printing substrates which comprises applying to said substrates a print paste composition of Claim 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08421957A GB2163766B (en) | 1984-08-30 | 1984-08-30 | Printing paste thickener compositions |
| GB8421957 | 1984-08-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1239491A true CA1239491A (en) | 1988-07-19 |
Family
ID=10566044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000489231A Expired CA1239491A (en) | 1984-08-30 | 1985-08-22 | Calcium control system |
Country Status (21)
| Country | Link |
|---|---|
| US (2) | US4693728A (en) |
| EP (1) | EP0173555B1 (en) |
| JP (2) | JPH0660265B2 (en) |
| KR (1) | KR930008213B1 (en) |
| AT (1) | ATE73472T1 (en) |
| AU (1) | AU579661B2 (en) |
| CA (1) | CA1239491A (en) |
| CS (1) | CS276715B6 (en) |
| DE (1) | DE3585577D1 (en) |
| DK (1) | DK167243B1 (en) |
| ES (1) | ES8700292A1 (en) |
| GB (1) | GB2163766B (en) |
| GR (1) | GR852067B (en) |
| HU (1) | HU201781B (en) |
| IE (1) | IE58656B1 (en) |
| IN (1) | IN165879B (en) |
| NO (1) | NO173020C (en) |
| NZ (1) | NZ213150A (en) |
| PT (1) | PT81038B (en) |
| YU (1) | YU45267B (en) |
| ZA (1) | ZA856538B (en) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786288A (en) * | 1983-10-07 | 1988-11-22 | Toray Industries Incorporated | Fabric treating method to give sharp colored patterns |
| GB2148317B (en) * | 1983-10-17 | 1987-05-20 | Kelco Ail Int Ltd | Print paste composition |
| GB2163766B (en) * | 1984-08-30 | 1988-01-27 | Kelco Ail Int Ltd | Printing paste thickener compositions |
| US4842919A (en) * | 1987-02-03 | 1989-06-27 | Minnesota Mining And Manufacturing Company | Pad forming method |
| US4868000A (en) * | 1988-08-31 | 1989-09-19 | Nestec S.A. | Mousse product |
| US5153317A (en) * | 1989-05-24 | 1992-10-06 | Merck & Co., Inc. | Composition and method for rheology controlled printing of fabric and carpet |
| US5079348A (en) * | 1989-05-24 | 1992-01-07 | Merck & Co., Inc. | Film-forming size composition |
| US5112445A (en) * | 1989-06-23 | 1992-05-12 | Merck & Co., Inc. | Gellan gum sizing |
| US5098635A (en) * | 1989-11-09 | 1992-03-24 | Copolymer Rubber & Chemical Corporation | Process for manufacturing friable rubber bales |
| GB8926904D0 (en) * | 1989-11-28 | 1990-01-17 | Unilever Plc | Thickening system |
| US5102446A (en) * | 1990-02-01 | 1992-04-07 | Aqualon Company | No-till liquid herbicide and fertilizer suspension |
| US5055111A (en) * | 1990-03-19 | 1991-10-08 | Aqualon Company | Oxidized polygalactomannan for improved textile washing of pad-dyed carpet |
| US5294455A (en) * | 1991-04-08 | 1994-03-15 | Petrella Limited | Food product |
| US5389393A (en) * | 1993-04-07 | 1995-02-14 | Kraft General Foods, Inc. | Quick-setting dessert gel mix |
| US6726930B1 (en) * | 1993-09-09 | 2004-04-27 | Penwest Pharmaceuticals Co. | Sustained release heterodisperse hydrogel systems for insoluble drugs |
| US5997937A (en) * | 1996-05-06 | 1999-12-07 | Kraft Foods, Inc. | Quick-setting gel mix |
| CA2203357A1 (en) * | 1996-05-06 | 1997-11-06 | Mark V. Hembling | Quick-setting gel mix |
| US5830240A (en) * | 1996-10-23 | 1998-11-03 | Solutia Inc. | Fibers and textile materials having enhanced dyeability and finish compositions used thereon |
| US5944852A (en) * | 1996-10-23 | 1999-08-31 | Solutia Inc. | Dyeing process |
| PT1117379E (en) * | 1998-10-07 | 2005-10-31 | Giltech Ltd | FOAMING AND FOAMING FORMULA |
| US6280782B1 (en) | 1999-11-08 | 2001-08-28 | The Pillsbury Company | Non-emulsion based, moisture containing fillings for dough products |
| ES2250217T3 (en) | 1999-12-08 | 2006-04-16 | National Institute Of Advanced Industrial Science And Technology | COMPOSITION OF BIODEGRADABLE RESIN. |
| JP5237818B2 (en) * | 2005-10-19 | 2013-07-17 | ヒルズ・ペット・ニュートリシャン・インコーポレーテッド | Process for producing a food composition |
| CA2652091C (en) * | 2006-05-19 | 2012-07-17 | Hercules Incorporated | Oxidized guar for oilfield servicing fluids |
| CN102665441B (en) * | 2009-12-22 | 2016-02-17 | Fmc有限公司 | For the water-dispersible composition of food applications |
| AU2011378770B2 (en) | 2011-10-14 | 2015-01-29 | Hill's Pet Nutrition, Inc. | Process for preparing a food composition |
| CN103924456B (en) * | 2014-04-17 | 2016-04-06 | 苏州润弘贸易有限公司 | A kind of production technology of reactive printing thickener |
| US20210315265A1 (en) * | 2018-07-31 | 2021-10-14 | Nicoventures Trading Limited | Aerosol generating substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB752336A (en) * | 1952-04-02 | 1956-07-11 | Dick Co Ab | Improvements in or relating to stencil duplicating inks |
| US3060032A (en) * | 1960-06-17 | 1962-10-23 | Gen Foods Corp | Freezable gels |
| US3282717A (en) * | 1963-04-23 | 1966-11-01 | Kelco Co | Print paste thickener |
| US3255021A (en) * | 1963-05-28 | 1966-06-07 | Staley Mfg Co A E | Method of preparing frozen seafood |
| US3349079A (en) * | 1964-04-06 | 1967-10-24 | Kelco Co | Gel forming alginate products and method of producing the same |
| US3764707A (en) * | 1970-03-04 | 1973-10-09 | Marine Colloids Inc | Algin salt-mannogalac- for gum containing aqueous cosmetic lotion |
| JPS5742750B2 (en) * | 1973-12-21 | 1982-09-10 | ||
| US4073653A (en) * | 1976-02-10 | 1978-02-14 | Merck & Co., Inc. | Printing paste compositions containing sodium cellulose sulfate, and processes therefor |
| IE48475B1 (en) * | 1978-09-08 | 1985-02-06 | Unilever Ltd | Processes for the preparation of gels,products obtained thereby,and their use |
| US4222740A (en) * | 1979-03-05 | 1980-09-16 | Armstrong Cork Company | Coloration method for textiles |
| NO153084C (en) * | 1979-08-01 | 1986-01-15 | Quaker Oats Ltd | PROCEDURE FOR THE MANUFACTURE OF IMMITTED FOOD PRODUCTS. |
| GB2058539B (en) * | 1979-09-19 | 1983-10-05 | Quaker Oats Ltd | Simulated food products and method of manufacturing therefor |
| JPS5655162A (en) * | 1979-10-11 | 1981-05-15 | Kibun Kk | Preparation of coagulated food, its seasoning, preparation of molded food, and its seasoning |
| US4436759A (en) * | 1982-03-26 | 1984-03-13 | Caribou Fisheries, Inc. | Production of shaped food products |
| IL64728A (en) * | 1982-01-08 | 1985-05-31 | Trilling David M | Production of shaped food products |
| GB2123856B (en) * | 1982-01-12 | 1985-05-09 | Kelco Ail Int Ltd | Printing on pretreated substrates |
| US4519803A (en) * | 1983-06-01 | 1985-05-28 | Kelco/Ail International Limited | Printing on pretreated substrates |
| GB2148317B (en) * | 1983-10-17 | 1987-05-20 | Kelco Ail Int Ltd | Print paste composition |
| GB2163766B (en) * | 1984-08-30 | 1988-01-27 | Kelco Ail Int Ltd | Printing paste thickener compositions |
-
1984
- 1984-08-30 GB GB08421957A patent/GB2163766B/en not_active Expired
-
1985
- 1985-08-15 YU YU1302/85A patent/YU45267B/en unknown
- 1985-08-20 NZ NZ213150A patent/NZ213150A/en unknown
- 1985-08-22 CA CA000489231A patent/CA1239491A/en not_active Expired
- 1985-08-26 CS CS856105A patent/CS276715B6/en unknown
- 1985-08-27 IE IE210585A patent/IE58656B1/en not_active IP Right Cessation
- 1985-08-27 US US06/770,114 patent/US4693728A/en not_active Expired - Lifetime
- 1985-08-27 GR GR852067A patent/GR852067B/el unknown
- 1985-08-27 EP EP85306076A patent/EP0173555B1/en not_active Expired - Lifetime
- 1985-08-27 AT AT85306076T patent/ATE73472T1/en not_active IP Right Cessation
- 1985-08-27 DE DE8585306076T patent/DE3585577D1/en not_active Expired - Fee Related
- 1985-08-28 ES ES546491A patent/ES8700292A1/en not_active Expired
- 1985-08-28 IN IN668/MAS/85A patent/IN165879B/en unknown
- 1985-08-28 ZA ZA856538A patent/ZA856538B/en unknown
- 1985-08-28 PT PT81038A patent/PT81038B/en not_active IP Right Cessation
- 1985-08-29 NO NO853402A patent/NO173020C/en unknown
- 1985-08-29 KR KR1019850006263A patent/KR930008213B1/en not_active IP Right Cessation
- 1985-08-29 AU AU46877/85A patent/AU579661B2/en not_active Ceased
- 1985-08-29 DK DK392185A patent/DK167243B1/en not_active IP Right Cessation
- 1985-08-29 HU HU853285A patent/HU201781B/en not_active IP Right Cessation
- 1985-08-30 JP JP60191805A patent/JPH0660265B2/en not_active Expired - Lifetime
-
1988
- 1988-06-10 US US07/205,415 patent/US4859208A/en not_active Expired - Lifetime
-
1993
- 1993-10-27 JP JP5268746A patent/JPH0749630B2/en not_active Expired - Lifetime
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