CA2551236A1 - Crosslinkable creping adhesive formulations - Google Patents
Crosslinkable creping adhesive formulations Download PDFInfo
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- CA2551236A1 CA2551236A1 CA002551236A CA2551236A CA2551236A1 CA 2551236 A1 CA2551236 A1 CA 2551236A1 CA 002551236 A CA002551236 A CA 002551236A CA 2551236 A CA2551236 A CA 2551236A CA 2551236 A1 CA2551236 A1 CA 2551236A1
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Abstract
Disclosed are adhesive formulations as creping process aids for producing an absorbent creped cellulosic sheet having a hid level of surface-perceived softness that comprises continuously forming a web of cellulosic papermaking fibers, adhering said web to a thermal drying means by means of adhesive compositions comprising polymers having at least one primary or secondary amine group in the backbone such as chitosan, polyvinylamine, polyvinyl alcohol-vinyl amine and polyaminoamide in combination with crosslinking agents such as dialdehydes or zirconium compounds having a valence of plus four including ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tartrate and creping said treated web from said thermal drying means. In the method for producing the absorbent creped cellulosic sheets, the zirconium crosslinking agent is advantageously applied directly and separately on the Yankee dryer at the time the base polymer is applied to the surface. Alternatively, when using dialdehydes, the dialdehydes are mixed with the base polymer just prior to application to the Yankee dryer surface without having the crosslinking reaction take place with the base polymer prior to reaching the heated Yankee surface. These sheets are useful in the manufacture of tissue and towel.
Description
CROSSLINKABLE CREPING ADHESIVE FORMULATIONS
This invention relates to papermakiag. More particularly, this invention is concerned with the°manufacture of grades of paper that are suitable for use in paper toweling, napkins, facial tissue, and bathroom tissue by methods that include creping utilizing novel adhesives used as creping process aids.
In the manufacture of tissue and towel products, a common step is the creping of the product. 2'his creping is done to provide desired aesthetic and performance properties to the product_ Many of the aesthetic properties of tissue and towel products rely more upon the perceptions of the consumer than on properties that can be measured quantitatively. Such thugs as softness, anti perceived bulk are not easily quantified, but have significant impacts on consumer axeptance. Since many of the properties of tissue and towel products are controlled or are at least influenced by the creping process, it is of interest to develop methods for controlling the creping process. Although the creping process is not well understood, it is known that changes in the process can result in significant changes in the product properties. A
need exists to provide a method for influencing the creping process by allowing the control of the adhesion of the tissue or towel substrate to the surface from which it is creped, most usually large cylindrical dryers known in the industry as Yankee dryers.
Paper is generally manufactured by suspending cellulosic fibers of appropriate Length in as aqueous medium and then removing most of the water to form a web.
The paper derives some of its structural integrity from the mechanical arrangement of the cellulosic fibers in the web, but most by far of the paper's strength is derived from hydrogen bonding which links the cellulosic fibers to one another. With paper intended for use as bathroom tissue, the degree of strength imparted by this interfiber bonding, while necessary to the utility of the product, results in a lack of perceived softness that is inimical to consumer acceptance. One common method of increasing the perceived softness of bathroom tissue is to crepe the paper. Creping is generally effected by fixing the cellulosic web to the surface of a dryer e.g. a drum dryer such as a Yankee drum thermal drying means with as adhesive/release agent combination and then scraping the web off of the surface by means of a creping
This invention relates to papermakiag. More particularly, this invention is concerned with the°manufacture of grades of paper that are suitable for use in paper toweling, napkins, facial tissue, and bathroom tissue by methods that include creping utilizing novel adhesives used as creping process aids.
In the manufacture of tissue and towel products, a common step is the creping of the product. 2'his creping is done to provide desired aesthetic and performance properties to the product_ Many of the aesthetic properties of tissue and towel products rely more upon the perceptions of the consumer than on properties that can be measured quantitatively. Such thugs as softness, anti perceived bulk are not easily quantified, but have significant impacts on consumer axeptance. Since many of the properties of tissue and towel products are controlled or are at least influenced by the creping process, it is of interest to develop methods for controlling the creping process. Although the creping process is not well understood, it is known that changes in the process can result in significant changes in the product properties. A
need exists to provide a method for influencing the creping process by allowing the control of the adhesion of the tissue or towel substrate to the surface from which it is creped, most usually large cylindrical dryers known in the industry as Yankee dryers.
Paper is generally manufactured by suspending cellulosic fibers of appropriate Length in as aqueous medium and then removing most of the water to form a web.
The paper derives some of its structural integrity from the mechanical arrangement of the cellulosic fibers in the web, but most by far of the paper's strength is derived from hydrogen bonding which links the cellulosic fibers to one another. With paper intended for use as bathroom tissue, the degree of strength imparted by this interfiber bonding, while necessary to the utility of the product, results in a lack of perceived softness that is inimical to consumer acceptance. One common method of increasing the perceived softness of bathroom tissue is to crepe the paper. Creping is generally effected by fixing the cellulosic web to the surface of a dryer e.g. a drum dryer such as a Yankee drum thermal drying means with as adhesive/release agent combination and then scraping the web off of the surface by means of a creping
2 blade. Creping, by breaking a significant number of interfiber bonds, increases the perceived softness of resulting bathroom tissue product.
In the past, common classes of thermosetting adhesive resins which have been used as creping adhesives have been represented by poly (aminoamide)-epichlorohydrin polymers (hereinafter referred to as PAE resins), such as those polymers sold under the tradenames Kymene, ltezosol, Cascamid, and Amrecs.
Each of these materials represent products sold respectively by the Hercules Chemical Company, the Houghton Company, the Borden Company, and Georgia-Pacific:
Although these materials are now In commercial use, our novel adhesive formulations are environmentally friendly and have lower in-use cost.
This invention provides adhesion ,which is equal or better than the adhesion characteristics available through the use of PAE resins but having none of the attendant environmental problems associated with the halogen moiety. The halogen free, particularly chloride free, creping adhesives of this invention prevent or inhibit chloride or halogen induced corrosion of the dryer, e.g. Yankee drum, surface and, also, are friendly to the environment and have a lower in use cost.
Obtaining and maintaining adhesion of tissue and towel products to dryers is an important factor in determining crepe quality. Inadequate adhesion results in poor or non-existing crepiag, whereas excessive adhesion may result in poor sheet quality and operational difficulties. Traditionally, creping adhesives alone or in combination with release agents have been applied to the surface of the dryer in order to provide the appropriate adhesion to produce the desired crepe. Various types of creping adhesives have been used to adhere fibrous webs to dryer surfaces such as Yankee dryers. Some examples of prior art creping adhesives are disclosed in U.S.
Patents 4,886,579; 4,528,316 and 4,501,640.
U.S. Patent No. 5,246,544 describes a creping adhesive that provides the ability to control coating mechanical properties and adhesion, and which can be more easily removed from dryer surfaces. The adhesive system described in said patent provides high adhesion of a fibrous web to dryer surface with low "friction".
Having low friction means that the fibrous web can easily be removed from the dryer surface.
Other references of Interest include U.S. Patents 5,232,553 and 4,684,439. All the prior art patents are of interest but do not disclose polymers having at least one primary or secondary amine group in the backbone such as chitosan, polyvinylamine, polyvinyl alcohol-vinyl amine, polyaminoamide and etc., in
In the past, common classes of thermosetting adhesive resins which have been used as creping adhesives have been represented by poly (aminoamide)-epichlorohydrin polymers (hereinafter referred to as PAE resins), such as those polymers sold under the tradenames Kymene, ltezosol, Cascamid, and Amrecs.
Each of these materials represent products sold respectively by the Hercules Chemical Company, the Houghton Company, the Borden Company, and Georgia-Pacific:
Although these materials are now In commercial use, our novel adhesive formulations are environmentally friendly and have lower in-use cost.
This invention provides adhesion ,which is equal or better than the adhesion characteristics available through the use of PAE resins but having none of the attendant environmental problems associated with the halogen moiety. The halogen free, particularly chloride free, creping adhesives of this invention prevent or inhibit chloride or halogen induced corrosion of the dryer, e.g. Yankee drum, surface and, also, are friendly to the environment and have a lower in use cost.
Obtaining and maintaining adhesion of tissue and towel products to dryers is an important factor in determining crepe quality. Inadequate adhesion results in poor or non-existing crepiag, whereas excessive adhesion may result in poor sheet quality and operational difficulties. Traditionally, creping adhesives alone or in combination with release agents have been applied to the surface of the dryer in order to provide the appropriate adhesion to produce the desired crepe. Various types of creping adhesives have been used to adhere fibrous webs to dryer surfaces such as Yankee dryers. Some examples of prior art creping adhesives are disclosed in U.S.
Patents 4,886,579; 4,528,316 and 4,501,640.
U.S. Patent No. 5,246,544 describes a creping adhesive that provides the ability to control coating mechanical properties and adhesion, and which can be more easily removed from dryer surfaces. The adhesive system described in said patent provides high adhesion of a fibrous web to dryer surface with low "friction".
Having low friction means that the fibrous web can easily be removed from the dryer surface.
Other references of Interest include U.S. Patents 5,232,553 and 4,684,439. All the prior art patents are of interest but do not disclose polymers having at least one primary or secondary amine group in the backbone such as chitosan, polyvinylamine, polyvinyl alcohol-vinyl amine, polyaminoamide and etc., in
3 combination with the dialdehydes or the zirconium crosslinking compounds having a valence of plus four such as ammonium zirconium carbonate, zirconium aectylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tartrate. These patents also do not relate to creping adhesives or the creping of tissue and towel from a Yankee dryer. U.S. Patents 5,374,334 and 5,382,323 relate to adhesives reacted with the erosslinking agent prior to establishing contact with the dryer surface. In our novel process the crosslinking agents are either charged to the dryer surface at the same time as the adhesive polymer or are mixed shortly prior to charging the polymer and crosslinking agent mixture to the Yankee surface without reacting the crosslinldag agent with the polymer.
SUMIvtAttY OF T»E INVENT,ION
The present invention provides creping adhesives which are friendly to the environment giving off no chlorine compound pollutants, can be applied directly to the dryer, e.g. Yankee from aqueous solution and are substantially less costly than cha presently available creping adhesives. The present invention provides an improved creping adhesive which provides the ability tv readily control glass transition (Tg) and adhesion and which can be more easily removed from dryer surfaces.
An advantageous feature of the present invention is that the adhesion properties of spc 'ctftc types of polymers or copolymers (hereinafter referred to as base polymers) can be systematically changed by varying the amount of crosslinking that may occur when the base polymer is dried onto the surface of a Yankee dryer with the zirconium or dialdehyde crosslinjdng agents. Because crosslink density influences the mechanical properties (i.e., modulus, brittleness, Tg), this permits the adjustment of adhesionlrelease of the fibrous substrate onto the surface of tire dryer. Base polymers having at least one primary or secondary amine groups in the backbone such as chitosan, polyvinylaminc, polyvinyl alcohol-vinyl amine, polyaminoamide and etc., crosslinked with dialdehydes yr zirconium compounds having a valence of plus four produces an adhesive friendly to the environment and which is much less costly than the PAE resin available on the market as discussed in the background section.
The invention also relates to a process for applying such base polymers without pre-
SUMIvtAttY OF T»E INVENT,ION
The present invention provides creping adhesives which are friendly to the environment giving off no chlorine compound pollutants, can be applied directly to the dryer, e.g. Yankee from aqueous solution and are substantially less costly than cha presently available creping adhesives. The present invention provides an improved creping adhesive which provides the ability tv readily control glass transition (Tg) and adhesion and which can be more easily removed from dryer surfaces.
An advantageous feature of the present invention is that the adhesion properties of spc 'ctftc types of polymers or copolymers (hereinafter referred to as base polymers) can be systematically changed by varying the amount of crosslinking that may occur when the base polymer is dried onto the surface of a Yankee dryer with the zirconium or dialdehyde crosslinjdng agents. Because crosslink density influences the mechanical properties (i.e., modulus, brittleness, Tg), this permits the adjustment of adhesionlrelease of the fibrous substrate onto the surface of tire dryer. Base polymers having at least one primary or secondary amine groups in the backbone such as chitosan, polyvinylaminc, polyvinyl alcohol-vinyl amine, polyaminoamide and etc., crosslinked with dialdehydes yr zirconium compounds having a valence of plus four produces an adhesive friendly to the environment and which is much less costly than the PAE resin available on the market as discussed in the background section.
The invention also relates to a process for applying such base polymers without pre-
4 crosslinking to achieve adhesion control on the paper machine through spray application. This invention also relates to creped fibrous webs, creped tissue and creped towel and a process for the manufacturing of these paper products utilizing the novel adhesives of~this invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will now be described in greater detail with reference to preferred embodiments and with the aid of the accompanying drawings which illustrate the application of the invention in a papermaking process employing a Yankee dryer as illustrative of the drying means (although it should be understood that the invention is also applicable to other drying means, e.g. through air dryers) and wherein:
Figure 1 illustrates a paper making process.
Figure 2 illustrates in detail the Yankee dryer employed in the scheme and the position from which the base polymer and the crosslinking agent, and if necessary, the softener can be sprayed on the Yankee or the web, Figure 3 illustrates the effect of glyoxal crosslinking agent on polyvinyl alcohol (PVOI-~ Yankee adhesion, as measured by peel force, for different molecular weight and hydrolysis degrees.
Figure 4 illustrates the effect of glyoxal crosslinking agent on polyvinyl alcohol-vinyl amine copolymer adhesion and blend with unfuactlonalized polyvinyl-alcohol, as measured by peel force with and without softener.
Figure 5 illustrates the GMT ( grams/3 inches ) versus the glyoxal level incorporated into the base polymer such as polyvinyl alcohol-vinyl amine copolymer, and blend with unfunctionalized polyvinyl alcohol, with and without softener.
DETAILED DESCRIPTYON OF THE ltIWENTION
In accordance with the present invention, a method is provided for producing a highly absorbent, eellulosic sheet having a high level of perceived softness that comprises continuously a) preparing an aqueous dispersion of cellulosic papermaking fibers, b) forming a web of said cellulosic papermaking ffbers, c) adhering the web to a dryer surface such as a Yankee dryer with base polymers wherein suitably the base polymer can have both primary and secondary amine groups or a mixture of primary and secondary amine groups. Representative base polymers include polyvinyl alcohol-vinyl amine copolymers, ehiiosan, polyvinylamine and polyammoanmde. The btSe polymers are cmsslmked with metenals such as disldehydes or arconium compounds having s valence of ptus four. The base potymecs having at least one primary or secoadsty arsine group or a mature of primary and secondary amine groups are prepared according io the methods disclosed is the following U.S. Patents:
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will now be described in greater detail with reference to preferred embodiments and with the aid of the accompanying drawings which illustrate the application of the invention in a papermaking process employing a Yankee dryer as illustrative of the drying means (although it should be understood that the invention is also applicable to other drying means, e.g. through air dryers) and wherein:
Figure 1 illustrates a paper making process.
Figure 2 illustrates in detail the Yankee dryer employed in the scheme and the position from which the base polymer and the crosslinking agent, and if necessary, the softener can be sprayed on the Yankee or the web, Figure 3 illustrates the effect of glyoxal crosslinking agent on polyvinyl alcohol (PVOI-~ Yankee adhesion, as measured by peel force, for different molecular weight and hydrolysis degrees.
Figure 4 illustrates the effect of glyoxal crosslinking agent on polyvinyl alcohol-vinyl amine copolymer adhesion and blend with unfuactlonalized polyvinyl-alcohol, as measured by peel force with and without softener.
Figure 5 illustrates the GMT ( grams/3 inches ) versus the glyoxal level incorporated into the base polymer such as polyvinyl alcohol-vinyl amine copolymer, and blend with unfunctionalized polyvinyl alcohol, with and without softener.
DETAILED DESCRIPTYON OF THE ltIWENTION
In accordance with the present invention, a method is provided for producing a highly absorbent, eellulosic sheet having a high level of perceived softness that comprises continuously a) preparing an aqueous dispersion of cellulosic papermaking fibers, b) forming a web of said cellulosic papermaking ffbers, c) adhering the web to a dryer surface such as a Yankee dryer with base polymers wherein suitably the base polymer can have both primary and secondary amine groups or a mixture of primary and secondary amine groups. Representative base polymers include polyvinyl alcohol-vinyl amine copolymers, ehiiosan, polyvinylamine and polyammoanmde. The btSe polymers are cmsslmked with metenals such as disldehydes or arconium compounds having s valence of ptus four. The base potymecs having at least one primary or secoadsty arsine group or a mature of primary and secondary amine groups are prepared according io the methods disclosed is the following U.S. Patents:
5,155,167;
5,194,492; 5,300,566; 4,574,150; 4,~86,08'f; 4,165,433; 3,892,731; 3,879,377;
2,926,154 and 2,926,116 which are hereby inoozpotated by ice into this spplicat>ao. T6e cellulosic sheet was creped from the Yankee dryer by a ctepittg blade thus providiatg a higher of perceived soflaess. Suitable paper produces obtained u~ag the novel adhesives include single and mufti ply tissue and bowel Useful polyaminoamides have the following rating unit structure:
O O
8 n -Rl-rn~ l~, -r>H c->~-c wherein Rt and R2 have two to eight aliphatic carbon amms and R3 has two to six carbon atoms.
The preferred polyvinyl alcohol and polyvinylamine copolymer has the 5ollowing structure:
CH HiC - CH
..
a where m and n have values of about I to 99 and about 99 to 1. A~dvantsgeously tha values of m and n are about 1 to 99 and about 2 to Z0. The polyvicyl alcohol-vinyl amine copolymer can have impurities whirl vorepsise the unlrydmlized starting product The structtue of as impure product is disclosed eh U S. Ps~a 5,300,566 and 5,194,492 and those prt~ txe iaooepaated i~o thit peot applieat~ by the exosslmioog sg~t spra3rod with the polyvinyl ataohol vinyl amine as shower is F'~e I at position S l is a dialde~yde such as glyvxsl et; gl~ualdehyde and epc., or s zirooaium oompouad having s valence of plus ~our such ss ammooima zi;oonium ca~at~e, zirconium scetylaceao~nate, gum acetate, arooaium carberuste, zirconium sulfate, ziroa0ium phosplu~ potassium gum c
5,194,492; 5,300,566; 4,574,150; 4,~86,08'f; 4,165,433; 3,892,731; 3,879,377;
2,926,154 and 2,926,116 which are hereby inoozpotated by ice into this spplicat>ao. T6e cellulosic sheet was creped from the Yankee dryer by a ctepittg blade thus providiatg a higher of perceived soflaess. Suitable paper produces obtained u~ag the novel adhesives include single and mufti ply tissue and bowel Useful polyaminoamides have the following rating unit structure:
O O
8 n -Rl-rn~ l~, -r>H c->~-c wherein Rt and R2 have two to eight aliphatic carbon amms and R3 has two to six carbon atoms.
The preferred polyvinyl alcohol and polyvinylamine copolymer has the 5ollowing structure:
CH HiC - CH
..
a where m and n have values of about I to 99 and about 99 to 1. A~dvantsgeously tha values of m and n are about 1 to 99 and about 2 to Z0. The polyvicyl alcohol-vinyl amine copolymer can have impurities whirl vorepsise the unlrydmlized starting product The structtue of as impure product is disclosed eh U S. Ps~a 5,300,566 and 5,194,492 and those prt~ txe iaooepaated i~o thit peot applieat~ by the exosslmioog sg~t spra3rod with the polyvinyl ataohol vinyl amine as shower is F'~e I at position S l is a dialde~yde such as glyvxsl et; gl~ualdehyde and epc., or s zirooaium oompouad having s valence of plus ~our such ss ammooima zi;oonium ca~at~e, zirconium scetylaceao~nate, gum acetate, arooaium carberuste, zirconium sulfate, ziroa0ium phosplu~ potassium gum c
6 zirconium sodium phosphate and sodium zirconium tartrate. The zirconium crosslinking agents and polyvinyl alcohol-vinyl amine base polymer are sprayed separately at the same time on the Yankee surface. The dialdehydes are mixed with the base polymer just prior to spraying so that the dialdehyde and base polymer have no practical chance to react prior to reaching the heated Yankee surface. The crosslinlang agent and base polymer are reacted directly on the Yankee surface.
Spraying the adhesive on the Yankee is the best mode of application of the adhesives.
Suitable dialdehydes are glyoxal, malonic, succinic, and glutarie dialdehyde_ Suitably these aldehydes can be represented by the following structural formula:
O O
H-C-(CHI-C-H
wherein n is an integer having a value of 0 to 3. The preferred aldehydes are glyoxal and giutaraldehyde. In some applications for the manufacture of tissue and towel, suitable softeners are utilized. The softeners are sprayed on the web as shown in Figure 2 from position 52 or 53.
The novel adhesives are environmentally friendly and are very capable of ready application to the Yankee surface from aqueous solution. Additionally the adhesives arc substantially less expcasive than present PAE resin products.
For the sake of simplicity, the invention wtll be described immediately herein below in the context of a conventional dry crepe wet-forming process. A
schematic drawing depicting a process ooafiguration is set forth in Figure 1.
The paper products, such as tissue and towel, of the present invention may be manufactured on any papermaking machine of conventional forming configurations such as fourdrinier, twin-wire, suction pressure roll or crescent forming configurations. The forming mode is advantageously water or foam. Figure I illustrates an embodiment of the present invention wherein a machine chest SO is used for preparing furnishes that may mutually be treated with chemicals having different functionality depending on the character of the various fibers, particularly fiber length and coarseness. The furnishes are transported through conduits 40 and 41 where the furnishes are delivered to the hcadbox of a crescent forming machine 10.
This Figure 1 includes a web-forming end or wet end with a liquid permeable foraminous
Spraying the adhesive on the Yankee is the best mode of application of the adhesives.
Suitable dialdehydes are glyoxal, malonic, succinic, and glutarie dialdehyde_ Suitably these aldehydes can be represented by the following structural formula:
O O
H-C-(CHI-C-H
wherein n is an integer having a value of 0 to 3. The preferred aldehydes are glyoxal and giutaraldehyde. In some applications for the manufacture of tissue and towel, suitable softeners are utilized. The softeners are sprayed on the web as shown in Figure 2 from position 52 or 53.
The novel adhesives are environmentally friendly and are very capable of ready application to the Yankee surface from aqueous solution. Additionally the adhesives arc substantially less expcasive than present PAE resin products.
For the sake of simplicity, the invention wtll be described immediately herein below in the context of a conventional dry crepe wet-forming process. A
schematic drawing depicting a process ooafiguration is set forth in Figure 1.
The paper products, such as tissue and towel, of the present invention may be manufactured on any papermaking machine of conventional forming configurations such as fourdrinier, twin-wire, suction pressure roll or crescent forming configurations. The forming mode is advantageously water or foam. Figure I illustrates an embodiment of the present invention wherein a machine chest SO is used for preparing furnishes that may mutually be treated with chemicals having different functionality depending on the character of the various fibers, particularly fiber length and coarseness. The furnishes are transported through conduits 40 and 41 where the furnishes are delivered to the hcadbox of a crescent forming machine 10.
This Figure 1 includes a web-forming end or wet end with a liquid permeable foraminous
7 support member 1 1 which rnay be of nay comrentional cec~fi~or~. Foraa~iao~
~pport member 11 may be canstruaed of any of several known materials including photo polyrrrer fabric, felt, fabric ~ a synthetic filament woven mesh base with a very fore synthetic fiber bait attached tn the mesh base. 'fire foraminous support member 11 is supported in a conventional manner ca mlls, including press roll 1 S acrd couch roll or pressing roll 16.
Form~g fabric 12 is supported on rolls 18 and 19 which ~re positioned relative to the press roll 15 for pressing the press wire 12 to aonvergs on the forarainous support member 11 at the cylindrical press roll 1 S at an awte eagle relative to the foraminous support member I I. The foram>nous support member 11 and the wire 12 move in the same direaron and at the same speed which is the same dir~on of r~otatiaa of the pressure roll 15. 1~e pressing wire iZ and the foramirtous support member 11 oomrerge at an upper surface of the forrrung roll I 5 to form a wedge-shaped space or nip into which two jets of water or foamed-liquid fiber dispersion is pressed between the prcs~ng wire 12 and the forarnirroas support member 11 to force fluid through the wire 12 into a saveaD 22 where it is collected for reuse in the process.
A wet nascent web W formed in the process is carried by the foraminous support member 11 to the pressing roll 16 where the wet nascent web W is transferred to the drum 26 of a Yankee dryer. Fluid is.pressed from the wet web W by pressing roll 16 as the web is transferred to the drum 26 of the Yurkee dryer where it is dried and creped by meatLS of a creping blade 27. The 5nished web is collected on a takaup roll 28.
A pit 44 is provided for collecting water squeezed from the nascent web W by the press roll 16 and the Uhle box 29. The woes collected in the pit 4.4 may be collected into a flow lure 45 for separate processing to remove susfa~t and fibers liom the water acrd to permit g of the water back to the p>pmmalang medtine 10. The liquid, suitably foamed liquid, is collected from the furnish irt the saveall 22 arid is retsurted through line 24 to a recycle process generally indicated by box S0.
Dewatering of the wet web is provided prig so the thermal drying operation, typically by anploying a ttoathentral dewasering trteaas. The ao~nthcraul dewawing step is usually accomplished by various mesas for atcpardng meclrsnical oompartiar to the web, such as . _ vacuum boxes, sbc boxes, ooscting press rolls, er eombi~an~s theneo~ For purposes of illustration of the method of this imentiorr, the wet web may be devvatered by subjecting same
~pport member 11 may be canstruaed of any of several known materials including photo polyrrrer fabric, felt, fabric ~ a synthetic filament woven mesh base with a very fore synthetic fiber bait attached tn the mesh base. 'fire foraminous support member 11 is supported in a conventional manner ca mlls, including press roll 1 S acrd couch roll or pressing roll 16.
Form~g fabric 12 is supported on rolls 18 and 19 which ~re positioned relative to the press roll 15 for pressing the press wire 12 to aonvergs on the forarainous support member 11 at the cylindrical press roll 1 S at an awte eagle relative to the foraminous support member I I. The foram>nous support member 11 and the wire 12 move in the same direaron and at the same speed which is the same dir~on of r~otatiaa of the pressure roll 15. 1~e pressing wire iZ and the foramirtous support member 11 oomrerge at an upper surface of the forrrung roll I 5 to form a wedge-shaped space or nip into which two jets of water or foamed-liquid fiber dispersion is pressed between the prcs~ng wire 12 and the forarnirroas support member 11 to force fluid through the wire 12 into a saveaD 22 where it is collected for reuse in the process.
A wet nascent web W formed in the process is carried by the foraminous support member 11 to the pressing roll 16 where the wet nascent web W is transferred to the drum 26 of a Yankee dryer. Fluid is.pressed from the wet web W by pressing roll 16 as the web is transferred to the drum 26 of the Yurkee dryer where it is dried and creped by meatLS of a creping blade 27. The 5nished web is collected on a takaup roll 28.
A pit 44 is provided for collecting water squeezed from the nascent web W by the press roll 16 and the Uhle box 29. The woes collected in the pit 4.4 may be collected into a flow lure 45 for separate processing to remove susfa~t and fibers liom the water acrd to permit g of the water back to the p>pmmalang medtine 10. The liquid, suitably foamed liquid, is collected from the furnish irt the saveall 22 arid is retsurted through line 24 to a recycle process generally indicated by box S0.
Dewatering of the wet web is provided prig so the thermal drying operation, typically by anploying a ttoathentral dewasering trteaas. The ao~nthcraul dewawing step is usually accomplished by various mesas for atcpardng meclrsnical oompartiar to the web, such as . _ vacuum boxes, sbc boxes, ooscting press rolls, er eombi~an~s theneo~ For purposes of illustration of the method of this imentiorr, the wet web may be devvatered by subjecting same
8 ' , ' ~ ' , ' ' , ° l , , = a t0 8 series of vacuum boxes atidlor slot beater. Thereafter, the web may be dewatered by sublec4ng same to the compressive 5otces exerted by nonthermal dewasering means such as, for example, uti>i~tg roll 15, followed by a pressure roll 16 ooacting wide a thermal drying means. The wet web is carried by the foramiaous conveying mesas 11. 12 thmu~
~e nonthamal dewate<ing menus, acct ~s dewatered to a fiber consistency of at lest about 5% up to about 54%, preferably at least 1 S~e up to about 45%, and mono preferably to a 5ber consistency of apProoonna~ely 40'%. ' The dewaterod web is applied to the surface of thermal drying means, preferably a th~nnal drying cylinder such as a Yankee drying cTrliader 26, employing the 'de or arcanium crosslinldng agent having a valence of plus four with the polyvinyl slcohol-vinyl amine copolymer. Under the definiti~ of "Yankee" is inducted all large cast-iron drying cylinders some of which may be ceramic coated on which towel, tissue, wadding, and machine-glazed papers are among ~e grades produced. Diameters typically range from 10.20 feet sad widths can approach 300 inches. A typical diaauta for s Yankee drying dnun is I2 feet.
Speeds in excess of 6000 ftJmin. at greater than 380,000 pounds are net uncotnmori. ' Dryers typically inooaporate a neater shaft and ere supported eh journals by two large anafrictio~n brings. Steam, up to 160 psig (Code ion for cast iron unfired pressure vessels) is supplied the front-side journal sad exhausted, along with condertsate, through the back-side journal. A typical steam pressure is 125 prig. Prasun rolls 16, one, or two usually baled between 200 and 500 pounds/lineu ir~cl~ are employed to press the sheet unifom~ly against the shell face. The sheet is rcmov~ed from the dryer several quadrants away, having been impaled ~witi~ properties characteristic of the desired paper product.
Aof the devvaterrd web to the cylinder surtax is facilitated by the mechanical compressive action exerted thereon, generally using ore or more press rolls 16 that form a nip is combination with drying means 26. This brims the web into morn uniform contact with the thermal dtyin6g surface.
Since w~e pr~a to use high adhesion creping, ac qu~ti~r the degree of ad6esiorr, we define adhaiott as the ~ocoe iet grams required to peal a 12 inch wide sheet a~ the aping cylinder at a 90 degree angle with the cteping blade in tht o$ load position.
We have found ' that using the crcping sdlsaive of this invaition, it is possible to control adhesion such thu the junction between the sheet and Yankee (26) exhibits rda~tivelyr high adhesion catnpared to
~e nonthamal dewate<ing menus, acct ~s dewatered to a fiber consistency of at lest about 5% up to about 54%, preferably at least 1 S~e up to about 45%, and mono preferably to a 5ber consistency of apProoonna~ely 40'%. ' The dewaterod web is applied to the surface of thermal drying means, preferably a th~nnal drying cylinder such as a Yankee drying cTrliader 26, employing the 'de or arcanium crosslinldng agent having a valence of plus four with the polyvinyl slcohol-vinyl amine copolymer. Under the definiti~ of "Yankee" is inducted all large cast-iron drying cylinders some of which may be ceramic coated on which towel, tissue, wadding, and machine-glazed papers are among ~e grades produced. Diameters typically range from 10.20 feet sad widths can approach 300 inches. A typical diaauta for s Yankee drying dnun is I2 feet.
Speeds in excess of 6000 ftJmin. at greater than 380,000 pounds are net uncotnmori. ' Dryers typically inooaporate a neater shaft and ere supported eh journals by two large anafrictio~n brings. Steam, up to 160 psig (Code ion for cast iron unfired pressure vessels) is supplied the front-side journal sad exhausted, along with condertsate, through the back-side journal. A typical steam pressure is 125 prig. Prasun rolls 16, one, or two usually baled between 200 and 500 pounds/lineu ir~cl~ are employed to press the sheet unifom~ly against the shell face. The sheet is rcmov~ed from the dryer several quadrants away, having been impaled ~witi~ properties characteristic of the desired paper product.
Aof the devvaterrd web to the cylinder surtax is facilitated by the mechanical compressive action exerted thereon, generally using ore or more press rolls 16 that form a nip is combination with drying means 26. This brims the web into morn uniform contact with the thermal dtyin6g surface.
Since w~e pr~a to use high adhesion creping, ac qu~ti~r the degree of ad6esiorr, we define adhaiott as the ~ocoe iet grams required to peal a 12 inch wide sheet a~ the aping cylinder at a 90 degree angle with the cteping blade in tht o$ load position.
We have found ' that using the crcping sdlsaive of this invaition, it is possible to control adhesion such thu the junction between the sheet and Yankee (26) exhibits rda~tivelyr high adhesion catnpared to
9 coaveatior~al ad~sives which include PAE resins. I~gb adhesion Ievel is preserved when our crosslinkable adhesive forms are used as the creping process aids in the presence of softener and debonder Specifically, when softener is used is the range of one (1) to about ten a
(10) pounds per t~, adhesion is good as defined by the peel force of about 300 tn about 900 grams per 12 inches, whey using a papermaldag machine having a speed of less than one hundred fifty feet per minute (150 Rlminute): Generally, when softener is added, adhesion is decreased Unlike ctional a~v~ of the PAE type and the like, utilization of our crosslinkable adhesive formulation in eonjvmct~ with softener, allows one to minimize the difference between air and Yankoe side friction of the crepcd product while preserving overall low friction, all of wbi~ promote high quality crepe strvchzre required for good tissue and towel sothuss.
Alternatively adhesion cad be asditectly measured as sheaf tension with the cxeping blade is an load positloa. Sheet teosioa should be in the 'range of 600 -1,500 grams per 12 inches. the sheet tension is mea~ued by the transducer idler roll positioned prior to take-up roll 28. If paper machine speed, basis weight, furnish g and other operadooal parameters are kept oonstsar, then sheet tension is a function of adhesion only.
Flute 2 ills the drying and crepiag of the cellulosic web to pry tissue and towel According to our process, both one pry and multiply towel and tissue are produced According to the press of the ion,1he novel adhesives each comprising base polymer and aaeslinmtg agent are ~tsyed directly on the Yankee (26) at position 51. Id the event it is desired to use soft~s, these are sprayed ca the air side of the web from position 52 or 53 as shown in Figure 2. WI>m using the rireooium aossliniaag agent then both the base polymer and the cxosslinh$ agent are sprayed separate~t but almost simultaneously on the heated Yankee surJ~.
The various oomponeatS of the adhesive farmula>ion, may aIi be dissolved, dispersed"
suspended, or emulsi5ed in a liquid carrying 9uid. It should be noted that the crossliaiang agents in our process are either spray~ad directly on the Yankee surfs with the base po>,ymer or is case of the dials are mixed with the base poIlrmer just prior to spraying. This liquid wtll generany be a non-tordc solvent such as water. The liquid ooaopone~ is usually presort is as amount of 90 to 99'i6 by weight of the total wdght of the cceping adhesive. The pH of the adhesive when it is applied to the desired sw~ace iu the papezmaldng operaxiott will normally bo about 7.5 to 11. The solvent preferably coansists essentially or completely of water.
If other types of solvents are added, they are generally added in small amouats.
Referring to the drawing in Figure 2, this represents ~e of a number of possible configurations used in processing tissue and towel products. In this particular arrangement, the trerisfer and impression fabric carries the formed, dewatered web W around fuming roll I S to the nip between press roll 16 and Yankee dryer 26. The fabric, web and dryer move in the directions indicated by the arrovus. Tfie entry of the web to the dryer is well around the roll from creping blade 27 which, as scheuia>xca>)y indicated, crepes the traveling web from the dryer as indicated at 27. The creped web W exiting fmm the dryer is wound into a soft creped tissue, or towel at roll Z8. To adhere the nascent web W to the surface of the dryer, a spray 51 of adhesive is applied tn the surface ahead of the nip between the press roll 16 and Yankee 26.
Alternately, the spray may be apphod to the traveling web W directly as shown at 53. Suitable apparatus for use with the present inveation are disclosed in U.S. Pateats 4,304,625 and 4,064,213; which are hereby incorporated by reference.
This illustration does not incorporate all the possible configurat;ons used in presenting a nascent web to a Yankee dryer. It is used only to describe how the adhesives of the preset invention can be used to promote adhesion and thereby influence the crepe of the product. The present invention caa be used with all other known procxsses that rely upon creping the web from a dryer surface. 1n the same manner, the method of application of the adhesive to the surface of the dryer or the web is not restricted to spray applications, althouEti these are general>y the simplest nnethod for adhesive application.
The preseat invention is useful For the preparation of fibrous webs which are cmped to increase the thickness and bulk of the web and tn pmvide texture to the web.
The invention is particularly useful in the preparation of final products such as facial tissue, toilet tissue, paper towels, and the Ii7ce. the fibrous web can be farmed fi~ara various types of wood pulp based fibers which are used to make the above produar such as hardwood kraft fibers, softwood la~aft~ fliers, hardwood sulfite 5bets, softwood sulfite fibers, high yield fibers such as chemo-thermo.meGhsaical pulps (CTS, therrmomech&iical pulps (Tl~) or re&riar mechsaical pulps (Rl~. Funiishes used may also oontaia or be totally comprised of rxycled fibers (i.e_, s~aidary fibers). The fibrous web, prior to application to the Yankee dryer, usually has a water catiteat of 40 to 80 wt. °/., more preferably 50 to 70 wt.
°i6. At the creping stage, the
Alternatively adhesion cad be asditectly measured as sheaf tension with the cxeping blade is an load positloa. Sheet teosioa should be in the 'range of 600 -1,500 grams per 12 inches. the sheet tension is mea~ued by the transducer idler roll positioned prior to take-up roll 28. If paper machine speed, basis weight, furnish g and other operadooal parameters are kept oonstsar, then sheet tension is a function of adhesion only.
Flute 2 ills the drying and crepiag of the cellulosic web to pry tissue and towel According to our process, both one pry and multiply towel and tissue are produced According to the press of the ion,1he novel adhesives each comprising base polymer and aaeslinmtg agent are ~tsyed directly on the Yankee (26) at position 51. Id the event it is desired to use soft~s, these are sprayed ca the air side of the web from position 52 or 53 as shown in Figure 2. WI>m using the rireooium aossliniaag agent then both the base polymer and the cxosslinh$ agent are sprayed separate~t but almost simultaneously on the heated Yankee surJ~.
The various oomponeatS of the adhesive farmula>ion, may aIi be dissolved, dispersed"
suspended, or emulsi5ed in a liquid carrying 9uid. It should be noted that the crossliaiang agents in our process are either spray~ad directly on the Yankee surfs with the base po>,ymer or is case of the dials are mixed with the base poIlrmer just prior to spraying. This liquid wtll generany be a non-tordc solvent such as water. The liquid ooaopone~ is usually presort is as amount of 90 to 99'i6 by weight of the total wdght of the cceping adhesive. The pH of the adhesive when it is applied to the desired sw~ace iu the papezmaldng operaxiott will normally bo about 7.5 to 11. The solvent preferably coansists essentially or completely of water.
If other types of solvents are added, they are generally added in small amouats.
Referring to the drawing in Figure 2, this represents ~e of a number of possible configurations used in processing tissue and towel products. In this particular arrangement, the trerisfer and impression fabric carries the formed, dewatered web W around fuming roll I S to the nip between press roll 16 and Yankee dryer 26. The fabric, web and dryer move in the directions indicated by the arrovus. Tfie entry of the web to the dryer is well around the roll from creping blade 27 which, as scheuia>xca>)y indicated, crepes the traveling web from the dryer as indicated at 27. The creped web W exiting fmm the dryer is wound into a soft creped tissue, or towel at roll Z8. To adhere the nascent web W to the surface of the dryer, a spray 51 of adhesive is applied tn the surface ahead of the nip between the press roll 16 and Yankee 26.
Alternately, the spray may be apphod to the traveling web W directly as shown at 53. Suitable apparatus for use with the present inveation are disclosed in U.S. Pateats 4,304,625 and 4,064,213; which are hereby incorporated by reference.
This illustration does not incorporate all the possible configurat;ons used in presenting a nascent web to a Yankee dryer. It is used only to describe how the adhesives of the preset invention can be used to promote adhesion and thereby influence the crepe of the product. The present invention caa be used with all other known procxsses that rely upon creping the web from a dryer surface. 1n the same manner, the method of application of the adhesive to the surface of the dryer or the web is not restricted to spray applications, althouEti these are general>y the simplest nnethod for adhesive application.
The preseat invention is useful For the preparation of fibrous webs which are cmped to increase the thickness and bulk of the web and tn pmvide texture to the web.
The invention is particularly useful in the preparation of final products such as facial tissue, toilet tissue, paper towels, and the Ii7ce. the fibrous web can be farmed fi~ara various types of wood pulp based fibers which are used to make the above produar such as hardwood kraft fibers, softwood la~aft~ fliers, hardwood sulfite 5bets, softwood sulfite fibers, high yield fibers such as chemo-thermo.meGhsaical pulps (CTS, therrmomech&iical pulps (Tl~) or re&riar mechsaical pulps (Rl~. Funiishes used may also oontaia or be totally comprised of rxycled fibers (i.e_, s~aidary fibers). The fibrous web, prior to application to the Yankee dryer, usually has a water catiteat of 40 to 80 wt. °/., more preferably 50 to 70 wt.
°i6. At the creping stage, the
11 fibrous web usually has a water coatent of less than 7 wt. °k, preferably less than 5 wt. %.
The final product, after creping and drying, has a basis weight of 7 to 30 pounds per ream.
The non-self crosslinkable base polymer of the present invention called the base polymer, has at least one primary or secondary amine groups in the backbone such as chitosaa, polyvinylamine, polyvinyl alcohol-vinyl amine, polyaminoamide and ere., or combinations thereof and the crosslinkinE agents are dialdehyde or zirconium compounds having a valence of plus four. Suitable dialdehydes include glyoxal, malonic dialdehyde, succinic dialdehyde and glucaraidehyde. Suitable zirconium crosslinking agents include ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zircoaium tartratc.
The non-self crosslinkable base polymer should be present in the creping adhesive in an amount sufficient to provide the desired results in the creping operation. If it is intended w spray the creping adhesive onto the surface of the Yankee dryer, the creping adhesive should have a viscosiry low enough to be easily sprayed yet high enough to provide a sufficient amount of adhesion. When the creping adhesive is sprayed onto the surface of the Yankee dryer, it should have a total solids content of about 0.01 to 0.5, preferably 0.03 to 0.2% by weight based on the total weight of the fiber. The solids content is constituted primarily by the base polymer and the dialdehyde or zirconium crosslinlang agent. The zirconium erosslinking agent having a valence of plus four is sprayed separately on the Yankee surface and only comes in contact with the bast polymer on the heated Yankee surface, whereby the combined action of drying and heating effect crosslinklng required for adhesion.
The crosslinking agent should be present on the Yankee surface in the creping adhesive formulation in an amount sufficient to provide changes is the mechanical properties of the base polymer once the solution has been evaporated and the polymer crosslinked. As the level of crosslinldng increases, the mechanical properties change with the crosslink density. Increased crosslinking generally will increase the Tg, increase the brittleness, hardness, and provide different responses to mechanical stresses than unerosslinked polymers.
Obtaining the appropriate crossliak density will depend not only on the relative concentration of added crosslinking agent but also on the molecular weight of the polymer. In geaeral, as the molecular weight of the starting polymer increases, the amount of
The final product, after creping and drying, has a basis weight of 7 to 30 pounds per ream.
The non-self crosslinkable base polymer of the present invention called the base polymer, has at least one primary or secondary amine groups in the backbone such as chitosaa, polyvinylamine, polyvinyl alcohol-vinyl amine, polyaminoamide and ere., or combinations thereof and the crosslinkinE agents are dialdehyde or zirconium compounds having a valence of plus four. Suitable dialdehydes include glyoxal, malonic dialdehyde, succinic dialdehyde and glucaraidehyde. Suitable zirconium crosslinking agents include ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zircoaium tartratc.
The non-self crosslinkable base polymer should be present in the creping adhesive in an amount sufficient to provide the desired results in the creping operation. If it is intended w spray the creping adhesive onto the surface of the Yankee dryer, the creping adhesive should have a viscosiry low enough to be easily sprayed yet high enough to provide a sufficient amount of adhesion. When the creping adhesive is sprayed onto the surface of the Yankee dryer, it should have a total solids content of about 0.01 to 0.5, preferably 0.03 to 0.2% by weight based on the total weight of the fiber. The solids content is constituted primarily by the base polymer and the dialdehyde or zirconium crosslinlang agent. The zirconium erosslinking agent having a valence of plus four is sprayed separately on the Yankee surface and only comes in contact with the bast polymer on the heated Yankee surface, whereby the combined action of drying and heating effect crosslinklng required for adhesion.
The crosslinking agent should be present on the Yankee surface in the creping adhesive formulation in an amount sufficient to provide changes is the mechanical properties of the base polymer once the solution has been evaporated and the polymer crosslinked. As the level of crosslinldng increases, the mechanical properties change with the crosslink density. Increased crosslinking generally will increase the Tg, increase the brittleness, hardness, and provide different responses to mechanical stresses than unerosslinked polymers.
Obtaining the appropriate crossliak density will depend not only on the relative concentration of added crosslinking agent but also on the molecular weight of the polymer. In geaeral, as the molecular weight of the starting polymer increases, the amount of
12 crosslidang agent necessary to provide particular levels of seal properwes ('Lo., Tg, britdeness, era) decreases. A discussion concerning the relationship between T'g and crosslinkiag of polymers is contained is the article by Stutz et a1, ~oumaI of Pg~l rmer Science. 28, 1483-1498 (1990), the entire contemn of which is hereby incorporated by reference.
In our process the ratio of the base polymer to the crosslinlang agent can be varied widely. the function of the crosslinkoog agedt is to control adhesion. 'Ihe weight ratio of the crosslinl~g agent to base poiynter may go up to 4:1. The preferred ratio is about 0.05:1 to about 2:1 _ The base polymer can be a homopolymer or a copolymer. It should be noted that in our process all the crossliddng was activated on the heated Yankee surface.
While the base polymer and crosslmlong agent are the major "active"
ingredients of the present invention, other materials can be insorpor~ted with beneficial results. Materials rail be added to modify the meciutaical properties of the crossliaked base polymers.
Some of these materials may actually be inoocporated into the crosslinked.potymer. Examples would include glycols (ethylene glycol ProPYI~ 815' ~). PdY~yl~ glY~~. and othcr polyols (simple sugars and oligosaxharides). Other compau~ts can be added to modify interfacial phenomena such as surface >msia~n ~ wetting of the adhesive solution. Nonionic surfactants such as the o~yl phawxy based Triton (Rohm & Leas, Inc.) surfactants or the Pluroaic or Tetronic (BASF Corp.) snots can be incorporated is the presort invention to improve surface spreading or wetting capabilities. ll~neral ods o~r other low molecular weight .
hydrocarbon oils or waxes can be included to modify interfacial phenomena and thereby corrtrvl adhesion.
The non-self-crvssliniang base polymer, polymer modifiers, surfactants, and anti-corrosion additives, will all be dissdved, dispersed, suspended, or emulsified in a liquid carryiJng fluid this liquid win usually be a rwn-toxic solvent such as water.
Irt our novel process the zirconium c~sslinfong aged such as amrnouium zdroomium carb~ste, zirconium acetylaatonate, gum moett~, uroonium mrbo~ame, zirconium sulfate, arc~ium phosphate, potassium iarconium carbonate, an~nium sodium phosphate and sodium zitoonium crosslinlang ageatr were sprayed dita~y on the Yankee or alternately the dialdehyde was added to the adhesive ~oormularion just prior to spry on the Yankee surFaco to avoid reaction with the brio po~lyma and the uosslin>ang agent prior to reaching the heated Yankee surface.
In our process the ratio of the base polymer to the crosslinlang agent can be varied widely. the function of the crosslinkoog agedt is to control adhesion. 'Ihe weight ratio of the crosslinl~g agent to base poiynter may go up to 4:1. The preferred ratio is about 0.05:1 to about 2:1 _ The base polymer can be a homopolymer or a copolymer. It should be noted that in our process all the crossliddng was activated on the heated Yankee surface.
While the base polymer and crosslmlong agent are the major "active"
ingredients of the present invention, other materials can be insorpor~ted with beneficial results. Materials rail be added to modify the meciutaical properties of the crossliaked base polymers.
Some of these materials may actually be inoocporated into the crosslinked.potymer. Examples would include glycols (ethylene glycol ProPYI~ 815' ~). PdY~yl~ glY~~. and othcr polyols (simple sugars and oligosaxharides). Other compau~ts can be added to modify interfacial phenomena such as surface >msia~n ~ wetting of the adhesive solution. Nonionic surfactants such as the o~yl phawxy based Triton (Rohm & Leas, Inc.) surfactants or the Pluroaic or Tetronic (BASF Corp.) snots can be incorporated is the presort invention to improve surface spreading or wetting capabilities. ll~neral ods o~r other low molecular weight .
hydrocarbon oils or waxes can be included to modify interfacial phenomena and thereby corrtrvl adhesion.
The non-self-crvssliniang base polymer, polymer modifiers, surfactants, and anti-corrosion additives, will all be dissdved, dispersed, suspended, or emulsified in a liquid carryiJng fluid this liquid win usually be a rwn-toxic solvent such as water.
Irt our novel process the zirconium c~sslinfong aged such as amrnouium zdroomium carb~ste, zirconium acetylaatonate, gum moett~, uroonium mrbo~ame, zirconium sulfate, arc~ium phosphate, potassium iarconium carbonate, an~nium sodium phosphate and sodium zitoonium crosslinlang ageatr were sprayed dita~y on the Yankee or alternately the dialdehyde was added to the adhesive ~oormularion just prior to spry on the Yankee surFaco to avoid reaction with the brio po~lyma and the uosslin>ang agent prior to reaching the heated Yankee surface.
13 Ntrogenous softeners/deboa~ders can suitably be added in the paper man process. The softener may suitably be added with the fiumsh, but is preferably sprayed from position 53 as shown:in Figure 2, or also sprayed to the sheet while the sheet is on the Yankee as shown in Figure 2 position SZ.
Representative softeners have the following structure:
[ (RCO) FDA] HX
wherein EDA is a diethylaretriamine residue, R is the residue of a Witty sad having $om I2 to 22 cadron atoms, and X is an anion or [ (RCONHCFIzCH~ zNR' ] F1X
wherein R is the residue of a fatty acid having firm 12 to Z2 carbon atoms, R' is a lower alkyl group, and X is an anion.
the preferred softener is QuasoR~ 202-JR and 209-JR made by Quaker Chemical Corporation which is a mixtinro of linear amiss amides and imidazalines of the following structure:
(i) O H H Xe H O
p1 1 I a Cs~~-C-N-CHrCHrN° -CHZ-Ct~-N-C CCnH~3 R' and (ii) . O H
~ I x. / I
CI~I~s-C N-CHI-CIA-1Va N
\ //
R' C
CmHa~
wherein X is an asioa As the nitrogenous cationic so~ner/dsbondcr reacts with a paper product duri~
~ornoa~iaa~, the soibmer/debonder either ionicat~r to cellulose sad reduces the nu~mbec of sties avm'Iahle Sor l~rdrog~ bondimig thereby ~areasmg the eat of 56e~ to-fiber bonding
Representative softeners have the following structure:
[ (RCO) FDA] HX
wherein EDA is a diethylaretriamine residue, R is the residue of a Witty sad having $om I2 to 22 cadron atoms, and X is an anion or [ (RCONHCFIzCH~ zNR' ] F1X
wherein R is the residue of a fatty acid having firm 12 to Z2 carbon atoms, R' is a lower alkyl group, and X is an anion.
the preferred softener is QuasoR~ 202-JR and 209-JR made by Quaker Chemical Corporation which is a mixtinro of linear amiss amides and imidazalines of the following structure:
(i) O H H Xe H O
p1 1 I a Cs~~-C-N-CHrCHrN° -CHZ-Ct~-N-C CCnH~3 R' and (ii) . O H
~ I x. / I
CI~I~s-C N-CHI-CIA-1Va N
\ //
R' C
CmHa~
wherein X is an asioa As the nitrogenous cationic so~ner/dsbondcr reacts with a paper product duri~
~ornoa~iaa~, the soibmer/debonder either ionicat~r to cellulose sad reduces the nu~mbec of sties avm'Iahle Sor l~rdrog~ bondimig thereby ~areasmg the eat of 56e~ to-fiber bonding
14 or covaleatly attaches to the aosslink~g agesst to produce improved softness due to enhanced subs~tivity of sod to fiber.
'Ihc presort itrveation may be used with a particular class of softener materials -. .
amide amine salts derived from partally acid neutralized amines. Such materials are disclosed in U.S. Patent No. 4,720,383; column 3, lines d4-41. Also relevant ue the following artides:
Evens, ~~! and Indusw. 5 July 1969, pp. 893-903; Egs:<, J Am O~1 Chemist's Soc., VoL 55 (1978), pp. 118-121; and ?rivedi et aL, ~~17 ~emist's Soy, June 1981, pp.
754.756. All of the above sre inoorporatvd herein by rrferenc~ As indicated therein, softeners are oiler available oommacially only as complex mixtures rather than as single compounds.
While this discussion will focus on the predonnit~nt species, it should be understood that commercially available mixtures would gen~aally be used to practice the inventior~
At this time, Q202-JR and 209~JR is a preferred soRer~er material which is derived by alkylatinE a coardertsation product of oleic acid and diethylenetriamine. Synthesis conditions using a defiaency of ally agent (e.g., diethyl sulfate) and only one atlcylating step, followed by pH adjuttmart to probotrate the tern-~rlated species, result in a mixture consisting of cationic ethylated arrd cationic nen-etitylated species. A minor proportion (e.g., about I O %) of the resulting amide amines ~yclize no itnidazoliae compounds.
Since these materials era cwt quaternary ammonium ootnpousd~ they are pH~sitive.
?herefore, in the practice of the present inva~tiotr wilt this class of chemicals, the pH in the headbox should be aPP~~Y 6 m 8, mere preferably o to '7 and most preferably 6.5 to 7.
The softener employed for treatment of the fwnish is provided at a treatment level that is sufficient to impart a percepd'bb degroe of saws ~ the paper product but Iess thaw an amount that would cause significant runnabiliry and sheet strength problems in the final commercial groduct Zhe amount of softener ettrployed, oa a 100 °!.
acxive basis, is preferably from about 0.1 pounds per ton of fiber in the furnish up to about 10 pounds per tea of fiber in the fumisb, dta more prefaced amount is from 2 to about 5 pounds per tnn of fiber in the furnish.
Figut~es 3 tiuough s d~ravstrste drat dialdd>yd~ are aosslinldug agenss when oortrbined with a base polymer such as polyvinyl atcohel and polyvinyl alcohol vinyl ..
amine copo)ymer, and blend thereof .
Figures 4 sad 5 illustrate that dialdehyde crosslinldng increases adhesion is the presence of softener, as evidenced by higher adhesion values as measured by peel force and lower geometric meap~ tensile (C~T~ parameters.
Fsthetics and tactile cansideratioas are extremely important for tissue produces as they often come into intimate c~atect with the most delicate parts of the bob is use. Consequently, demand is quite high for products wrth improved tactile qualities, particularly sof~ss.
However, as tissue products are &equeatly used to wroid contact with that which the consumer would greatly prefer not to touch, sofas alone is not sufficie~ stra~gth is also required.
Merely providing a product with improved properties is not generally su~cieat, tile "on the shelf' appearance of the product must suggest both streagtlz and roflness where cottsuraess must be able to sense iug~by handling packaged product Appearance is critical;
bulk, weight, compressibility, tinruless, te~cture and ether qualities perceived as indicis of strength and softness are also requirod TAPPI 401 OM 88 (Revised 1988) provides a procedure for the identification of the types of f bets present in a sample o~f paper or paperboard and es>;matioa of their quality.
Analysis of the amount of the sofbmer/debonder chemicals retained ca the tissue paper can be performed by any method accepted is the applicable art For the most sertsitive~cases, we prefer to x-ray photoelectron sptopy ESCA to measure nitrogen levels. Normauy, the backg~d level is quire high and the variation between measut emeats quite high, so use of several replicates is a relatively modern ESCA system such as the Perlda Elmer Corporation's model 5600 is requirod m obtain more precise measuremetrts. the level of cati~ic nitrogenous sofleaer/debonder such as Quasofl~ 202-JR can alternatively be determined by solvent eon of the Quasoft~ Z02-JR by as organic solvont followed by liquid chromatography detertreioation of the softane</debonder.
Tensile stca>gtit of tissue produced in accordance with the present invention is measured in the machine direction sad cTOSS-machine direction on as Instroa tense testxc with the gauge largth set to 4 incites- the: ma of tissue tied is assumed to be 3 iad~s wide by 4 inches laag. A 20 pound load cell with heavywaght grips applied to the total width of the sample is employed ?he msaimutn load is recorded for each direction. 1be results are r~ortad in units of "~ p~ 3-inch": a store complete rene~iag of the un~x would be "grams per 3-inch by 4-inch strip".
., Soibzess is a quality that dins not lead itself to easy quantification. J D.
Bates, in "Softness Index Fact or Mrage?", T~ Vo148 (1965), No. 4, pp. 63A-64A, indicates that the two most important readily quantifiable properties for predicting perceived softness are (a) rougfness and (b) what may be reserved tp as stifi~ss modules. ?'issue and produced according to the present invention have a more pleasing texture as measured by reduced values of either o~r both toughness or sues modules (relative to cool samples).
~ SurFace roughness can be evaluated by rnessuthtg geourctric mean deviatiwm in the coeff cleat of friction using a Kawabata KES-SE Fraction Tester equipped wide a fingerprint type sensing unit using the low sensitivity range. A 25 g stylus weight is used, and the instnunent readoux is divided by 20 to obtain the rneaa deviation in the .~.oeff dent of friction.
The geometric mean . deviation in the coe~cient of friction (Cdr) is then the square root of the product of the deviation in the machine direction and the crass-m~h>ne direction, thereafter is referred to as friction,, The stifi~ss modules is determined by the procedure for measuring tensile described above, except that a sample width of 1 inch is used and the modules recorded is the geometric mean of the ratio of SO grams load over percent strain obtained from the load-strain curve.
The STI!! values set fords in tables 1, 6, 7 and 8 are obtained by the method disclosed in the publication of the pa# the ?Fssue Jl~aldrrg ConjErrnct, Ocrnber S-b,1989 in Karlstad, Sweden entitled ~'a~erization of CteDe Structure by lmaae Analvsis_ Ma~anus Folk, S?FI, Sweden, pp. 39-S0. 1a our method, the tissue is placed under s stereo microscope with the Yankee side up and t7luminated in the 14m with oblique t'Iluminatiort roughly 10 degrees out of place. ><mages (9) are collected at a magnification of 16X at S1Zx512x256 resolution and cortated for the nonuoifotmiiy in illumination. The images are segmented (ttansfvrmed from greylevel to binary) such that 50~~ of the area is shadow.
Nure equally spaced scans are oonducbed on each image and the shadow lengths determia~ed and saved in a don base, The data are fi~od mte~ctively m as Erlang distribution to deterntine 8~e best fit STFI, length is related to crepe coarseness - i.e. ~a lower STPT number oon~sponds to a finer crepe structure which is turn corrta'butes to higher pa~aved sods.
F.xaanple 1 This example ~usuates the general papecmabnE Prod u~i~a8 our adhesive formulations and optional softa~as. Further datz are set 5oatlr in Tables 1 and 2.
A fiunish of 50 % Northern hardwood kta$ and SO ~/o Northern softwrood kra$
was PreP~- ~ P8 ~ ae ~~ wire former with a Yankee dryer speed of 100 ft per minute. Two~ths of a pound of base polymer with specified crosslinkiag agent amount per ton of furnish was sprayed directly on t'he Yankee; the amotmt of soi~ener sprayed on the Yankee side of the sheet is set forth in Table 1. Ibe crepir~ angle was maintained t at 72°. The bevel was 8°. The Yankee temperature was 101° C. The adhesive fonnalatia~as were sprayed from position 51, as shown in Figure 2, erectly on the Yankee, while the softeners, if used, were sprayed from position 52, as shown in Figure 2, which is the air side of the sheet on the Yankee.
~,~vvr~n ~> ~ ~i ~ > v> > .P r~
~' ~ ~~~c°c~
V V ~ r a ~a ~ ~ ~~~~~~ ~~.
"ss_s~~~
L
~, a ~
e< ~e 8 ey N
.~~~ V~rr~~'u ~ 11 pros g~ ~ w w v wig w~~ w i w w iw _ _ N
v v - a a a $ CS w 'B ° w w ~r .~ ,~~, w Q' ,...
.. ..
..~'° ~ 8 ~ _ » a ~ ~ ~w ..
w =~= w 'r~' __ __ w w ~ i ~ ~ $i ~ V ~ a 1~
F,xatnple 2 Examples 2 end 3 ~lust~te the many taethod for one and two ply tissues. The adhaivr and so~aoer data are not prwvldsd in these examples but are set ford is the subsequent examples.
A fiunish of sOYe Sovthan hardwood krsft and SO% Southaa so~ood kraR was prepared The papermaldng machine was an ~cliaed wire former with a Yankee dryer speed of 1852 feet per minute. the operati~ag ds~ 5or the p>penmaldqg process are set forth is Tsble 2. A hid basis wagbt bax sheet was prepared Table 2 ONE PLY TISSUE SHEET VALUE UNITS
(l~,v~t wr~cxr~
Fspeea/reet speea l8svls19 ~ ~ tvn~.
Furnish s0'Ye SWK (NaheolsPisu) so y t3wx (rraheota .
cue) (~Y) ~ hP
S~~~ _. _ _ H
MD/CD t~7e ratio 2.0 - 2.s Basis we~ht 16.6 lbJream~
Dry stock #bw 16 ' lb./mia Yankee s~oeam/Acod t~anp.100100 (start pts.) psig/deg. F
lnfiared heater ON
MoiSttu~C 4 %
Calendar load "tow load"
Red crepe 18 X
~e blade bevel 15 deg.
~ReaZn = 3000 Sq. R
. zo Example 3 A fu<aush of 50 ~/e 5outhera hardwood lQaft sod 50 % Southern softwood kraft was prepared, The PaParma~ag machine was as ~d~ed wire former with a Yankee dryer spoed of 3450 feet per urinate. The opera~tiag data ~pr $ie papermalong process are set forth is Table 3. A low basis weight base sheet was prepared.
?able 3 TWO PLY TISSUE SHEET VALI1E UNTI'S
(GIGHT WEIGHT? .
Foxing speed ' 3450 fYmin. ' Reel crepe 18 Yankee steam pressure 75 ' ' psi wet end hood temperaturesso deg. F
.
Jet/wire ratio 0.94 Headbox slice 0.500 in Refiner $ow 48 gaUmia Total headbox Sow 1980 gaUmin.
Refining (soflvuood 42 hp only) Basis oveight 9.6 Ib./ream IVl~pisture 4 Crepe blade baud 15 deg.
tReam = 3000 Sq. feet Example 4 Table 4 pro .codes the chemical code designation and dof the adhesives, crosslinlaarg agents, softener's, and release agents employed is Examples 1, 5, 6, 7 arid 8.
Table 4 CHEMICAL COIN'I'S
DESIGNATION
H8290 (PAE'} Houghton Rezosol~ 8290 adhesive (polyaminoamid~-epichlorohydrin) Al ' Polyvinyl alcohol = 6 cool h vinyl amine copolymer GLYOXAL Crosslinkarg agent fior Al, supplied by Hoedut Celanese as 40 % solution AZC Ammonium rirc~ium carbo~te (cmssvabag ageat for Al), supplied by esium Ele lrra as 20 % solution ACOT~ 20 202-JR Quaker Quasoft 20~JR softener (fatl3r diamide quat based on di ere tri aad C14-C18 uasaturated acids _ Hou ton 565 release mineral oil bas AIItVOL -107 Polywmyl Alcohol (Mol. Wt = 40,000 g/mol, hydrolysis = 98 cool%), lied Air Products and Chemicals Ina AZItVOL - 540 Potyvmyl Alcohol (Viol. Wt ~ 155,000 g/mol, I~ydrolysis = 88 cool%), lied Air Products acrd Chemicals,1r>c.
AlIiVOL - 350 Polyvinyl Akxhol (Mol. Wt =155,000 g/urol, Iiydro~is = 98 cool%), s lied Air Products and Chemicals Inc.
A1RVOL - 205 Po~rvi~l Alcohol (MQL Vl~t = 40,000 g/mol, Hydrolysis 88 moil%), s lied Air Products and Chemicals, lna Fanmple 5 This oxinnple gives the a~siv~e 5ormulations 5or papermabng process descaa'bed in Examples 6, 7 and 8. In Tables 5, 6 and ~ daxs has bees set forth ~or each of the 1 ~ ceps.
table 5 summarizes these cxatupla and lists the cell number, base pa~maer, glyoxal, ammonium arconium ~rbooste, soRmer, rdcase agent aad states arh~ha lire furnish was re5rred or unrefined aad givrs the bssis wright of the paper ~ ?he sheet teasion values aad sidedness parsaneters are not given is this table but are set Eo~rth in ?abies 6, 7 and 8 where applicable ~o, ~0 ~o ~0 ~D ~C ~ ~0, ~ ~ ~o b ~p ~o ~0 ~0 t V ~o ~o ~o ~ ~o ~o ~d ~ ~ ~D ~o ~ ~ e; a a o~
r .r ..r w~ r r r r wr w h ..
., ...
V
H V1 ~ ~ H H ~ ~ H H iV !'~1 N t'1 Z ~ ~ ~ ~ N ~ ~ Z ~ ~'' .r r ~r ~
H ~ v1 H w1 H H H H r1 H h H V1 Y1 ~' !V !V fV !~ fV fV !V iV !V !V !~ !V !V ~ h Z ~ G O O O O O C O C O O 0 C
O O O O O O O O O O O, O~ O v a 1~1 ~ ~ w w .r r ' - ~., w .~ r I i j i, .o w ~ _, I' ; s = s ~ : ; ; ~ ! . I
<:. a 0 0 o c o o~, o o I I ! ! !' ! ! I Q o o ! t I o m w r w 11 ~r wi ~ 11 ~ ~
l~~lt< d x~ < < < < < a~ < < < < ~ < ~ <
~v w f'1 PI f H 1p 1~ 11 a ,0., a."r ~ w w "h, w ~ ..
v 7. ' ' . ~ . '~ .
Example 6 ?his example ill~utr~ that whoa the adhesive c~sisting of PVOH YAM copolymer crosslinked with AZC is used, sheet tensiamalues are obtained which are equivalent or better rhea the values obtaused for the commercial PwE control product. The base shear for the two pry tissue was prepared according to tha ptneess of Example 3. The description of the additives, avsstinldng agents, and soft~aarrs,r~e set forth in Table S. Sheet tec~ion and corresponding base sheet properties achiav~od with the PVOH~VAM oopolynner crosslinked with glyoxal or ammo~ium zirconium cacbaaate package are at least as good or better to the u~ndesitable chlorine oo~aining Houghton 8290 (PAS adtresiva: ?ha dsta is set forth in Table 6. The amrnoruum zircooiuta c:rbonata package is superior to the PAE resin package and also to the glyoxa! crosslinbr~g package as evrideaced by louver STFI Length and friction parameters.
It should be notcd~ tk~at glyoxal is added to the PVOH VAM copolymer just prior to spraying on the Yankee dryer while the ammonium zirconium cubvaate is sprayed separately but simultaneously with the PVOFi-VAM copolymer.
. 24 Z
e~ D ew :..
M
r~ .
v N
s [u ~~", ~ ~ ~
..r H
ode a o vv a a ~ ~.
v~ a: o~ o~
H a x ~~~~
~" o ''~ ~ a y. ~ .. * ... * .. 'H ~, ~ ~ .
a Z pp h~~
~~~~~~,~~'~p~~ '~ ~b~
~ ~~~3 o a ~.
~~
. ~ ~ ~ . ~' . . . ~.
-. .._.
_.,.
Example ~
lhis example dlusa~a~ that using the trowel adhesive formulations with softeners facilitated the production of low sidedness one pIy tissue the base sheet for the oee pIy tissue was prepared according w the papermaking process of Example 2.
The data for this Example are set ~ordi in ?ablw ~. The data in ?able 7 clearly demonsn~te the adhesive a~pacity of aaunotlium arconium carbonate and glyoxsl crosslialang agents. In this example softeners are used to r~aduce the sidedness of the one ply tissue. The data demonstrate that our novel adhesive formulations are compatible with softeners.
, .. ,.~ ,.~ ..
O
C O C . O 0 0 !i O ~ O O C p Y1 ~ 0~ !~ !~ Q
_ x ~ H H N H H
~v W V ~ H ~ ~ ~ n F1 Z ~ w w w r N
a n h ~ b r ~' .F
__ ~ _ ~ ~' E
yc r: ~o .o N ~ !1 f~ ~ fV b w M i1 ~w i1 ' ii H ii ~
H . , ;~ ~ ~~~ _ w ~ N ,r GrG., '<'~ (<~, ~s., '< ~, ~, ' ac: ss s s~ a s~ saes sect !V O N N O r N O O !V t~ ~ D ~ (V Q !~V N ~ O h O ~ O O ~~~ C O O ~ O O O ~ O 0 ~ ~ G O C '~ 0 _.
N w p o~ .. oe ~ v, _ _ _ :.
This example illustcat~ that using our ravel adhesive formulations, high sheet tension is maintained, while giving the ~e ply tissue a Low sidedness parameter relanv~e m PA.» control The base sheet for one ply was prepared according to the papermalang process of Example 2.
?he difference between Exaanples 7 and 8 is that in this example the furnish was refined. The data. in Table s demonstrate adhesive capacity of the base polymer whey coming in contact on the Yaalcce surface with the dialdehyde or zirconium erosslinldng agent in tile presence of a softener resulting is louver stiffness values relative to PAE oontroL Using the refined furnish higher sheet tension values are obtained in the presence of a soi~mer while still having a good sidednGSS parzaneter.
t d d a h A
eNn e~ H ~ ,h,~
O O O p p p , x v a O p ~ O p C
~D C1 ~G ~ a r . tN1 M
r h h !'~~ b ~ CV
w \D ~ f1 h o a ~ o .°.:
..
' ~ ~'~"' ... - ~ ~o W o e~ e., -. a a h r. 00 Des 1~~~
x o a. ~
_~~ r: ~r ~.~.~. ~.~.
~'a~~a~ ~~ : ~ s N N N eV O .-. er ~ O
o~ooRoop..:'~pd~ooo-~o do-~oa ' ~ ~., s ~o ~~ ,~, ' ~ ~~ - ~~,. ..
;., . . .
'Ihc presort itrveation may be used with a particular class of softener materials -. .
amide amine salts derived from partally acid neutralized amines. Such materials are disclosed in U.S. Patent No. 4,720,383; column 3, lines d4-41. Also relevant ue the following artides:
Evens, ~~! and Indusw. 5 July 1969, pp. 893-903; Egs:<, J Am O~1 Chemist's Soc., VoL 55 (1978), pp. 118-121; and ?rivedi et aL, ~~17 ~emist's Soy, June 1981, pp.
754.756. All of the above sre inoorporatvd herein by rrferenc~ As indicated therein, softeners are oiler available oommacially only as complex mixtures rather than as single compounds.
While this discussion will focus on the predonnit~nt species, it should be understood that commercially available mixtures would gen~aally be used to practice the inventior~
At this time, Q202-JR and 209~JR is a preferred soRer~er material which is derived by alkylatinE a coardertsation product of oleic acid and diethylenetriamine. Synthesis conditions using a defiaency of ally agent (e.g., diethyl sulfate) and only one atlcylating step, followed by pH adjuttmart to probotrate the tern-~rlated species, result in a mixture consisting of cationic ethylated arrd cationic nen-etitylated species. A minor proportion (e.g., about I O %) of the resulting amide amines ~yclize no itnidazoliae compounds.
Since these materials era cwt quaternary ammonium ootnpousd~ they are pH~sitive.
?herefore, in the practice of the present inva~tiotr wilt this class of chemicals, the pH in the headbox should be aPP~~Y 6 m 8, mere preferably o to '7 and most preferably 6.5 to 7.
The softener employed for treatment of the fwnish is provided at a treatment level that is sufficient to impart a percepd'bb degroe of saws ~ the paper product but Iess thaw an amount that would cause significant runnabiliry and sheet strength problems in the final commercial groduct Zhe amount of softener ettrployed, oa a 100 °!.
acxive basis, is preferably from about 0.1 pounds per ton of fiber in the furnish up to about 10 pounds per tea of fiber in the fumisb, dta more prefaced amount is from 2 to about 5 pounds per tnn of fiber in the furnish.
Figut~es 3 tiuough s d~ravstrste drat dialdd>yd~ are aosslinldug agenss when oortrbined with a base polymer such as polyvinyl atcohel and polyvinyl alcohol vinyl ..
amine copo)ymer, and blend thereof .
Figures 4 sad 5 illustrate that dialdehyde crosslinldng increases adhesion is the presence of softener, as evidenced by higher adhesion values as measured by peel force and lower geometric meap~ tensile (C~T~ parameters.
Fsthetics and tactile cansideratioas are extremely important for tissue produces as they often come into intimate c~atect with the most delicate parts of the bob is use. Consequently, demand is quite high for products wrth improved tactile qualities, particularly sof~ss.
However, as tissue products are &equeatly used to wroid contact with that which the consumer would greatly prefer not to touch, sofas alone is not sufficie~ stra~gth is also required.
Merely providing a product with improved properties is not generally su~cieat, tile "on the shelf' appearance of the product must suggest both streagtlz and roflness where cottsuraess must be able to sense iug~by handling packaged product Appearance is critical;
bulk, weight, compressibility, tinruless, te~cture and ether qualities perceived as indicis of strength and softness are also requirod TAPPI 401 OM 88 (Revised 1988) provides a procedure for the identification of the types of f bets present in a sample o~f paper or paperboard and es>;matioa of their quality.
Analysis of the amount of the sofbmer/debonder chemicals retained ca the tissue paper can be performed by any method accepted is the applicable art For the most sertsitive~cases, we prefer to x-ray photoelectron sptopy ESCA to measure nitrogen levels. Normauy, the backg~d level is quire high and the variation between measut emeats quite high, so use of several replicates is a relatively modern ESCA system such as the Perlda Elmer Corporation's model 5600 is requirod m obtain more precise measuremetrts. the level of cati~ic nitrogenous sofleaer/debonder such as Quasofl~ 202-JR can alternatively be determined by solvent eon of the Quasoft~ Z02-JR by as organic solvont followed by liquid chromatography detertreioation of the softane</debonder.
Tensile stca>gtit of tissue produced in accordance with the present invention is measured in the machine direction sad cTOSS-machine direction on as Instroa tense testxc with the gauge largth set to 4 incites- the: ma of tissue tied is assumed to be 3 iad~s wide by 4 inches laag. A 20 pound load cell with heavywaght grips applied to the total width of the sample is employed ?he msaimutn load is recorded for each direction. 1be results are r~ortad in units of "~ p~ 3-inch": a store complete rene~iag of the un~x would be "grams per 3-inch by 4-inch strip".
., Soibzess is a quality that dins not lead itself to easy quantification. J D.
Bates, in "Softness Index Fact or Mrage?", T~ Vo148 (1965), No. 4, pp. 63A-64A, indicates that the two most important readily quantifiable properties for predicting perceived softness are (a) rougfness and (b) what may be reserved tp as stifi~ss modules. ?'issue and produced according to the present invention have a more pleasing texture as measured by reduced values of either o~r both toughness or sues modules (relative to cool samples).
~ SurFace roughness can be evaluated by rnessuthtg geourctric mean deviatiwm in the coeff cleat of friction using a Kawabata KES-SE Fraction Tester equipped wide a fingerprint type sensing unit using the low sensitivity range. A 25 g stylus weight is used, and the instnunent readoux is divided by 20 to obtain the rneaa deviation in the .~.oeff dent of friction.
The geometric mean . deviation in the coe~cient of friction (Cdr) is then the square root of the product of the deviation in the machine direction and the crass-m~h>ne direction, thereafter is referred to as friction,, The stifi~ss modules is determined by the procedure for measuring tensile described above, except that a sample width of 1 inch is used and the modules recorded is the geometric mean of the ratio of SO grams load over percent strain obtained from the load-strain curve.
The STI!! values set fords in tables 1, 6, 7 and 8 are obtained by the method disclosed in the publication of the pa# the ?Fssue Jl~aldrrg ConjErrnct, Ocrnber S-b,1989 in Karlstad, Sweden entitled ~'a~erization of CteDe Structure by lmaae Analvsis_ Ma~anus Folk, S?FI, Sweden, pp. 39-S0. 1a our method, the tissue is placed under s stereo microscope with the Yankee side up and t7luminated in the 14m with oblique t'Iluminatiort roughly 10 degrees out of place. ><mages (9) are collected at a magnification of 16X at S1Zx512x256 resolution and cortated for the nonuoifotmiiy in illumination. The images are segmented (ttansfvrmed from greylevel to binary) such that 50~~ of the area is shadow.
Nure equally spaced scans are oonducbed on each image and the shadow lengths determia~ed and saved in a don base, The data are fi~od mte~ctively m as Erlang distribution to deterntine 8~e best fit STFI, length is related to crepe coarseness - i.e. ~a lower STPT number oon~sponds to a finer crepe structure which is turn corrta'butes to higher pa~aved sods.
F.xaanple 1 This example ~usuates the general papecmabnE Prod u~i~a8 our adhesive formulations and optional softa~as. Further datz are set 5oatlr in Tables 1 and 2.
A fiunish of 50 % Northern hardwood kta$ and SO ~/o Northern softwrood kra$
was PreP~- ~ P8 ~ ae ~~ wire former with a Yankee dryer speed of 100 ft per minute. Two~ths of a pound of base polymer with specified crosslinkiag agent amount per ton of furnish was sprayed directly on t'he Yankee; the amotmt of soi~ener sprayed on the Yankee side of the sheet is set forth in Table 1. Ibe crepir~ angle was maintained t at 72°. The bevel was 8°. The Yankee temperature was 101° C. The adhesive fonnalatia~as were sprayed from position 51, as shown in Figure 2, erectly on the Yankee, while the softeners, if used, were sprayed from position 52, as shown in Figure 2, which is the air side of the sheet on the Yankee.
~,~vvr~n ~> ~ ~i ~ > v> > .P r~
~' ~ ~~~c°c~
V V ~ r a ~a ~ ~ ~~~~~~ ~~.
"ss_s~~~
L
~, a ~
e< ~e 8 ey N
.~~~ V~rr~~'u ~ 11 pros g~ ~ w w v wig w~~ w i w w iw _ _ N
v v - a a a $ CS w 'B ° w w ~r .~ ,~~, w Q' ,...
.. ..
..~'° ~ 8 ~ _ » a ~ ~ ~w ..
w =~= w 'r~' __ __ w w ~ i ~ ~ $i ~ V ~ a 1~
F,xatnple 2 Examples 2 end 3 ~lust~te the many taethod for one and two ply tissues. The adhaivr and so~aoer data are not prwvldsd in these examples but are set ford is the subsequent examples.
A fiunish of sOYe Sovthan hardwood krsft and SO% Southaa so~ood kraR was prepared The papermaldng machine was an ~cliaed wire former with a Yankee dryer speed of 1852 feet per minute. the operati~ag ds~ 5or the p>penmaldqg process are set forth is Tsble 2. A hid basis wagbt bax sheet was prepared Table 2 ONE PLY TISSUE SHEET VALUE UNITS
(l~,v~t wr~cxr~
Fspeea/reet speea l8svls19 ~ ~ tvn~.
Furnish s0'Ye SWK (NaheolsPisu) so y t3wx (rraheota .
cue) (~Y) ~ hP
S~~~ _. _ _ H
MD/CD t~7e ratio 2.0 - 2.s Basis we~ht 16.6 lbJream~
Dry stock #bw 16 ' lb./mia Yankee s~oeam/Acod t~anp.100100 (start pts.) psig/deg. F
lnfiared heater ON
MoiSttu~C 4 %
Calendar load "tow load"
Red crepe 18 X
~e blade bevel 15 deg.
~ReaZn = 3000 Sq. R
. zo Example 3 A fu<aush of 50 ~/e 5outhera hardwood lQaft sod 50 % Southern softwood kraft was prepared, The PaParma~ag machine was as ~d~ed wire former with a Yankee dryer spoed of 3450 feet per urinate. The opera~tiag data ~pr $ie papermalong process are set forth is Table 3. A low basis weight base sheet was prepared.
?able 3 TWO PLY TISSUE SHEET VALI1E UNTI'S
(GIGHT WEIGHT? .
Foxing speed ' 3450 fYmin. ' Reel crepe 18 Yankee steam pressure 75 ' ' psi wet end hood temperaturesso deg. F
.
Jet/wire ratio 0.94 Headbox slice 0.500 in Refiner $ow 48 gaUmia Total headbox Sow 1980 gaUmin.
Refining (soflvuood 42 hp only) Basis oveight 9.6 Ib./ream IVl~pisture 4 Crepe blade baud 15 deg.
tReam = 3000 Sq. feet Example 4 Table 4 pro .codes the chemical code designation and dof the adhesives, crosslinlaarg agents, softener's, and release agents employed is Examples 1, 5, 6, 7 arid 8.
Table 4 CHEMICAL COIN'I'S
DESIGNATION
H8290 (PAE'} Houghton Rezosol~ 8290 adhesive (polyaminoamid~-epichlorohydrin) Al ' Polyvinyl alcohol = 6 cool h vinyl amine copolymer GLYOXAL Crosslinkarg agent fior Al, supplied by Hoedut Celanese as 40 % solution AZC Ammonium rirc~ium carbo~te (cmssvabag ageat for Al), supplied by esium Ele lrra as 20 % solution ACOT~ 20 202-JR Quaker Quasoft 20~JR softener (fatl3r diamide quat based on di ere tri aad C14-C18 uasaturated acids _ Hou ton 565 release mineral oil bas AIItVOL -107 Polywmyl Alcohol (Mol. Wt = 40,000 g/mol, hydrolysis = 98 cool%), lied Air Products and Chemicals Ina AZItVOL - 540 Potyvmyl Alcohol (Viol. Wt ~ 155,000 g/mol, I~ydrolysis = 88 cool%), lied Air Products acrd Chemicals,1r>c.
AlIiVOL - 350 Polyvinyl Akxhol (Mol. Wt =155,000 g/urol, Iiydro~is = 98 cool%), s lied Air Products and Chemicals Inc.
A1RVOL - 205 Po~rvi~l Alcohol (MQL Vl~t = 40,000 g/mol, Hydrolysis 88 moil%), s lied Air Products and Chemicals, lna Fanmple 5 This oxinnple gives the a~siv~e 5ormulations 5or papermabng process descaa'bed in Examples 6, 7 and 8. In Tables 5, 6 and ~ daxs has bees set forth ~or each of the 1 ~ ceps.
table 5 summarizes these cxatupla and lists the cell number, base pa~maer, glyoxal, ammonium arconium ~rbooste, soRmer, rdcase agent aad states arh~ha lire furnish was re5rred or unrefined aad givrs the bssis wright of the paper ~ ?he sheet teasion values aad sidedness parsaneters are not given is this table but are set Eo~rth in ?abies 6, 7 and 8 where applicable ~o, ~0 ~o ~0 ~D ~C ~ ~0, ~ ~ ~o b ~p ~o ~0 ~0 t V ~o ~o ~o ~ ~o ~o ~d ~ ~ ~D ~o ~ ~ e; a a o~
r .r ..r w~ r r r r wr w h ..
., ...
V
H V1 ~ ~ H H ~ ~ H H iV !'~1 N t'1 Z ~ ~ ~ ~ N ~ ~ Z ~ ~'' .r r ~r ~
H ~ v1 H w1 H H H H r1 H h H V1 Y1 ~' !V !V fV !~ fV fV !V iV !V !V !~ !V !V ~ h Z ~ G O O O O O C O C O O 0 C
O O O O O O O O O O O, O~ O v a 1~1 ~ ~ w w .r r ' - ~., w .~ r I i j i, .o w ~ _, I' ; s = s ~ : ; ; ~ ! . I
<:. a 0 0 o c o o~, o o I I ! ! !' ! ! I Q o o ! t I o m w r w 11 ~r wi ~ 11 ~ ~
l~~lt< d x~ < < < < < a~ < < < < ~ < ~ <
~v w f'1 PI f H 1p 1~ 11 a ,0., a."r ~ w w "h, w ~ ..
v 7. ' ' . ~ . '~ .
Example 6 ?his example ill~utr~ that whoa the adhesive c~sisting of PVOH YAM copolymer crosslinked with AZC is used, sheet tensiamalues are obtained which are equivalent or better rhea the values obtaused for the commercial PwE control product. The base shear for the two pry tissue was prepared according to tha ptneess of Example 3. The description of the additives, avsstinldng agents, and soft~aarrs,r~e set forth in Table S. Sheet tec~ion and corresponding base sheet properties achiav~od with the PVOH~VAM oopolynner crosslinked with glyoxal or ammo~ium zirconium cacbaaate package are at least as good or better to the u~ndesitable chlorine oo~aining Houghton 8290 (PAS adtresiva: ?ha dsta is set forth in Table 6. The amrnoruum zircooiuta c:rbonata package is superior to the PAE resin package and also to the glyoxa! crosslinbr~g package as evrideaced by louver STFI Length and friction parameters.
It should be notcd~ tk~at glyoxal is added to the PVOH VAM copolymer just prior to spraying on the Yankee dryer while the ammonium zirconium cubvaate is sprayed separately but simultaneously with the PVOFi-VAM copolymer.
. 24 Z
e~ D ew :..
M
r~ .
v N
s [u ~~", ~ ~ ~
..r H
ode a o vv a a ~ ~.
v~ a: o~ o~
H a x ~~~~
~" o ''~ ~ a y. ~ .. * ... * .. 'H ~, ~ ~ .
a Z pp h~~
~~~~~~,~~'~p~~ '~ ~b~
~ ~~~3 o a ~.
~~
. ~ ~ ~ . ~' . . . ~.
-. .._.
_.,.
Example ~
lhis example dlusa~a~ that using the trowel adhesive formulations with softeners facilitated the production of low sidedness one pIy tissue the base sheet for the oee pIy tissue was prepared according w the papermaking process of Example 2.
The data for this Example are set ~ordi in ?ablw ~. The data in ?able 7 clearly demonsn~te the adhesive a~pacity of aaunotlium arconium carbonate and glyoxsl crosslialang agents. In this example softeners are used to r~aduce the sidedness of the one ply tissue. The data demonstrate that our novel adhesive formulations are compatible with softeners.
, .. ,.~ ,.~ ..
O
C O C . O 0 0 !i O ~ O O C p Y1 ~ 0~ !~ !~ Q
_ x ~ H H N H H
~v W V ~ H ~ ~ ~ n F1 Z ~ w w w r N
a n h ~ b r ~' .F
__ ~ _ ~ ~' E
yc r: ~o .o N ~ !1 f~ ~ fV b w M i1 ~w i1 ' ii H ii ~
H . , ;~ ~ ~~~ _ w ~ N ,r GrG., '<'~ (<~, ~s., '< ~, ~, ' ac: ss s s~ a s~ saes sect !V O N N O r N O O !V t~ ~ D ~ (V Q !~V N ~ O h O ~ O O ~~~ C O O ~ O O O ~ O 0 ~ ~ G O C '~ 0 _.
N w p o~ .. oe ~ v, _ _ _ :.
This example illustcat~ that using our ravel adhesive formulations, high sheet tension is maintained, while giving the ~e ply tissue a Low sidedness parameter relanv~e m PA.» control The base sheet for one ply was prepared according to the papermalang process of Example 2.
?he difference between Exaanples 7 and 8 is that in this example the furnish was refined. The data. in Table s demonstrate adhesive capacity of the base polymer whey coming in contact on the Yaalcce surface with the dialdehyde or zirconium erosslinldng agent in tile presence of a softener resulting is louver stiffness values relative to PAE oontroL Using the refined furnish higher sheet tension values are obtained in the presence of a soi~mer while still having a good sidednGSS parzaneter.
t d d a h A
eNn e~ H ~ ,h,~
O O O p p p , x v a O p ~ O p C
~D C1 ~G ~ a r . tN1 M
r h h !'~~ b ~ CV
w \D ~ f1 h o a ~ o .°.:
..
' ~ ~'~"' ... - ~ ~o W o e~ e., -. a a h r. 00 Des 1~~~
x o a. ~
_~~ r: ~r ~.~.~. ~.~.
~'a~~a~ ~~ : ~ s N N N eV O .-. er ~ O
o~ooRoop..:'~pd~ooo-~o do-~oa ' ~ ~., s ~o ~~ ,~, ' ~ ~~ - ~~,. ..
;., . . .
Claims (111)
1. A creped fibrous web made using, as the creping adhesive, adhesive composition comprising an organic polymer having in the polymer backbone amine groups selected from primary and secondary amine groups and mixtures thereof, and a crosslinking agent selected from zirconium compounds wherein the zirconium has a valency of plus four.
2. The creped fibrous web of Claim 1 wherein the organic polymer having primary and secondary amine groups is selected from the group consisting of chitosan, polyvinylamine, polyvinyl alcohol-vinyl amine and polyaminoamide.
3. The creped fibrous web of Claim 1 or 2 wherein the zirconium compound is selected from the group consisting of ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate;
zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tartrate.
zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tartrate.
4. The creped fibrous web of Claim 1 or 2 wherein the zirconium compound is ammonium zirconium carbonate.
5. The creped fibrous web of Claim 1 or 2 wherein about 0.1 to about 0.8 pounds of the adhesive formulation are added for each ton of cellulosic papermaking fibers in the aqueous furnish.
6. The creped fibrous web of Claim 1 or 2 wherein about 0.1 to about 10 pounds of the cationic softener/debonder are added for each ton of the cellulosic papermaking fibers in the aqueous furnish.
7. The creped fibrous web of Claim 6 wherein the nitrogenous softener/debonder is selected from the group consisting of imidazolines, amido amine salts, linear amido amines, tetravalent ammonium salts, and mixtures thereof.
8. The creped fibrous web of Claim 7 wherein the salt has the following structure:
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is an anion.
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is an anion.
9. The creped fibrous web of Claim 6 wherein the salt has the following structure:
[(RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is an anion.
[(RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is an anion.
10. The creped fibrous web of Claim 6 wherein the softener/debonder is a mixture of linear amido amines and imidazolines of the following structure:
wherein X is an anion.
wherein X is an anion.
11. A creped fibrous web made using, as a creping adhesive, an adhesive composition comprising polyvinyl alcohol-vinyl amine copolymer of the following structure:
wherein m and n have values of about 1 to 99 and about 99 to 1 respectively, and a crosslinking agent selected from zirconium compounds wherein the zirconium has a valency of plus four.
wherein m and n have values of about 1 to 99 and about 99 to 1 respectively, and a crosslinking agent selected from zirconium compounds wherein the zirconium has a valency of plus four.
12. The creped fibrous web of Claim 11 wherein the zirconium compound is selected from the group consisting of ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tartrate.
13. The creped fibrous web of Claim 11 wherein the zirconium compound is ammonium zirconium carbonate.
14. The creped fibrous web of Claim 11 wherein about 0.1 to about 0.8 pounds of the adhesive formulation are added for each ton of cellulosic papermaking fibers in the aqueous furnish.
15. the creped fibrous web of Claim 11 wherein about 0.1 to about 10 pounds of the cationic softener/debonder are added for each ton of the cellulosic papermaking fibers in the aqueous furnish.
16. the creped fibrous web of Claim 15 wherein the nitrogenous softener/debonder is selected from the group consisting of imidazolines, amido amine salts, linear amido amines, tetravalent ammonium salts, and mixtures thereof.
17. The creped fibrous web of Claim 16 wherein the salt has the following structure:
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is an anion.
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is an anion.
18. The creped fibrous web of Claim 15 wherein the salt has the following structure:
[(RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is as anion.
[(RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is as anion.
19. The creped fibrous web of Claim 15 wherein the softner/debonder is a mixture of linear amido amines and imidazolines of the following structure:
wherein X is an anion.
wherein X is an anion.
20. A creped towel made using, as the creping adhesive, adhesive composition comprising an organic polymer having in the polymer backbone amine groups selected from primary and secondary amine groups and mixtures thereof, and a crosslinking agent selected from zirconium compounds wherein the zirconium has a valency of plus four.
21. The creped towel of Claim 20 wherein the organic polymer is selected from the group consisting of chitosan, polyvinylamine, polyvinyl alcohol-vinyl amine and polyaminoamide.
22. The creped towel of Claim 20 or Claim 21 wherein the zirconium compound is selected from the group consisting of ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tartrate.
23. The creped towel of Claim 20 or Claim 21 wherein the zirconium compound is ammonium zirconium carbonate.
24. The creped towel of Claim 20 or Claim 21 wherein about 0.1 to about 0.8 pounds of the adhesive formulation are added for each ton of cellulosic papermaking fibers in the aqueous furnish.
25. the creped towel of Claim 20 or Claim 21 wherein about 0.1 to about 10 pounds of the cationic softener/debonder are added for each ton of the cellulosic papermaking fibers in the aqueous furnish.
26. The creped towel of Claim 25 wherein the nitrogenous softener/debonder is selected from the group consisting of imidazolines, amido amine salts, linear amido amines, tetravalent ammonium salts, and mixtures thereof.
27. The creped towel of Claim 26 wherein the salt has the following structure:
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is as anion.
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is as anion.
28. The creped of Claim 25 wherein the salt has the following structure:
[(RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is an anion.
[(RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is an anion.
29. The creped towel of Claim 25 wherein the softener/debonder is a mixture of linear amido amines and imidazolines of the following structure:
wherein X is an anion.
wherein X is an anion.
30. A creped towel made using, as a creping adhesive, an adhesive composition comprising polyvinyl alcohol-vinyl amine copolymer of the following structure:
wherein m and n have values of about 1 to 99 and about 99 to 1 respectively, and a crosslinking agent selected from zirconium compounds wherein the zirconium has a valency of plus four.
wherein m and n have values of about 1 to 99 and about 99 to 1 respectively, and a crosslinking agent selected from zirconium compounds wherein the zirconium has a valency of plus four.
31. The creped towel of Claim 30 wherein the zirconium compound is selected from the group consisting of ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tartrate.
32. The creped towel of Claim 30 wherein the zirconium compound is ammonium zirconium carbonate.
33. the creped towel of Claim 30 wherein about 0.1 to about 0.8 pounds of the adhesive formulation are added for each ton of cellulosic papermaking fibers in the aqueous
34. The creped towel of Claim 30 wherein about 0.1 to about 10 pounds of the cationic softener/debonder are added for each ton of the cellulosic papermaking fibers in the aqueous furnish.
35. The creped towel of Claim 34 wherein the nitrogenous softener/debonder is selected from the group consisting of imidazolines, amido amine salts, linear amido amines, tetravalent ammonium salts, and mixtures thereof.
36. The creped towel of Claim 35 wherein the salt has the following structure:
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is an anion.
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is an anion.
37. The creped towel of Claim 34 wherein the salt has the following structure:
[(RCONHCH2CH2)2NR]HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is an anion.
[(RCONHCH2CH2)2NR]HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is an anion.
38. The creped towel of Claim 34 wherein the softener/debonder is a mixture of linear amide amines and imidazolines of the following structure:
wherein X is an anion.
wherein X is an anion.
39. A creped tissue made using, as the creping adhesive, adhesive composition comprising an organic polymer having in the polymer backbone amine groups selected from primary and secondary amine groups and mixtures thereof, and a crosslinking agent selected from zirconium compounds wherein the zirconium has a valency of plus four.
40. The creped tissue of Claim 39 wherein the organic polymer is selected from the group consisting of chitosan, polyvinylamine, polyvinyl alcohol-vinyl amine and polyaminoamide.
41. The creped tissue of Claim 39 or Claim 40 wherein the zirconium compound is selected from the group consisting of ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tartrate.
42. The creped tissue of Claim 39 or Claim 40 wherein the zirconium compound is ammonium zirconium carbonate.
43. The creped tissue of Claim 39 or Claim 40 wherein about 0.1 to about 0.8 pounds of the adhesive formulation are added for each ton of cellulosic papermaking fibers in the aqueous furnish,
44. The creped tissue of Claim 39 or Claim 40 wherein about 0.1 to about 10 pounds of the cationic softener/debonder are added for each ton of the cellulosic papermaking fibers in the aqueous furnish.
45. The creped tissue of Claim 44 wherein the nitrogenous softener/debonder is selected from the group consisting of imidazolines, amido amine salts, linear amido amines, tetravalent ammonium salts, and mixtures thereof.
46. The creped tissue of Claim 45 wherein the salt has the following structure:
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is as anion.
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is as anion.
47. The creped tissue of Claim 44 wherein the salt has the following structure:
[(RCONHCH2CH2)2NR]HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is as anion.
[(RCONHCH2CH2)2NR]HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is as anion.
48. The creped tissue of Claim 44 wherein the softener/debonder is a mixture of linear amido amines and imidazolines of the following structure:
wherein X is an anion.
wherein X is an anion.
49. A creped tissue made using, as a creping adhesive, an adhesive composition comprising polyvinyl alcohol-vinyl amine copolymer of the following structure:
wherein m and n have values of about 1 to 99 and about 99 to 1 respectively, and a crosslinking agent selected from zirconium compounds wherein the zirconium has a valency of plus four.
wherein m and n have values of about 1 to 99 and about 99 to 1 respectively, and a crosslinking agent selected from zirconium compounds wherein the zirconium has a valency of plus four.
50. The creped tissue of Claim 49 wherein the zirconium compound is selected from the group consisting of ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tartrate.
51. The creped tissue of Claim 49 wherein the zirconium compound is ammonium zirconium carbonate.
52. The creped tissue of Claim 49 wherein about 0.1 to about 0.8 pounds of the adhesive formulation are added for each ton of cellulosic papermaking fibers is the aqueous furnish.
53. The creped tissue of Claim 49 wherein about 0.1 to about 10 pounds of the cationic softener/debonder are added for each ton of the cellulosic papermaking fibers in the aqueous furnish.
54, The creped tissue of Claim 53 wherein the nitrogenous softener/debonder is selected from the group consisting of imidazolines, amido amine salts, linear amido amines, tetravalent ammonium salts, and mixtures thereof.
55. The creped tissue of Claim 54 wherein the salt has the following structure:
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is an anion.
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is an anion.
56. The creped tissue of Claim 53 wherein the salt has the following structure:
((RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty and having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is as anion.
((RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty and having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is as anion.
37. The creped tissue of Claim 33 wherein the softener/debonder is a mixture of linear amido amines and imidazolines of the following structure:
wherein X is an anion.
wherein X is an anion.
58. A creping adhesive composition comprising an organic polymer having in the polymer backbone amine groups selected from the group consisting of primary and secondary amines or mixtures of primary and secondary amines and a crosslinking agent far crosslinking the polymer to itself and to the fibrous web said agent being selected from zirconium compounds having a valency of plus four.
59. The adhesive composition of Claim 58 wherein the organic polymer is selected from the group consisting of chitosan, polyvinylamine, polyvinyl alcohol-vinyl amine and polyaminoamide.
60. The creping adhesive of Claim 58 or Claim 59 wherein the zirconium compound is selected from the group consisting of ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tartrate.
61. The creping adhesive of Claim 58 or Claim 59 wherein the zirconium compound is ammonium zirconium carbonate.
62. A creping adhesive composition comprising polyvinyl alcohol-vinyl amine copolymer of the following structure:
wherein m and n have values of about 1 to 99 and about 99 to 1 respectively, crosslinkable at the drying surface with zirconium compounds having a valence of plus four suitable for ionic crosslinking with cellulosic paper products.
wherein m and n have values of about 1 to 99 and about 99 to 1 respectively, crosslinkable at the drying surface with zirconium compounds having a valence of plus four suitable for ionic crosslinking with cellulosic paper products.
63. The creping adhesive of Claim 62 wherein the zirconium compound is selected from the group consisting of ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tartrate.
64. The creping adhesive of Claim 62 wherein the zirconium compound is ammonium zirconium carbonate.
65. A method of creping a fibrous web which includes adhering it to a dryer surface with a creping adhesive composition and thereafter creping it from the surface characterised in that said adhesive composition comprises an organic polymer having in the polymer backbone amine groups selected from primary and secondary amine groups and mixtures thereof, and a crosslinking agent for crosslinking the polymer to itself and to the fibrous web, said agent being selected from dialdehydes and zirconium compounds wherein the zirconium has a valency of plus four and the crosslinking agent is added directly on the Yankee with the copolymer without prior mixing with the copolymer, or the crosslinking agent is added to the copolymer just prior to spraying without reacting the crosslinking agent with the copolymer.
66. The method of creping a fibrous web of Claim 65 wherein the organic polymer having primary and secondary amine groups is selected from the group consisting of chitosin, polyvinylamine, polyvinyl alcohol-vinyl amine and polyaminoamide.
67. The method of Claim 65 or Claim 66 wherein the zirconium compound is selected from the group consisting of ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tartrate.
68. The method of Claim 65 or Claim 66 wherein the zirconium compound is ammonium zirconium carbonate.
69, The method of Claim 65 or Claim 66 wherein about 0.1 to about 0.8 pounds of the adhesive are added for each ton of cellulosic papermaking fibers in the aqueous furnish.
70. The method of Claim 65 or Claim 66 wherein the dialdehyde has the following structure:
wherein n is an integer having a value of 0 to 3.
wherein n is an integer having a value of 0 to 3.
71 The method of Claim 65 or Claim 66 wherein the dialdehyde is glyoxal.
72, The method of Claim 65 or Claim 66 wherein about 0.1 to about 10 pounds of cationic softener/debonder are added for each ton of the cellulosic papermaking fibers in the aqueous furnish.
73. The method of Claim 72 wherein a nitrogenous softener/debonder is selected from the group consisting of imidazolines, amido amine salts, linear amido amines, tetravalent ammonium salts, and mixtures thereof.
74. The method of Claim 73 wherein the salt has the following structure:
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is an anion.
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is an anion.
75. The method of Claim 74 wherein the salt has the following structure:
[(RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is an anion.
[(RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is an anion.
76. The method of Claim 73 wherein the softener/debonder is a mixture of linear amido amines and imidazolines of the following structure:
wherein X is an anion.
wherein X is an anion.
77. A method of creping a fibrous web which includes adhering it to a dryer surface with a creping composition and thereafter creping it from the surface characterised in chat said adhesive composition comprises a polyvinyl alcohol-vinyl amine copolymer of the following structure:
wherein m and n have values of 1 to 99 and 99 to 1 respectively, and a crosslinking agent for crosslinking the polymer to itself and to the fibrous web, said agent being selected from dialdehydes and zirconium compounds wherein the zirconium has a valence of plus four and the crosslinking agent is added directly on the Yankee with the copolymer without prior mixing with the copolymer, or the crosslinking agent is added to the copolymer just prior to spraying without reacting the crosslinking agent with the copolymer.
wherein m and n have values of 1 to 99 and 99 to 1 respectively, and a crosslinking agent for crosslinking the polymer to itself and to the fibrous web, said agent being selected from dialdehydes and zirconium compounds wherein the zirconium has a valence of plus four and the crosslinking agent is added directly on the Yankee with the copolymer without prior mixing with the copolymer, or the crosslinking agent is added to the copolymer just prior to spraying without reacting the crosslinking agent with the copolymer.
78. The method of Claim 66 or Claim 77 wherein a towel is recovered.
79, The method of Claim 77 wherein the zirconium compound is selected from the group consisting of ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tartrate.
80. The method of Claim 77 wherein the zirconium compound is ammonium zirconium carbonate.
81. The method of Claim 77 wherein about 0.1 to about 0.8 pounds of the adhesive are added for each ton of cellulosic papermaking fibers in the aqueous furnish.
82. The method of Claim 77 wherein the dialdehyde has the following structure:
wherein n is as integer having a value of 0 to 3.
wherein n is as integer having a value of 0 to 3.
83. The method of Claim 77 wherein the dialdehyde is glyoxal.
84. The method of Claim 77 wherein about 0.1 to about 10 pounds of cationic softener/debonder are added for each ton of the cellulosic papermaking fibers is the aqueous furnish.
85. The method of Claim 84 wherein a nitrogenous softener/debonder is selected from the group consisting of imidazolines, amido amine salts, linear amido amines, tetravalent ammonium sans, and mixtures thereof.
86. The method of Claim 85 where;n the salt has the following structure:
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty add having from 12 to 22 carbon atoms, and X is an anion.
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty add having from 12 to 22 carbon atoms, and X is an anion.
87. The method of Claim 86 wherein the salt has the following structure:
[(RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is an anion.
[(RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is an anion.
88. The method of Claim 85 wherein the softener/debonder is s mixture of linear amido amines and imidazolines of the following structure:
wherein X is an anion.
wherein X is an anion.
89. A method of creping a fibrous web to recover a tissue which includes adhering it to a dryer surface with a creping adhesive composition and thereafter creping it from the surface characterised in that said adhesive composition comprises an organic polymer having in the polymer backbone amine groups selected from primary and secondary amine groups and mixtures thereof, and a crosslinking agent for crosslinking the polymer to itself and to the fibrous web, said agent bring selected from dialdehydes and zirconium compounds wherein the zirconium has a valency of plus four and the crosslinking agent is added directly on the Yankee with the copolymer without prior mixing with the copolymer, or the crosslinking agent is added to the copolymer just prior to spraying without reacting the crosslinking agent with the copolymer.
90. The method of creping a fibrous web to produce a tissue of Claim 89 wherein the organic polymer having primary and secondary amine groups is selected from the group consisting of chitosan, polyvinylamine, polyvinyl alcohol-vinyl amine and polyaminoamide.
91. The method of Claim 89 or Claim 90 wherein the zirconium compound is selected from the group consisting of ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate. potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tactrate.
92. The method of Claim 89 or Claim 90 wherein the zirconium compound is ammonium zirconium carbonate.
93. The method of Claim 89 or Claim 90 wherein about 0.1 to about 0.8 pounds of the adhesive are added for each ton of cellulosic papermaking fibers in the aqueous-furnish.
94. The method of Claim 89 or Claim 90 wherein the dialdehyde has the following structure:
wherein n is an integer having a value of 0 to 3.
wherein n is an integer having a value of 0 to 3.
95. The method of Claim 89 or Claim 90 wherein the dialdehyde is glyoxal.
96. The method of Claim 89 or Claim 90 wherein about 0.1 to about 10 pounds of cationic softener/debonder are added for each ton of the cellulosic papermaking fibers in the aqueous furnish.
97. The method of Claim 96 wherein a nitrogenous softener/debonder is selected from the group consisting of imidazolines, amido amine salts, linear amido amines, tetravalent ammonium salts, and mixtures thereof.
98. The method of Claim 97 wherein the salt has the following structure:
[(RCO)2EDA]HX
wherein EDA is a diethylenctriamine residue, R is the residue of a fatty acid having from 12 to 32 carbon atoms, and X is an anion.
[(RCO)2EDA]HX
wherein EDA is a diethylenctriamine residue, R is the residue of a fatty acid having from 12 to 32 carbon atoms, and X is an anion.
99. The method of Claim 98 wherein the salt has the following structure:
[(RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is an anion .
[(RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is an anion .
100. The method of Claim 97 wherein the softener/debonder is a mixture of linear amido amines and imidazolines of the following structure:
wherein X is an anion.
wherein X is an anion.
101. A method of creping a fibrous web to recover a tissue which includes adhering it to a dryer surface with a creping composition and thereafter creping it from the surface characterised in that said adhesive composition comprises a polyvinyl alcohol-vinyl amine copolymer of the following structure:
wherein m and n have values of 1 to 99 and 99 to 1 respectively, and a crosslinking agent for crosslinking the polymer to itself and to the fibrous web, said agent being selected from dialdehydes and zirconium compounds wherein the zirconium has a valence of plus four and the crosslinking agent is added directly on the Yankee with the copolymer without prior mixing with the copolymer, or the crosslinking agent is added to the copolymer just prior to spraying without reacting the crosslinking agent with the copolymer.
wherein m and n have values of 1 to 99 and 99 to 1 respectively, and a crosslinking agent for crosslinking the polymer to itself and to the fibrous web, said agent being selected from dialdehydes and zirconium compounds wherein the zirconium has a valence of plus four and the crosslinking agent is added directly on the Yankee with the copolymer without prior mixing with the copolymer, or the crosslinking agent is added to the copolymer just prior to spraying without reacting the crosslinking agent with the copolymer.
102. The method of Claim 101 wherein the zirconium compound is selected from the group consisting of ammonium zirconium carbonate, zirconium acetylacetonate, zirconium acetate, zirconium carbonate, zirconium sulfate, zirconium phosphate, potassium zirconium carbonate, zirconium sodium phosphate and sodium zirconium tartrate.
103. The method of Claim 101 wherein the zirconium compound is ammonium zirconium carbonate.
104. The method of Claim 101 wherein about 0.1 to about 0.8 pounds of the adhesive are added for each ton of cellulosic papermaking fibers in the aqueous furnish.
105. The method of Claim 101 wherein the dialdehyde has the following structure:
wherein n is an integer having a value of 0 to 3.
wherein n is an integer having a value of 0 to 3.
106. The method of Claim 101 wherein the dialdehyde is glyoxal.
107. The method of Claim 101 wherein about 0.1 to about 10 pounds of cationic softener/debonder are added for each ton of the cellulosic papermaking fibers in the aqueous furnish.
108. The method of Claim 107 wherein a nitrogenous softener/debonder is
108. The method of Claim 107 wherein a nitrogenous softener/debonder is
108. The method of Claim 107 wherein a nitrogenous softener/debonder is selected from the group consisting of imidazolines, amido amine salts, linear amido amines, tetravalent ammonium salts, and mixtures thereof.
109. The method of Claim 108 wherein the salt has the following structure:
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is an anion.
[(RCO)2EDA]HX
wherein EDA is a diethylenetriamine residue, R is the residue of a fatty acid having from 12 to 22 carbon atoms, and X is an anion.
110. The method of Claim 109 wherein the salt has the following structure:
[(RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is an anion.
[(RCONHCH2CH2)2NR']HX
wherein R is the residue of a fatty acid having from 12 to 22 carbon atoms, R' is a lower alkyl group, and X is an anion.
111. The method of Claim 108 wherein the softener/debonder is a mixture of linear amido amines and imidazolines of the following structure:
wherein X is an anion.
wherein X is an anion.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US44394195A | 1995-05-18 | 1995-05-18 | |
| US08/443,941 | 1995-05-18 | ||
| CA002176898A CA2176898C (en) | 1995-05-18 | 1996-05-17 | Crosslinkable creping adhesive formulations |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002176898A Division CA2176898C (en) | 1995-05-18 | 1996-05-17 | Crosslinkable creping adhesive formulations |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2551236A1 true CA2551236A1 (en) | 1996-11-19 |
Family
ID=36998216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002551236A Abandoned CA2551236A1 (en) | 1995-05-18 | 1996-05-17 | Crosslinkable creping adhesive formulations |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2551236A1 (en) |
-
1996
- 1996-05-17 CA CA002551236A patent/CA2551236A1/en not_active Abandoned
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