Source: http://www.google.com/patents/US5633309?dq=6,202,008
Timestamp: 2017-05-29 12:03:52
Document Index: 665691710

Matched Legal Cases: ['§176', '§175', '§176', '§176', '§175', '§176']

Patent US5633309 - Creping adhesives containing oxazoline polymers - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsA creping adhesive containing about 1% to about 25% polyoxazoline by weight, which imparts softness and resistance to bleaching, to a cellulosic web, and methods of using same are provided....http://www.google.com/patents/US5633309?utm_source=gb-gplus-sharePatent US5633309 - Creping adhesives containing oxazoline polymersAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS5633309 APublication typeGrantApplication numberUS 08/595,939Publication dateMay 27, 1997Filing dateFeb 6, 1996Priority dateDec 8, 1994Fee statusPaidAlso published asUS5602209Publication number08595939, 595939, US 5633309 A, US 5633309A, US-A-5633309, US5633309 A, US5633309AInventorsJoseph F. Warchol, Cynthia D. Walton-BongersOriginal AssigneeHoughton International, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (18), Non-Patent Citations (4), Referenced by (24), Classifications (19), Legal Events (16) External Links: USPTO, USPTO Assignment, EspacenetCreping adhesives containing oxazoline polymers
US 5633309 AAbstract
A creping adhesive containing about 1% to about 25% polyoxazoline by weight, which imparts softness and resistance to bleaching, to a cellulosic web, and methods of using same are provided.
1. A creping adhesive concentrate comprising:(a) about 35 percent by weight of aqueous polyamide-epichlorohydrin resin, said resin being the reaction product of about 5 percent by weight epichlorohydrin and about 20 percent by weight of the aqueous polyamide produced from a reaction of about 18 percent by weight caprolactam, 30 percent by weight carboxylic acid, about 25 percent by weight of an amine, and water; (b) between about 1 percent by weight and 25 percent by weight of an oxazoline polymer of the structure: ##STR3## where R is selected from the group consisting of an aryl group containing from 6 to 11 carbon atoms or an alkyl group containing from 1 to 11 carbon atoms, and n is an integer which provides said polymer with a molecular weight of from about 5000 to about 1,000,000; and (c) the balance water. 2. The creping adhesive according to claim 1 wherein the acid is itaconic acid and the amine is diethylene triamine.
3. The creping adhesive according to claim 1 wherein said oxazoline polymer is present in an amount of about 3 percent by weight.
4. The creping adhesive according to claim 1 wherein the oxazoline polymer is polyethyloxazoline.
5. The creping adhesive according to claim 4, wherein the polyethyloxazoline has a molecular weight of about 500,000.
6. A creping adhesive concentrate comprising about 1 percent to about 25 percent by weight of solids in water, said solids comprising an oxazoline polymer which is dispersable in water and a cross-linked polyamide-epihalohydrin resin.
7. The creping adhesive concentrate according to claim 6, wherein the oxazoline polymer has the structure ##STR4## where R is selected from the group consisting of an aryl group containing from 6 to 11 carbon atoms or an alkyl group containing from 1 to 11 carbon atoms, and n is an integer which provides said polymer with a molecular weight of from about 5000 to about 1,000,000.
8. The creping adhesive according to claim 7, wherein the molecular weight of the oxazoline polymer is between about 50,000 to about 500,000.
9. The creping adhesive according to claim 6, wherein the adhesive comprises a total of about 10 percent by weight solids.
10. The concentrate according to claim 6 wherein said resin is the reaction product of a polyamide produced from the reaction of a lactam, an amine and an acid.
11. The concentrate according to claim 10 wherein said acid is a carboxylic acid.
12. The concentrate according to claim 11 wherein said carboxylic acid is adipic acid or itaconic acid.
13. The concentrate according to claim 10 wherein said amine is diethylenetriamine.
14. The adhesive according to claim 13 wherein the reaction product results from the reaction of about 18 wt % caprolactam, about 30 wt % itaconic acid, and about 25 wt % diethylenetriamine.
15. The creping adhesive according to claim 14 wherein the oxazoline polymer is polyethyloxazoline.
16. The creping adhesive according to claim 15 wherein the polyethyloxazoline has a molecular weight of about 500,000.
17. The concentrate according to claim 10 wherein said lactam is caprolactam.
This is a continuation of application Ser. No. 08/352,371, filed Dec. 8, 1994, (now abandoned).
This invention relates generally to the field of manufacture of creping adhesives with application to tissue and toweling products, and particularly to the properties imparted by creping adhesives to the paper machine runnabilty and the resulting paper softness.
A wide variety of creping adhesives are known in the art. The paper industry's demand for faster paper machine speeds, less down time due to doctor blade changes and paper breaks, and softer and more uniform paper necessitates development of new and better creping adhesives. Desirable qualities for new and better creping adhesives that will improve paper machine runnability include: increased adhesion, dispersibility, uniform coating, and resistance to bleach out.
In one aspect, the present invention provides a creping adhesive concentrate comprising about 0.01% to about 25% by weight solids, including a polyoxazoline, and a polyamide polymer resin. Preferably, the polyoxazoline is a polyethyloxazoline; and the resin is selected from the resins described below. The creping adhesive of the invention coats more evenly, allowing the surface of the paper to be more uniform and improving paper machine runnability. Additionally, this creping adhesive provides the paper with a higher adhesion than currently available products.
The present invention provides a creping adhesive composition and methods of use which produce superior paper machine runnability in terms of adhesive strength, dispersibility, and resistance to bleach out in the creping and drying process of cellulosic webs useful for facial tissue, bathroom tissue, paper towels, or other such products. Bleach out is a decrease in adhesive strength of the creping adhesive due to addition of bleach in between dye changes.
Thus, the invention provides a creping adhesive concentrate formed of between about 5 to about 25% solids by weight, and preferably about 10% solids by weight. The solids comprise between about 1 weight percent (wt %) to about 5 wt % polyoxazoline, and preferably about 3 wt % polyoxazoline, between about 5 wt % to about 7 wt % polyamide polymer, and the balance water, but not excluding the use of other adjuvants including but not limited to corrosion inhibitors, preservatives, metal salts (eg. sodium, potassium, and ammonium salts of borates, oxyanions, and phosphates), and pH adjusters. All percentages provided herein are by weight unless otherwise indicated.
The oxazoline polymers according to this invention are water-soluble, or at least dispersible in water at the concentrations employed. These polymers can be either substituted oxazoline homopolymers or copolymers. In either event, the polymers have recurring units of the general formula ##STR1## where R is any organic radical which does not significantly decrease the water-solubility or water-dispersibility of the polymers. However, R may be any substituent selected from the group consisting of a substituted or unsubstituted aryl group containing from 6 to 11 carbon atoms or a substituted or unsubstituted alkyl group containing from 1 to 11 carbon atoms. The substituent R may therefore be alkyl, such as methyl, ethyl, propyl, butyl, isobutyl, etc, or aryl, such as a phenyl group or substituted phenyl group. Preferably, the substituent R, in at least about 50 percent of said units, is alkyl containing from 1 to 11 carbon atoms. Most preferably, the alkyl is ethyl. The symbol n is an integer which provides said polymer with a molecular weight of from about 5000 to about 1,000,000, preferably 50,000 to 500,000. Generally, n is the molecular weight of the polymer divided by the molecular weight of the monomer. For example, the preferred monomer ethyloxazoline, has a molecular weight of 99.13 (˜100). When the desired polyethyloxazoline molecular weight is about 5000, n is about 50; when the desired polyethyloxazoline molecular weight is about 1,000,000, n is about 10,000.
The polyamide resin component of the creping adhesive of this invention may be included in an amount up to that concentration which produces gel. For example, the polyamide resin may make up between about 1-25 wt % of the total solid content in the creping adhesive concentrate. This polyamide resin can be selected readily by one of skill in the art from among known and commercially available resins. Suitable resins known to those of skill in the art include but are not limited to the polyamide resins provided in the Code of Federal Regulations (CFR) 21 parts: §176.170, §175.300 and §176.180, which are incorporated by reference herein.
Particularly well suited for use in the creping adhesive of the invention are the polyamide resins described in Munjat, U.S. Pat. No. 3,869,342 and U.S. Pat. No. 3,869,343, incorporated by reference herein. One desirable resin has the composition of Table I, which contains approximately 15% solids. Other polyamide resins described in these latter patents are also desirable for use in the adhesive compositions of this invention.
The polyamide resin component of the preferred embodiment is a polyamide-epichlorohydrin resin that has a polyamide base polymer consisting of the reaction product of itaconic acid, diethylenetriamine, and caprolactam (see Table I part B). The polyamide base polymer is then crosslinked by epichlorohydrin and the pH adjusted with sulfuric acid to produce the polyamide-epichlorhydrin resin used in the preferred embodiment (see Table I part A).
TABLE I______________________________________Components       Percentage, by weight______________________________________Part A:polyamide base polymer            15-25H2 O        60-80epihalohydrin    1-8where the polyamide base polymer contains approximately 50%solids and is formed by the reaction of:Part B:caprolactam      15-25H2 O        21-55itaconic acid    20-40diethylene triamine            15-30______________________________________
Desirably, the halogen of the epihalohydrin of these formulations is chlorine. However, other suitable halogens, e.g. bromide, may be readily substituted by one of skill in the art. This formulation for a suitable polyamide resin may be adjusted as needed or desired. For example, one of skill in the art can readily substitute a suitable polybasic carboxylic acid, a diacid, or a triacid, for itaconic acid. Examples of suitable substitutes include sebacic acid, dodecanedioic acid, dimers or trimers of oleic acid, reactions with acrylic acid and the like. Similarly, one of skill in the art can readily substitute another amine base for the exemplified diethylene triamine used in the resin. See 21 C.F.R. §176,170, §175.300, and §176.180 for examples of other suitable acids and bases which may be used in the preparation of the resins.
As another example of a polyamide resin formula, one of skill in the art can readily select an alternative pH adjuster and thus, substitute another appropriate acid or base capable of adjusting the pH to between about 4 to about 8 for the sulfuric acid (see example 1). One of skill in the art can readily substitute an inorganic acid such as phosphoric acid or an organic acid such as citric acid for the exemplified sulfuric acid used to adjust the pH. Similarly, one of skill in the art can readily select from among the known preservatives. For example, suitable preservatives include KATHON®, PABA®, and triazines.
The water used in preparing the compositions of the invention is preferably soft water, i.e., water which is free of calcium and magnesium, although such soft water is not a requirement. Prior to use, a creping adhesive concentrate of the invention is diluted using water to about 0.01 percent to about 4 percent solids.
Currently, the presently preferred embodiment of the creping adhesive of the invention contains about 7% of the polyamide-epichlorohydrin (anhydrous) resin of Example 1, about 3% polyethyloxazoline with a molecular weight of about 500,000, corrosion inhibitors (preferably 0.6% sebacic acid, 0.55% triethanolamine, and 0.25% monoethanolamine), 0.2% preservative (preferably KATHON®), and the balance water. The addition of 3% polyethyloxazoline has been found to increase the adhesive strength of the polyamide resin by about 20%. This resulting composition, creping adhesive A is described in detail in Example 2 and is about 10±0.5% solids as determined by a conventional evaporation test, has a pH of between 5.8 and 6.4.
Alternatively, the creping adhesives of the invention may comprise polyoxazoline with multipolymer systems, rather than the two polymer systems described above. For example, the polyoxazoline may be combined with such components as polyvinylamides, polyvinylalcohols (PVA), glyoxylated polyvinylamides, polyethylene oxide, polyethylenimine, polyvinylpyrrolidone, and carbowax. As with other polymer systems, polyoxazoline can be readily added into these multipolymer systems. Desirable formulations includes a combination of polyvinylalcohol and polyethyloxazoline; a combination of polyethylenimine and polyethyloxazoline; and a combination of modified polyethylenimine and polyethyloxazoline.
This creping adhesive, and all the adhesives of the invention, are used by applying it to a creping cylinder, e.g. a Yankee Dryer, or equivalent equipment, for example by spraying directly onto a dryer.
Thus, the present invention provides a method for manufacturing paper products. The method of the invention provides improved dispersibility, adhesion, coating and thus, paper machine runnability, i.e., there are fewer problems in paper runs and thus a decrease in the number of times a machine must be stopped and re-started. Thus, the use of the creping adhesive of the invention results in more usable paper, which has even edges and color and fewer holes. The method of the invention also improves resistance to bleach out when paper colors are changed. Improved paper softness may also result.
Preferably, the creping adhesives of the invention are applied directly to a drying cylinder used in the preparation of cellulosic web used to make tissue products. For example, the creping adhesives are desirably sprayed onto the cylinder, e.g. a Yankee dryer, at a rate of between about 25 to 100 cc/minute, and preferably about 30 cc/minutes, operating at ambient temperature However, one of skill in the art may adjust this rate as needed, depending upon such variables such as, e.g., furnish, stock, creping adhesive concentration, other chemicals present, and the dryer conditions.
Preparation of a Polyimide Resin
TABLE II______________________________________Components:      Percentage, by weight______________________________________Part A:Polyamide base polymer            20.8H2 O        74.2epichlorohydrin  4.6H2 2SO4            0.2preservative     0.2            100.0,where the polyamide base polymer contains approximately 50%solids and is formed by the reaction of:Part B:caprolactam      17.98%H2 O        26.41itaconic acid    31.02diethylene triamine            24.59            100.00______________________________________
The polyamide-epichlorohydrin resin and the polyamide base polymer were prepared using the processes described in U.S. Pat. No. 3,869,342 and U.S. Pat. No. 3,869,343.
Preparation of a Creping Adhesive
Trial on Tissue Machine
To repair a low spot in the dryer, the mill had to spray metalize the front edge of the dryer with a stainless steel coating. Shortly afterwards, a continuous creping system was installed. The continuous creping system is designed for use with an index blade steel. Soon after the installation of the creping system, the system was found to be unable to run in the continuous mode due to a rough area where the stainless steel was bonded to the cast iron. As the blade contacted the front edge, it became worn and caused drag marks on the sheet and tears on the front edge.
The mill attempted to solve this problem using other commercially available adhesive products as instructed by the manufacturer to attempt to obtain improvement in the ability to run the continuous blade system.
Creping adhesive A, prepared as described in Example 2 above, and a release agent comprising emulsifiable mineral oil [Houghton] were used in this test run.
Release--40 cc/min
This example provides data showing the adhesive strength of exemplary creping adhesives of the invention as measured on the Tinius-Olsen Testing Machine Model 5000 [Tinius Olsen Testing Machine Co.; Willow Grove, Pa.] by a 180° Peel Test Method, which is a modification of the ASTM method D903.
1. Steel plates [Catalog No. 101-A-2, SAE 1010 cold rolled heavy gauge steel plates, Metaspec Colo.; San Antonio, Tex. or equivalent] were submerged in a petroleum ether bath for at least 2 hours to remove the rust preventative coating. The plates were then washed with CERFAK® 1400 surfactant, rinsed with acetone, and then air-dried.
5. The sample plate was placed in the testing machine's lower clamp, after first debonding about 1" of the bound fabric from the metal plate. The fabric "tail" was 180° from the upper clamp. The "tail" was then placed into the testing machine's upper clamp such that it was bent back upon itself.
To demonstrate that the components of the invention are synergistic, not additive in effect, dual samples of the polyamide resin of Example 1 with (a) polyethyloxazoline low molecular weight (approx. 50,000), (b) polyethyloxazoline having a molecular weight of approx. 200,000 MW or (c) polyethyloxazoline having a molecular weight of approx. 500,000 MW, were run on the above-described test. In addition, blanks of each version of polyethyloxazoline (no polyamide resin) were run. The adhesive strength data are provided in Table III below.
TABLE III______________________________________                  Adhesive Strength                  Pounds per inch______________________________________Polyamide Resin        1.377Polyamide Resin + 1% polyethyloxazoline                  1.416(50,000 MW)1% polyethyloxazoline (50,000 MW)                  0Polyamide Resin + 1% polyethyloxazoline                  1.590(200,000 MW)1% polyethyloxazoline (200,000 MW)                  0Polyamide Resin + 1% polyethyloxazoline                  1.700(500,000 MW)1% polyethyloxazoline (500,000 MW)                  0______________________________________
TABLE IV______________________________________                  Adhesive Strength                  Pounds per inch______________________________________Polyamide Resin        1.31Polyamide Resin + 1% polyethyloxazoline                  1.70(500,000 MW)Polyamide Resin + 5% polyethyloxazoline                  1.79(500,000 MW)______________________________________
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