A water based thixotropic adhesive gel is disclosed which consists essentially of: water; partially hydrolyzed polyvinyl alcohol, or wherein a portion of the polyvinyl alcohol is replaced with polyvinylpyrrolidone; a water-soluble high viscosity thickening agent polymer which is compatible with the polyvinyl alcohol and which imparts thixotropic properties to the gel; a water-soluble plasticizer for the polyvinyl alcohol; and a watersoluble defoamer in proportion of ingredients so that the viscosity of the adhesive will break down when a flexible tube or squeeze bottle dispenser is finger-pressed and have a sufficiently low viscosity to allow for easy extrusion from an orifice having a diameter of about 0.06 to 0.12 inches. When pressure is released, after the desired amount of adhesive has flown out of the dispenser, the adhesive quickly reverts to very close to its original gel state so that it will not run on a vertical surface on porous and semiporous surfaces such as paper. An article of manufacture is also provided whereby the adhesive gel containing the above ingredients is in a flexible dispenser from which the adhesive can be dispensed by finger-pressure.
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1. An article of manufacturing manufacture comprising:
A. a flexible dispenser wherein the dispenser has a dispensing opening of from about .[∅011 to 0.12 #x2205;0028 to about 0.018 square inches and contains a clear adhesive gel which can be dispensed therefrom by finger-pressure to form a glue line which does not run when extruded on paper in a vertical position; B. said clear adhesive gel comprising: (1) about 70% to 93% of water; (2) about 5% to 25% of a partially hydrolyzed polyvinyl alcohol: (3) about 0.5% to 3% of a water soluble plasticizer for the polyvinyl alcohol; (4) a water soluble defoamer in an amount sufficient to prevent air bubbles from destroying the clarity of the gel; and (5) a water soluble thickening agent polymer compatible with the polyvinyl alcohol and in an amount sufficient to provide the gel with a thixotropic index of about 1.5 to 4.5, said thickening agent selected from the group consisting of sodium carboxymethylcellulose, sodium alginate and xanthan gum. 12. An article of manufacture comprising:
A. a clear flexible plastic dispenser wherein the dispenser has a dispensing opening if of from about .[∅011 to 0.12 #x2205;0028 to about 0.018 square inches and contains a clear adhesive gel which can be dispensed therefrom by finger-pressure to form a glue line which does not run when extruded on paper in a vertical position: B. clear adhesive gel comprising of: (1) about 70% to 93% of water: (2) about 5% to 25% of a partially hydrolyzed polyvinyl alcohol: (3) about 0.5% to 3% of a water soluble plasticizer for the polyvinyl alcohol; (4) a water soluble defoamer in an amount sufficient to prevent air bubbles from destroying the clarity of the gel; and (50 (5) about 0.5% to 1.5% of a water soluble thickening agnet agent polymer compatible with the polyvinyl alcohol to impart a thixotropic index to the gel of about 1.5 to 4.5, said thickening agent selected from the group consisting of sodium carboxymethylcellulose, sodium alginate and xanthan gum. 2. The article of
3. The article of
4. The article of
5. The article of
6. The article of
7. The article of
10. The article of
15. The gel of
16. The gel of
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This 2on one substrate to another in a vertical plane, otherwise, the substrate which is not held in place but rather depends on the wet glue for positioning would slip off of the vertical surface of the first substrate. The wet tack of the gel of this invention preferably vanes from about 225 g per square inch to over 600 grams per square inch and preferably from about 250 to 500 grams per square inch.
Determinations for the rate of set are performed on a white paper pad. A glue line is placed on smooth white paper of a 5.5×8.5 inches paper pad. The single glue line is placed in about the middle of the pad parallel to the length of the paper. This glue is then spread evenly by the use of a No. 22, WIRE-CATOR which is supplied by the Leneta Company. The WIRE-CATOR is also referred to as a wire wrap rod. The WIRE-CATOR draws down a uniform thickness of film from the single glue line. Use of the No. 22 WIRE-CATOR draws down a glue line to a thickness of 1.5 rail.
A second sheet of the same paper has one of its narrow ends raised so that it can be grasped by the fingers. The second sheet is pressed over the first sheet. The two pieces are then slowly pulled apart by lifting the raised end of the second sheet and holding the first sheet down in place. The time that it takes to encounter fiber tearing bond is the rate of set. The preferred rate of set for the gels of this invention is from about 16 seconds to 35 seconds and preferably from about 18 to 32 seconds.
The values for both the wet tack and rate of set recited herein are obtained at 25°C and a relative humidity of 35%.
This example shows the composition, preparation and properties of an adhesive gel of this invention as well as use of an article of this invention.
| ______________________________________ |
| Ingredient Parts By Weight |
| ______________________________________ |
| Deionized water 83.51 |
| Polyvinyl alcohol1 |
| 13.33 |
| Sodium salt of 1.00 |
| Carboxymethylcellulose2 |
| DEFOAMER3 0.25 |
| Ethyl parahydroxybenzoate |
| 0.05 |
| Benzoic Acid 0.10 |
| Propylene Glycol 1.75 |
| Blue dye4 0.01 |
| ______________________________________ |
| 1 VINOL 523 which is a partially hydrolyzed polyvinyl alcohol |
| supplied by Air Products and Chemicals, Inc. |
| 2 CMC 7HX4 which is supplied by the Aqualon Company of Wilmington, |
| Delaware. |
| 3 DEFOAMER 622 which is a monofunctional polyalkoxylated polyether |
| defoamer supplied by the Thomas W. Dunn Corp of Ridgefield, N.J. |
| 4 No. 5601, FD&C Blue No. 1 which is supplied by Warner Jenkinson |
| Cosmetic Colors of South Plainfield, New Jersey. |
The adhesive of Example 1 was prepared by slowly adding the polyvinyl alcohol and CMC to water under fast agitation in a jacketed tank equipped with agitators. The CMC is preferably dry blended with a portion of the polyvinyl alcohol before addition to the water. The defoamer was then added. A small portion of the total amount of water in the gel can be obtained from steam condensation when the mixture is heated in contact with steam. The ethyl parahydroxybenzoate and benzoic acid were then mixed in the composition and the temperature of the mixture was raised to 85°C to 90°C with slow agitation for about 15 to 20 minutes until the composition was smooth and homogeneous. The composition was then cooled to 50°C with continued slow agitation. The blue dye was then added which had been prepared in advance by mixing 2 parts of the dye with 98 parts of water. Mixing was continued until the batch color was uniform.
The adhesive was then filled into 3 fluid ounce clear, low density polyethylene tubes 12 having a cap 22 and nozzle 24 and opening 26 of 0.073 inches in diameter. After filling, the back end of tubes 12 are heat sealed to form a crimp 14 having flap 16 extending therefrom as shown in Fig Land FIG. 1 and FIG. 2. The portion of the tube 12 in direct contact with the gel 40 was transparent with a slight blue tint. The portion of tube 12 which was not in direct contact with the gel was translucent.
All of the examples set forth herein were performed in much the same manner as with EXAMPLE 1.
The adhesive gel of Example 1 was transparent with a blue tint, easily dispensed with finger-pressure from the resilient plastic tube 12 having an orifice 26 of 0.073 inches diameter. It had wet tack of 435 g (grams) per square inch and a time of set of 25 seconds. It was free of air bubbles, and when dispensed from such tube and orifice on to a sheet of paper held vertically, it formed a uniform, thin, horizontal bead of adhesive which did not run and formed fiber tearing adhesive bonds on drying to a clear film. The gel can be dispensed in a steady stream through the dispenser orifice. The strong wet tack held a second sheet of paper in place on the vertical surface while the lengthy time of set permitted sliding and repositioning of the second sheet on the first before permanent adhesive bonds were formed. The gel washed out of clothing both before and after drying. This product exhibited all the advantages set forth in the hereinabove Summary of Invention. It had a thixotropic index of about 2. The viscosity of the adhesive gel when measured at 25°C with an RVF Brookfield viscometer with a No. 6 spindle was as follows:
Initial ly, Initially, after manufacture, and at a speed 2 of RPM, a viscosity of 50,000 to 60,000 cps.
Initially, after manufacture, and at a speed of 20 RPM, a viscosity of 24,000 to 28,000 cps.
After standing for about 12 hours and at a speed of 2 RPM, a viscosity of 70,000 to 80,000 cps.
After standing for about 12 hours and at a speed of 20 RPM, a viscosity of 30,000 to 40,000 cps.
After one month from manufacture, the viscosity was not over 100,000 cps when measured at a speed of 2 RPM. The adhesive of this invention had a pH of 4.8.
This example provides another formulation having the advantageous properties of this invention and illustrates the use of a lower viscosity polyvinyl alcohol. The blue dye, CMC and defoamer were the same as in EXAMPLE 1.
| ______________________________________ |
| Ingredient Parts By Weight |
| ______________________________________ |
| Deionized water 76.84 |
| Blue dye 0.01 |
| Polyvinyl alcohol* 20.00 |
| CMC 1.0 |
| Defoamer 0.25 |
| Ethyl parahydroxybenzoate |
| 0.05 |
| Benzoic acid 0.10 |
| Propylene glycol 1.75 |
| ______________________________________ |
| *VINOL 205 which is a product supplied by Air Products and Chemicals, Inc |
This gel had a viscosity of 67,500 cps at 2 RPM and 21,000. cps AT 20 RPM when measures at 25°C with a Brookfield RVF viscometer having a No. 6 spindle. The thixotropic index was 2.4 and it had a wet tack of 250 g per square inch.
This example illustrates the use of smaller quantities of the polyvinyl alcohol and CMC which produced product having the advantageous properties of this invention.
| ______________________________________ |
| Ingredient Parts By Weight |
| ______________________________________ |
| Deionized water 85.4 |
| Blue dye 0.01 |
| Defoamer 0.25 |
| Polyvinyl alcohol* |
| 11.6 |
| CMC 0.87 |
| Propylene Glycol |
| 1.75 |
| Preservative** 0.10 |
| ______________________________________ |
| *VINOL 540 which is supplied by Air Products and Chemicals, Inc. for a |
| partially hydrolyzed polyvinyl alcohol having a high viscosity and a |
| percent hydrolysis of 87% to 98%. |
| **KATHON LX 1.5 which is a mixture of |
| 5chloro-2-methyl-4-isothiazolin-3-one and 2methyl-4-isothiazolin-3-one |
| which is supplied by Rohm and Haas Co. |
The blue dye, defoamer and CMC used in EXAMPLE 3 were the same as that of EXAMPLE 1.
This example illustrates the formula of a composition of this invention which contains a substantial quantity of polyvinylpyrroliodine.
| ______________________________________ |
| Ingredient Parts By Weight |
| ______________________________________ |
| Deionized Water 83.51 |
| Defoamer 0.25 |
| Polyvinyl alcohol 6.67 |
| CMC 1.00 |
| Polyvinylpyrrolidone* |
| 6.66 |
| Propylene Glycol 1.75 |
| Blue dye 0.01 |
| Ethyl parahydroxybenzoate |
| 0.05 |
| Benzoic acid 0.10 |
| ______________________________________ |
| *LUVISCOL K90 which is supplied by B.A.S.F. Akhengesellschaft. |
The adhesive gel of this EXAMPLE 4 had a viscosity of 35,000 cps at 2 RPM and 20,000 cps at 2 RPM when measured by use of a Brookfield RVF viscometer at 25°C with a No. 6 spindle. The thixotropic index was 1.75 and the wet tack was 250 g per square inch. The polyvinyl alcohol, CMC, and blue dye were the same as that used in EXAMPLE 1.
This example illustrates a composition of this invention which used xanthan gum as the thickening agent polymer.
| ______________________________________ |
| Ingredient Parts By Weight |
| ______________________________________ |
| Deionized water 83.51 |
| Blue dye 0.01 |
| Polyvinyl alcohol 13.33 |
| Xanthan gum1 1.00 |
| Defoamer 0.25 |
| Ethyl parahydroxybenzoate |
| 0.05 |
| Benzoic acid 0.10 |
| Propylene glycol 1.75 |
| ______________________________________ |
| KELAZAN, KELZAN, an industrial grade xanthan gum |
| supplied by the Kelco Division of Merck & Co. |
The gel of EXAMPLE 5 had a viscosity of 62,000 cps and 13,500 cps for a thixotropic index of about 4.6. The viscosity was measured at 25° C. by use of a Brookfield RVF viscometer with a No. 6 spindle. This product had a wet tack of 400 grams per square inch.
This example shows the use of sodium alginate as the thickening agent polymer for preparing a gel adhesive of this invention. The remaining ingredients are the same as those used in EXAMPLE 1.
| ______________________________________ |
| Ingredient Parts By Weight |
| ______________________________________ |
| Deionized water 83.51 |
| Blue dye 0.01 |
| Polyvinyl alcohol 13.33 |
| Sodium alginate* 1.00 |
| Defoamer 0.25 |
| Ethyl parahydroxybenzoate |
| 0.05 |
| Benzoic acid 0.10 |
| Propylene glycol 1.75 |
| ______________________________________ |
| *KELGIN MV which is supplied by the Kelco Division of Merck & Co. |
The gel of this EXAMPLE 6 had a viscosity of 35,000 cps and 23,000 cps when measured at 2 RPM and at 20 RPM respectively with a Brookfield RVF viscometer at 25°C using a No. 6 spindle. It had a thixotropic index of about 1.5 and a wet tack of 335 g per square inch.
This example shows incompatibility of hydroxypropyl methylcellulose as the thickening agent polymer.
This formulation was unsatisfactory since a thick layer of the hydroxypropyl/methlcellulose hydroxypropyl methylcellulose separated and formed on top of the sample.
| ______________________________________ |
| Ingredient Parts by Weight |
| ______________________________________ |
| Deionized water 83.51 |
| FD&C No. 1 (2% aqueous solution) |
| 0.01 |
| Polyvinyl alcohol 13.33 |
| Hydroxypropyl methylcellulose* |
| 1.00 |
| Defoamer 0.25 |
| Ethyl parahydroxybenzoate |
| 0.05 |
| Benzoic acid 0.10 |
| Propylene glycol 1.75 |
| ______________________________________ |
| *METHOCEL K 15 MS which is supplied by the Dow Chemical Co. Apart from th |
| hydroxypropyl methylcellulose, the remaining ingredients were the same as |
| that of EXAMPLE 1. |
The substitution of hydroxyethyl cellulose for the hydroxypropyl methylcellulose of the formulation in EXAMPLE 7 also gave unsatisfactory results since a thick layer of the hydoxyethyl cellulose separated out of the formula.
Anderson, John, Columbus, Peter S., Patel, Yogeshbhai B.
| Patent | Priority | Assignee | Title |
| 5990205, | Aug 18 1997 | Mattel, Inc.; Mattel, Inc | Polyvinyl-based kneading and molding play composition |
| 7348378, | Dec 18 2003 | 3M Innovative Properties Company | Adhesive |
| 7560507, | Dec 18 2003 | 3M Innovative Properties Company | Adhesive |
| 8550131, | Jan 02 2013 | Liquid Squeeze, LLC | Liquid dispensing device, system and method |
| Patent | Priority | Assignee | Title |
| 3442845, | |||
| 3896073, | |||
| 4251400, | Nov 03 1971 | ELMER S PRODUCTS, INC | Hot and cold water redispersible polyvinyl acetate adhesives |
| 4722954, | Feb 14 1985 | DOW CHEMICAL COMPANY, THE, 2030 DOW CENTER, ABBOTT ROAD, MIDLAND, MICHIGAN 48640 | Formation of solid polymeric material comprising a latex and a filler mixture of silica and xanthan gum |
| 4767839, | Jul 06 1987 | Allied-Signal Inc. | Alternating aliphatic-aromatic poly(esteramide) |
| 5190997, | Jul 10 1985 | OMNOVA SERVICES, INC | Adhesive composition |
| EP210052, |
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