Paper sizing composition.
Abstract
A stable paper sizing composition comprising a dispersion of ketene dimer and a pH adjusted vinylamine containing polymer is disclosed. The method of preparing the stable sizing composition and the method of using the stable sizing composition is also disclosed.
Term
No projected expiry on record.
- Priority
- Filed
- Granted
- Today
6 claims: 6 independent, 0 dependent
- 1CLAIMS REIVINDICACIONES A method of gluing paper that includes:Un método para encolar papel que comprende: adjust the pH of a vinylamine-containing polymer to give it 3.0 using an acid selected from the group, consisting of chlornhydric acid, methylsulfonic acid, hydrobromic acid, acid, nitric, formic acid and combinations thereof, producing a clear homogeneous solution, 2 ) mix the pH that. adjust to the 0-vinylamine-containing polymer with a ketene dimer dispersion, 3) hold the mixture of the vinylamine-containing polymer and the ketene dimer dispersion for at least one hour;4) Apply the mixture of the vinylamine-containing polymer and the ketene dimer dispersion to the pulp slurry or into. the gluing press. ajustar el pH de un polímero que contiene vinilamina débalo de 3.0 utilizando un ácido seleccionado del grupo, que consiste de ácido clornidrico, ácido metilsulfónico, ácido bromhídrico, ácido, nítrico, ácido fórmico y combinaciones de los mismos, produciendo una solución homogénea clara, 2) mezclar el pH que. se ajusta al polímero que contiene 0 vinilamina con una dispersión de dímero de cetena, 3) mantener la mezcla del polímero que contiene vinilamina y la dispersión, de dímero de cetena durante al menos una hora;4) aplicar la mezcla del polímera que contiene vinilamina y la dispersión de dímero de cetena a la lechada de pasta papelera o en. la prensa de encolado.
- 2The method according to claim 2. El método de conformidad con la reivindicación 1, en donde el pH del polímero que contiene vinilamina ajustada, se ajusta a hasta 2.5 o menos, 1, where the pH of the adjusted vinylamine-containing polymer is adjusted to up to 2.5 or less,
- 33 - The method according to claim 3 - El método de conformidad con la reivindicación 0 2, where the pH of the adjusted vinylamine-containing polymer is adjusted s 2.1 and 2.5. 0 2, en donde el pH del polímero que contiene vinilamina ajustada, se ajusta s 2.1 y 2.5.
- 4El método de conformidad con la reivindicación Four. The method according to claim 1, en donde el pH del polímero que contiene vinilamina se ajusta con acido clorhídrico. 1, wherein the pH of the vinylamine-containing polymer is adjusted with hydrochloric acid.
- 5A paper gluing method comprising:1) adjusting the pH of a vinylamine-containing polymer below 3> u using an acid selected from the group consisting of hydrochloric acid, methylsulfonic acid, hydrobromic acid, nitric acid, formic acid and combinations- of 5 the same, producing a clear homogeneous solution, 2) mix: the pH of the vinylamine-containing polymer adjusted with, a ketene dimer dispersion, wherein the ketene dimer is stabilized with a starch having a degree of substitution (DS) less than Q.05, before combining with 10 vinylamine, and where the loss of the active ketene dimer is not more than 10% in 4 weeks of storage at 32 ° C. 5. Ün método para encolar papel que comprende: 1) ajustar el pH de un polímero que contiene vinilamina debajo de 3>u utilizando un ácido seleccionado del grupo que consiste de acida clorhídrico, ácido metilsulfónice, acido bromhídrico, ácido nítrico, ácido fórmico y combinaciones- de 5 los mismos, produciendo una solución homogénea clara, 2) mezclar: el pH del polímero que contiene vinilamina ajustada con, una dispersión de dímero de cetena, en donde el dímero de cetena se estabiliza con un almidón que tiene un grado de sustitución (DS) menor a Q.05, antes de combinarse con 10 vinilamina, y en donde la pérdida del dímero de cetena activo es no es mayor de 10% en 4 semanas de almacenamiento a 32°C.
- 66, El método dé conformidad con la reivindicación 6, The method according to claim 5, en donde el pl-l del polímero que contiene vinilamina ajustada se ajusta a. 2.5 o menos. 5, wherein the pl-l of the adjusted vinylamine-containing polymer conforms to. 2.5 or less. 15 7. El método de conformidad con la reivindicación fifteen 7. The method according to claim S, en donde el pH del polímero que contiene, vinilamina ajustada se ajusta, a entre 2.1 y 2.5. S, where the pH of the polymer it contains, adjusted vinylamine is adjusted, to between 2.1 and 2.5. 3. The method according to claim 3. El método de conformidad con la reivindicación 5, en donde el ρΠ del polímero que contiene vinilamina se 20 ajusta con ácido clorhídrico. 5, where the ρΠ of the vinylamine-containing polymer is adjusted with hydrochloric acid.
Independent claims6
156 paragraphs in 5 sections, as filed
DIVISIONAL DEPUTY DIRECTOR OF PATENT FUND EXAMINATION BIOTECHNOLOGICAL, PHARMACEUTICAL AND CHEMICAL AREAS
EMELIA HERNÁNDEZ PRIEGO
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MX 2019 103106
PAPER GLUING COMPOSITION ·
FIELD OF XA INVENTION
This invention relates to improvements in gluing paper with aqueous ketene dimer dispersions and the stability of ketene dimer dispersions containing vinylamine-containing polymers.
BACKGROUND OF THE INVENTION
Weisgerber (US 2,961,366) teaches the use of polyvinylamine to improve retention of the ketene dimer by paper fibers, the increased retention resulting in a higher degree of sizing. In his teachings, Weisgerber indicated that polyvinylamine can be added separately from the sizing agent to the pulp slurry, although the preferred mode of addition was aqueous emulsion of the ketene dimer just prior to adding the ketene dimer to the system. of papermaking.
Since Weisgerber taught the addition of polyvinylamine to the aqueous ketene dimer emulsion just before adding the emulsion to the papermaking system, he had no interest in the long-term stability of the mixture. However, for aqueous alkyl ketene dimer emulsions to be commercially available they must be stable for extended periods of time. The aqueous emulsions of the ketene dimer must be stable both physically and chemically. Physical stability refers to the sufficiently stable viscosity at which the emulsions remain pumpable and dilutable until added to the papermaking system. Chemical stability refers to keeping the test for ketene dimer in the emulsion at a high level until added to the papermaking system.
The physical stability of ketene dimer emulsions has been the subject of several patents. For example, Edwards, et al. (US 4,861,376) teaches that combining small amounts of low molecular weight carboxylic acids with cationic starch, sodium lignosulfonate, and aluminum sulfate increases the colloidal stability of ketene dimer dispersions for more than four weeks at 32 ° C. Schimid, et al. (US2008 / 0041546 Al) also describes stable sizing compositions of reactive sizing agents. The emulsions of your invention are stabilized with a mixture of cationic starch with a DS> / = 0.05 anionic dispersant and a linear nitrogen-containing polymer. Although physical stability is demonstrated, chemical stability is not discussed.
Stable starch dispersions of the ketene dimer are well known in the industry, see, eg, US 4,861,376 to Edwards, et al., Or US
4,964,915 for Blixt, et al. Simple mixtures of these stabilized dispersions of ketene dimer with commercial polyvinylamine result in physically unstable products that gel within minutes. Mixtures of stabilized dispersions of ketene dimer starch and polyvinylamine, which have been pH adjusted as described in US 2008/0041546 Al, are also physically unstable, solidified in storage (see Example 5 of US 2008/0041546 To the).
SUMMARY OF THE INVENTION
It has been found that dispersions of ketene dimer containing vinylamine-containing polymers, such as polyvinylamine, that are both physically and chemically stable can be made by simple post-addition of the vinylamine-containing polymer to an adjustment ketene dimer dispersion. Adequate pH of the polymer co-containing vinylamine. Stable blends are achieved using polyvinylamine-containing polymers, such as polyvinylamine, which has been adjusted to a pH below about 3.3. It has also been found that aging these sizing compositions for a period of time before addition to the papermaking system can improve sizing efficiency.
A paper gluing composition is described.
The composition comprises a dispersion of the ketene dimer and a pH adjusted vinylamine containing polymer which are stable and provide improved sizing efficiency where the pH of the pH adjusted vinylamine containing polymer is below 3.3.
A method for preparing the stable size composition is described. The method comprises 1) adjusting the pH of a vinylamine containing polymer to below about 3.3, and 2) mixing the pH adjusted vinylamine containing polymer with a ketene dimer dispersion.
A method for gluing paper is described. The method comprises 1) adjusting the pH of a vinylamine-containing polymer to below about 3.3, 2) mixing the vinylamine-containing polymer adjusted pH with a ketene dimer dispersion, 3) support the mixture of the vinylamine-containing polymer and the ketene dimer dispersion for at least one hour and 4) apply the mixture of the vinylamine-containing polymer and the ketene dimer dispersion to the pulp slurry in a process of papermaking or applied to the gluing press.
In a preferred embodiment of the invention, the ketene dimer dispersion is a ketene dimer dispersion that is stabilized with starch.
DETAILED DESCRIPTION OF THE INVENTION
This invention provides paper sizing compositions comprising dispersions of ketene dimer and vinylamine-containing polymer, such as polyvinylamine, that are stable and provide improved sizing efficiency. Stable paper size compositions contain a vinylamine-containing polymer, a dispersant system, and an alkyl ketene dimer. These sizing compositions are prepared by 1) adjusting the pH of the polymer to below about 3.3 before mixing with the ketene dimer dispersion and then 2) mixing the polymer with a ketene dimer dispersion, and 3) aging in a manner Optional this blend before introducing into the papermaking system for optimal gluing performance. Preferably the ketene dimer dispersion is stabilized with starch.
The gluing compositions of the present invention are both physically and chemically stable. For purposes of this patent, a dispersion is said to be physically stable if the viscosity does not exceed approximately 400 cps for 4 weeks of storage at 32 ° C. The dispersion is said to be chemically stable if the test loss is not more than about 10% during the same 4 weeks of storage at 32 ° C. Assay refers to the amount of ketene dimer present in the initial emulsion formulation. The ketene dimer can be reacted with water over time to form what is commonly referred to as the diketone, which results in a loss of assay. Dicetone is not an effective sizing agent, so it is desirable to keep this loss to a minimum.
Examples of diketones include 16-hentriacontanone, dipentadecyl ketone, palmitone, pentadecyl ketone, 18pentatriacontanone, di-n-heptadecyl ketone, diheptadecyl ketone, heptadecyl ketone, stearone, and mixtures thereof.
Any of the ketene dimers known in the art can be used in the process of the present invention. The ketene dimex * s used as sizing agents are dimers having the formula:
wherein Rl and R2 are alkyl radicals, which may be saturated or unsaturated, having from 6 to 24 carbon atoms, preferably more than 10 carbon atoms and more preferably from 14 to 16 carbon atoms. Rl and
R2 can be the same or different. These ketene dimers are well known for example from the patent
2,785,067, description of which is incorporated herein by reference.
Suitable ketene dimers include decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosylketene dimers, as well as ketene dimers prepared from palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid, myristoleic acid, isostearic acid and eleostearic. The ketene dimer can be a single species or can contain a mixture of species. The most preferred ketene dimers are alkyl ketene dimers prepared from linear C12-C22 saturated natural fatty acids, oleic acid, isostearic acid, or mixtures thereof.
Suitable ketene dimers used as sizing agents are also known as: 4 ~ hep t ade c i1i den- 3 -hexade c i1-2 -Oxe t anona, · 2 ~ hexade c i1-3 hydroxy-3-Eicosenoic acid , β-lactone (6CI); Cetilcetena dimer; Hexadecylketene dimer; Palmitilcetena dimer;
4-heptadecyliden-3-tetradecyl-2-Oxetanone; 3-hexadecyl-4 pent.ad.ee i 1 iden-2 -Oxetanone; 4-pentadecyliden-3-tetradecyl-2Oxetanone; Miristilcetena dimer; Tetradecylketene dimer; 4- (15-meti.lhexadeciliden) -3- (14-met.ilpentadecil) -2-Oxetanone; dimer Isostear.ilcet.ena; 4- (8Z) -8-heptadecen-l-yliden-3- (7Z) 7-hexadecen-1-yl-2-Oxetanone; 4- (8-heptadecen.il i deno) -3- (7hexadecenil) -2-Oxetanone; 4- (8Z) -8-heptadeceniliden-3- (7Z) -7 hexadecenil-2-Oxetanone (9CI); Oleicocetena dimer; and mixtures thereof.
Starch stabilized dispersions of ketene dimers are well known in the art. Such dispersions comprise a cationic starch, an anionic dispersant, and may contain some levels of aluminum sulfate or a polyaluminium salt. Cationic starch is any water soluble starch that carries enough cationic amino groups to supply the positively charged starch in solution. The degree of preference substitution is less than 0.05 and more preferably less than 0.048 and greater than 0.042. Preferred starches are cationic waxy corn starches with quaternary amino groups as the loading source, such as StaLok 169 (sold by Tate & Lile). Suitable anionic dispersants include lignosulfonates, polynaphthalene sulfonates, and polymers containing styrene sulfonate. Sodium lignosulfonate is preferred. Examples of such dispersions can be found in US Patent No. 4,964,915 to Blixt, et al., US Patent No. 4,861,376 to Edwards, et al., And US Patent No. 3,223,544 to Savina, descriptions of which are incorporated in this for reference, as well as the references contained in these documents.
The pH of the starch stabilized ketene dimer emulsion used in the present invention is preferably below 5.0, more preferably below 4.5, and most preferably 4.3 or below.
Technically, the term emulsion refers to a two-phase system with liquid droplets in a continuous liquid medium, and the term dispersion refers to a two-phase system with solid particles in a continuous liquid medium. The physical state of the alkyl ketene dimer depends on the temperature of the system and the fatty acids used to prepare the ketene dimer; the alkyl ketene dimer in commercial sizing agents can be liquid or solid. As a result, the two terms are used interchangeably when referring to commercial sizing agents in industry and in this patent.
These emulsions can include other common additives for gluing emulsions, such as biocides, antifoams, etc.
The term "vinylamine-containing polymers" is understood to mean vinylamine homopolymers (eg, fully hydrolyzed polyvinylamine or polyvinylformamide), vinylamine copolymers with other comonomers, partially hydrolyzed polyvinylformamide, partially hydrolyzed vinylformamide copolymers, vinylamine terpolymers, homo-polymers. vinylamine made by Hofmann's modification of acrylamide polymers. Examples of such polymers can be found in US Patent No. 6,159,340 to Niessner, et al.
The vinylamine-containing polymer used in the process of the present invention is preferably selected from the group consisting of vinylamine homopolymer (i.e. polyvinylamine), vinylamine copolymer, vinylamine terpolymers, homo and vinylamine copolymers manufactured by the Hofmann modification of acrylamide polymers or chemically modified vinylamine-containing polymers after polymerization. The most preferred vinyl amine containing polymer in the process of the present invention is polyvinylamine.
The molecular weight of the polymers of the present invention is important for use as a papermaking additive. If he. molecular weight is very low, the polymer may have poor retention on the pulp fiber. If the molecular weight is very high, the polymer tends to coagulate before bonding with the fiber, which reduces the effectiveness of the polymer. The molecular weight (Mw) of the vinylamine-containing polymers used to prepare the present invention are in the range of 4,000; 10,000; 20,000; 50,000; 75,000; 100,000; 150,000; or 2 00,000 to 4 0 0,000; 45 0,000; 500,000; 600,000; 700,000;
800,000; or 1,000,000; preferably from 4,000 to 1,000,000 Daltons, most preferably from 10,000 to 1,000,000 Daltons, most preferably in the range of 20,000 to 800,000 Daltons, most preferably in the range of 50,000 to 700,000 Daltons, most preferably in the range of 75,000 to 600,000 Daltons, most preferably in the range of 100,000 to 500,000 Daltons, most preferred in the range of 150,000 to 450,000 Daltons, and most preferably in the range of 200,000 to 400,000 Daltons.
The vinylamine-containing polymer used in the process herein can be a fully or partially hydrolyzed polyvinylformamide. The percent hydrolysis of polyvinylformamide, for example, to generate vinylamine-containing polymers used to prepare the present invention is in the range of 10; twenty; 30; 40; or 50 to 60; 70; 80; 90; or 100; preferably 30 to 100%, more preferably 4 to 100%, more preferred in the 50 to 100% range, more preferred in the 60 to 100% range, more preferred in the 70 range to 100%, more preferably in the range of 80 to 100, much more preferred in the range of 90 to 100%,
In addition to the primary amine portions, the partially hydrolyzed polyvinylformamide and vinylamine copolymers usually randomly comprise distributed amidine functional groups. The level of amidine is functionally dependent on hydrolysis conditions such as time, temperature, caustic amount, and other factors.
To prepare the sizing compositions of this invention, the pH of the vinylamine-containing polymer, such as polyvinylamine, must first be adjusted to the stable pH below about 3.3. A pH below 3.0 is preferred, more preferably below 2.5, and much more preferably a pH between 2.1 and 2.5. The pH adjusted polymer of vinylamine must be a clear and homogeneous solution. The pH adjustment can be done using mineral or organic acids. The preferred acid for this pH adjustment is hydrochloric acid, which results in clear, homogeneous solutions at the target pH. The use of sulfuric acid, for example, results in a heterogeneous polyvinylamine solution that is not usable. Organic acids (eg formic acid) can also be used. Other commercially available acids include methylsulfonic acid, hydrobromic acid, phosphoric acid, and nitric acid.
The pH adjusted polymer is added to the alkyl ketene dimer dispersion with good agitation at a level that achieves the desired casting performance. Polymer levels of 0.5% to 100%, based on alkyl ketene money, can be used. Polymer levels of 5% to 50%, based on the alkyl ketene dimer, are preferred. Higher levels of polymer provide higher levels of bond development. The final emulsion pH should be less than about pH 3.
The sizing compositions of this invention can be used immediately, although it has been found that for optimal sizing the blends can be held or aged for several hours before being used. Aging sizing compositions significantly increases the amount of sizing developed with a given amount of alkyl ketene dimer and polymer, significantly boosting casting efficiency. It is preferred that a minimum waiting time, for aging the composition, be one hour or much more preferably three hours. Preferably the waiting time is from about 3 hours to about 8 hours. The composition can be kept for more than 8 hours. Waiting time greater than 8 hours does not add any additional significant increase to performance.
Sizing agents prepared by the invention can be used in internal sizing where the sizing devices are added to the pulp slurry in the wet part of the. papermaking process, or surface gluing in which the gluing dispersions are applied in the gluing press or coater. This invention can also be used on one or both parts of a two-part gluing system. For example, one wall can be mixed internally with wood pulp and a second part applied to the gluing press, a common practice in papermaking.
The amount of sizing agent either added to the pulp or applied as a surface sizing is about 0.005 to 5% by weight of the reactive sizing agent, based on the dry content of the pulp, i.e. fibers and optional filler, and preferably from 0.01 to 1% by weight. The dosage mainly depends on the quality of the pulp or paper to be glued, the gluing compound used and the desired gluing level.
Chemicals conventionally added to pulp in paper or cardboard production, such as processing aids (eg, retention aids, drainage aids, contaminating control additives, etc.) or other functional additives (eg, dry or wet strength, dyes, optical brightening agents, etc.) can be used in combination with the sizing agents of this invention.
The following examples are provided for the purpose of illustrating the present invention. All parts and percentages are by weight unless otherwise indicated.
In the following examples, sizing evaluations were performed using a model scale paper machine designed to simulate a commercial Fourdrinier, including pulp preparation, refinement, and storage. The pulp was gravity fed from the machine box to a constant level pulp tank. From there, the pulp was pumped to a series of in-line mixers where wet-part additives were added, then to the primary fan pump. Pulp 15 was diluted with turbulence in the fan pump at approximately 0.2% solids. Furthermore, chemical additions can be made to the pulp entering or leaving the fan pump. The pulp was pumped from the primary fan pump to a second secondary fan pump, where the chemical additions were made to the inlet pulp, then to a flow spreader and to a slider, where it was deposited on the Fourdrinier wire. 30.48 cm (12 inches) wide. Immediately after deposition on the wire, the sheet was dehydrated under vacuum 25 using three vacuum boxes; the consistency of the suction roller was normally 14-15%.
The wet sheet was transferred from the suction roll to a motor-driven moisture absorption filter. At this point, the water was removed from the sheet and filter by vacuum suction boxes operated from a vacuum pump. The sheet is further dehydrated in a single felt press and left the press section with 38-40% solids.
Evaluations were performed on a recycled and simulated cardboard paper pulp for coating using a mixture of recycled media (80%) and old newsprint (20%) with a refined Canadian standard of 350 cc with 2.75% sodium lignosulfonate added to simulate anionic waste. The hardness and alkalinity were 126 ppm and 200 ppm, respectively. Additional levels for all additives were provided in weight percent based on the dry weight of the fiber. 0.3% cationic dentate corn starch (Sta-Lok 300, Tate & Lyle) was added to the thick pulp before adding the sizing agent. No other wet part additive was used. The pulp temperature was maintained at 55 ° C. The pH of the inlet box was controlled to 7.5 with caustic soda.
A sheet of 171 g / m2 (105 lbs / 3000 ft2 ream) was formed and dried in seven dryer cylinders for 7% portions (surface temperature of the dryer cylinder at 90 ° C) and passes through a single contact pulp by calender roll 6 contact 5. Sizing HST and Cobb were measured on naturally aged cardboard in a fourth CT (50% RH, 25 ° C) for a minimum of 7 days.
AKD Emulsion: Hercon® 100 Gluing Agent, a cationic starch stabilized emulsion of the alkyl ketene dimer (Hercules Incorporated, Wilmington DE). The pH specification for this product is 2.1-4.2.
Polyvinylamine 1: A cationic polymer which was obtained by hydrolysis of poly-N-vinyl.ilformamide with a nominal 100% degree of hydrolysis. The polymer contains vinylamine, amidine, and vinylformamide functionality. Available from Hercules Incorporated as Hercobond® 6363 (Hercúlea Incorporated, Wilmington DE).
Polyvinylamine 2: A cationic polymer which was obtained by hydrolysis of poly-N-vinylformamide with a nominal 50% degree of hydrolysis. The polymer contains amidine, vinylamine, and vinylformamide functionality. Available from Hercules Incorporated as Hercobond® 6350 (Hercules Incorporated, Wilmington DE).
Example 1: Adjusting the polymer pH to low pH provides stable mixes
PH adjustment of polyvinylamine resin:
35% HC1 was slowly added to Polyvinylamine 1 with good stirring. The pH was monitored as HC1 was added. The amount of HC1 was adjusted as necessary to achieve the desired pH target. The pH was rechecked after several hours to ensure that the pH was stable. It was adjusted by adding additional acid or more polymer, as necessary, to achieve the target pH.
Preparation of the mixture:
The pH adjusted polyvinylamine was added slowly to the starch stabilized AKD emulsion, while stirring. A sufficient amount of pH adjusted polyvinylamine was added to provide 12.5% polymer based on an alkyl ketene dimer.
The physical and chemical stability of these mixtures was determined as it was made and after aging for 2 and 4 weeks in an oven at 32 ° C. Viscosity was used as a measure of physical stability. Viscosity was measured with a Brookfield viscometer at 60 rpm, using the appropriate head. Chemical stability was determined using an IR method to determine the level of active alkyl ketene dimer in the emulsions.
Table 1. Impact of polymer pH on the physical and chemical stability of the gluing composition, using hydrochloric acid for pH adjustment.
<td rowspan="2"></td><td colspan="3">Physical stability</td><td colspan="4">Chemical stability</td>
<td colspan="3">Brookfield Viscosity 60 Γ £ ίΠ</td><td colspan="3">Diarero Trial</td><td>Lost</td>
<td>pH of íVtei</td><td>coico was made</td><td>2 weeks to 32<sup>and</sup>C</td><td>4 seroanas at 32'C</td><td>it was made</td><td>2 sessanAS at 32 * C</td><td>4 weeks to 32<sup>and</sup><2</td><td>of testing</td>
<td>Iajustada</td><td>(Cps)</td><td>(cps)</td><td>(cps)</td><td>% in weigh</td><td>9 o »weight</td><td>in weigh</td><td></td>
<td> 2.1</td><td> 96</td><td> 130</td><td> 118</td><td> 10.4</td><td> 10</td><td> 9.6</td><td> 8%</td>
<td> 2.5</td><td> 76</td><td> 108</td><td> 96</td><td> 10.2</td><td> 9.6</td><td> 9.4</td><td> 8%</td>
<td> 2.9</td><td> 124</td><td> 169</td><td> 176</td><td> 10.4</td><td> 10.0</td><td> 9.5</td><td> 9%</td>
<td> 3.3</td><td> 260</td><td> 448</td><td> 388</td><td> 10.6</td><td> 9.8</td><td> 9.4</td><td> 11%</td>
<td> 3.7</td><td> 375</td><td> 522</td><td>582, ν »little</td><td> 10.7</td><td> 9.80</td><td> 9.6</td><td> 10%</td>
<td> 5.0</td><td> 312</td><td>mellified</td><td>from gal</td><td> 10.9</td><td> 8.80</td><td></td><td> 19%</td>
<td>to adjust</td><td>gelrfioadc</td><td> —</td><td></td><td> —</td><td> —</td><td> --</td><td> »«.</td>
Clearly, at pH 3.3 and above emulsions containing (polyvinylamine) PVAm resin increase in viscosity and loss of physical stability. At pH 5, chemical stability was poor. It is preferred that the PVam is set below 3.0 before combining with the ketene dimer.
Example 2: Organic acids can also be used for pH adjustment.
The pH adjustment of the resin and preparation of the mixtures was the same as in Example 1, substituting hydrochloric acid for formic acid.
Table 2. Impact of polymer pH on the physical and chemical stability of the gluing composition, using formic acid for pH adjustment.
<td rowspan="3">pH of PVAa after adjustment</td><td colspan="3">Physical Stability í</td><td colspan="3">Chemical stability</td>
<td colspan="3">Bxookfi viscosity ^ ld. 60 rpm</td><td colspan="2">Díjoero's Essay</td><td rowspan="2">Loss of « Test %</td>
<td>(cps)</td><td>2 weeks at 32 * 0 (cps)</td><td>4 sheets to SJ'Cl<sup>50</sup>® * 'hizc (cps) |<sup>4 cocoa</sup></td><td>2 soiaanas at 32<sup>9</sup> C% by weight</td><td>4 weeks at 32 ° C wt%</td>
<td> 3.8</td><td>Ϊ48</td><td> 347</td><td>g-slIFIC cactus | i 0.1</td><td> 9.5</td><td> 9.0</td><td> 11%</td>
<td> 2.1</td><td> 78</td><td> 84</td><td> 85 | 10.6</td><td> 9.8</td><td> 9.6</td><td> 9%</td>
As with hydrochloric acid, adjusting a low pH provided physical stability.
An attempt was made to adjust the turned below
PVAm with sulfuric acid, although the resin is a useless heterogeneous viscous mass due to a pH of around
Example 3; The sizing performance for the sizing composition of this invention is far superior to that of mixing by mixing the resin with the sizing agent at the point of addition:
A sizing composition prepared as described in Example 1 using Polyvinylamine 1 adjusted to pH 2.1. This gluing composition was evaluated on a model papermaking machine, as described above after aging for 1 hour, 5 hours and 24 hours. Compared with Hercon 100 sizing agent without polymer, and with polymer added to the point of addition (T'd at point of addition) in the same proportion as the alkyl ketene dimer used in the sizing compositions (12.5% based on the dimer). Gluing was measured using the Hercules Gluing Test (Tappi Method T 530) and the Cobb Test (Tappi Method T 441). In the larger Hercules Gluing Test numbers (longer penetration times) they indicated improved gluing performance. The lower Cobb Test numbers (lower water absorption) indicated improved gluing performance. The results are presented in Table 3.
Table 3. Aging the sizing compositions of this invention significantly boosts casting efficiency.
<td></td><td></td><td>HST</td><td>20% FA ÍNK</td><td>CCBB TEST</td><td>SOAK 2 MINUTES</td>
<td></td><td></td><td> 5</td><td>REFL.</td><td>2 Reps</td><td>IN WATER</td>
<td></td><td>Dimer</td><td>Seconds</td><td></td><td>g / m square</td><td></td>
<td></td><td>Addicton%</td><td>Half</td><td>Standard deviation</td><td>Half</td><td>Standard deviation</td>
<td>Without PVAm</td><td> 0.100</td><td> 3</td><td></td><td> 321</td><td> 3.54</td>
<td>Without PVAm</td><td>0.2ÓÓ</td><td> 12</td><td></td><td> 161</td><td> 7.07</td>
<td>Without PVAm</td><td> 0,300</td><td> 39</td><td> 1.48</td><td> 66</td><td> 2.83</td>
<td></td><td></td><td></td><td></td><td></td><td></td>
<td>PVAm T'd at sdidcc point</td><td> 0.050</td><td> 2</td><td></td><td> 332</td><td> 3.54</td>
<td>PVAm Td at rush point</td><td> 0.150</td><td> 22</td><td> 1.41</td><td> 74</td><td> 1.41</td>
<td>PVAm Td at point of addition</td><td> 0.250</td><td> 165</td><td> 8.00</td><td> 35</td><td> 0.71</td>
<td>Example 1: aging during i hr.</td><td> 0.050</td><td></td><td></td><td> __</td><td> _..........</td>
<td>Example l: erive.edrriiento during 11r.</td><td> 0.150</td><td> 60</td><td> 2.77</td><td> 34</td><td> 0.00</td>
<td>Example i: ensx? ToQfni «nto for 1 hr.</td><td> 0.250</td><td> 276</td><td> 14.30</td><td> 31</td><td> 0.00</td>
<td></td><td></td><td></td><td></td><td></td><td></td>
<td>Example 1: aging for 5 hr.</td><td> 0.050</td><td></td><td></td><td> 269</td><td> 9.90</td>
<td>The beginning <; aging for 5 hr.</td><td> 0.150</td><td> ¿3</td><td> 0.58</td><td> 35</td><td> 2.12</td>
<td>Example: aging. For 5 hr</td><td> 0.250</td><td> 379</td><td> 19.60</td><td> 30</td><td> 0.00</td>
<td>Example 1: aging for 24 years</td><td> 0.050 ;</td><td> ..............._..............</td><td></td><td> 273</td><td> 3.54</td>
<td>Example 1: aging for 24 hr.</td><td> 0.150 !</td><td> 84</td><td> 2.30</td><td> 33</td><td> 0.00</td>
<td>Example »1: aging for 24 hr.</td><td> 0.250</td><td> 383</td><td> 13.15</td><td> 30</td><td> 0.71</td>
This example demonstrates the improved sizing performance of the sizing compositions of this invention. As Weisgerber teaches, adding PVAm to an AKD emulsion improves gluing performance; compare<sup>!</sup>Without PVAm 'with' PVAm T'd at the point of addition. However, with the aged size compositions of this invention, it is possible to develop an even higher level of size with the same amounts of alkyl ketene dimer and polymer; Compare 'PVAm T'd at point of addition' with any of 5 data sets in 'Example 1'.
Example 4: A sizing composition was prepared using Polyvinylamine 2, as described in Example 1, adjusting the pH of the polyvinylamine to 2.1. This product, named as Example 4, was compared to Example 1 on the model paper machine as described above, after the size composition was aged for several days. The results are summarized in Table 4.
Table 4. Polyvinylamine with a lower level of hydrolysis can also be used in the sizing compositions of this invention.
<td></td><td></td><td>H8T</td><td></td><td>COB8 TEST</td><td></td>
<td></td><td></td><td>5í? Eps</td><td></td><td>2 Reps</td><td></td>
<td></td><td></td><td>2¿% FA Ínk / 80% RefÍ</td><td></td><td>2min / WATER</td><td></td>
<td></td><td>Dlmeix)</td><td>seconds</td><td></td><td>g.'m square</td><td></td>
<td></td><td>% of addition</td><td>You measure</td><td>Dev. Esisnd.</td><td>Macha</td><td>Dev. Stand</td>
<td>Without PVAra</td><td> 0.1</td><td> 5</td><td> 0,00</td><td> 257.0</td><td> 5.66</td>
<td>FVAm</td><td> 0.2</td><td> 15</td><td> 0.84</td><td> 129 5</td><td> 0.71</td>
<td>Without PVAm</td><td> 0.3</td><td> 49</td><td> 3.29</td><td> 61.5</td><td> 2.12</td>
<td></td><td></td><td></td><td></td><td></td><td></td>
<td>Example 4</td><td> 0.05</td><td> 5</td><td> 0.00</td><td> 198.0</td><td> 8.49</td>
<td>Example 4</td><td> 0.15</td><td> 74</td><td> 4.51</td><td> 37.0</td><td> 2.83</td>
<td>Example 4</td><td> 0.25</td><td> 345</td><td> 11.90</td><td> 29.0</td><td> 1.41</td>
<td></td><td></td><td></td><td></td><td></td><td></td>
<td>Example i</td><td> 0.05</td><td> 6</td><td> 0.00</td><td> 137.5</td><td> 2.12</td>
<td>Example 1</td><td> 0 15</td><td> 118</td><td> 6.89</td><td> 30.0</td><td> 0.00</td>
<td>Ejsmpko 1</td><td> 0.25</td><td> 390</td><td> 34.15</td><td> 26.5</td><td> 0.71</td>
Both polyvinylamines resulted in a substantial gluing improvement, as reflected in higher HST gluing numbers and lower Cobb numbers.
Example 5. Varied ratios of ketene dimer to polyvinylamine
The sizing compositions were prepared as in Example 1 by varying the ratio ratio of polyvinylamine to dimer. Polyvinylamine 1 adjusted to pH 2.1 with hydrochloric acid was used in all cases. These gluing compositions were evaluated on the model paper machine as described above. The results of the gluing tests on the prepared cardboard are listed in Table 5.
Table 5. Increasing the amount of the polyvinylamine resin improves the gluing performance.
<td></td><td></td><td colspan="2">HST</td><td colspan="2">| OE COBB TEST</td>
<td></td><td></td><td colspan="2">20% FA</td><td colspan="2">| soak 2 minutes</td>
<td></td><td></td><td colspan="2">80% Reflection</td><td colspan="2">| in water</td>
<td>% of PVAm</td><td></td><td colspan="2">Seconds</td><td colspan="2">j Qlm square</td>
<td>based on dimer</td><td>Dimer%</td><td>Half</td><td>Dev. EsSand</td><td>Half</td><td>Dev. Esiand.</td>
<td> 0</td><td> 0.100</td><td> 8</td><td> 1</td><td> 236</td><td> 4.95</td>
<td></td><td> 0.200</td><td> 39</td><td> 2</td><td> 79</td><td> 3.54</td>
<td></td><td> 0.300</td><td> 133</td><td> 3</td><td> 41</td><td> 0.71</td>
<td> 5</td><td> 0.050</td><td> 10</td><td> 1</td><td> 158</td><td> 39.60</td>
<td></td><td> 0.150</td><td> 128</td><td> 6</td><td> 33</td><td> 1.41</td>
<td></td><td> 0.250</td><td> 831</td><td> 10</td><td> 32</td><td> 1.41</td>
<td> 10</td><td> 0.050</td><td> 7</td><td> 0</td><td> 240</td><td> 2.12</td>
<td></td><td> 0.150</td><td> 152</td><td> 5</td><td> 35</td><td> 2.12</td>
<td></td><td> 0.250</td><td> 966</td><td> 45</td><td> 27</td><td>b.ób</td>
<td> 19</td><td> 0.050</td><td> 7</td><td> 0</td><td> 220</td><td> 2.83</td>
<td></td><td> 0.150</td><td> 172</td><td> 4</td><td> 34</td><td> 1.41</td>
<td></td><td> 0.250</td><td> 1608</td><td> 147</td><td> 31</td><td> 2.83</td>
As demonstrated by these data, increasing the amount of polyvinylamine in the blend improves the sizing performance, although significant increases are observed in relatively low levels of polymer.
Example 6:
A size composition was prepared as described in Example 1 using Polyvinylamine 1 adjusted to pH 2.1. This gluing composition was evaluated on a commercial paper machine after aging for 1 week. It was compared to Hercon 118 sizing agent, which is a promoted alkyl ketene dimer emulsion (Hercules Incorporated, Wilmington DE). Gluing was measured using the Cobb Test. The results are presented in Table 6. The sizing composition of this invention was able to meet the sizing goals at a 24% lower addition level than the title product.
Table 6. Commercial evaluations showed improvements in efficiency
<td></td><td>addition index | deAKD,%</td><td>2 min Cobb, g / m squared average</td><td>10 minutes. Cobb, average g / m squared</td><td>% improvement</td>
<td>sanding: white top coat # 42 Hercon 118</td><td> 0.175</td><td> 43</td><td> 107</td><td></td>
<td>Example 6</td><td>0.133 i</td><td> 46</td><td> 113</td><td> 24.1</td>
This example shows that the amount of sizing used for the inventive material is approximately 24% less than the commercial material while resulting in a normal level of support for Cobb.
Contents5
29 members in 15 offices
Priority claims7
| Document | Office | Kind | Date |
|---|---|---|---|
| 28782209 | United States of America | P | |
| 61287822 | United States of America | – | |
| 2010060984 | United States of America | W | |
| 61287822 | – | – | – |
| PCTUS2010060984 | – | – | – |
| US20090287822P | – | – | – |
| WO2010US60984 | – | – | – |
Members29
| Document | Office | Kind | |
|---|---|---|---|
| CA2784322A1 | Canada | A1 | |
| US2011146926A1 | United States of America | A1 | |
| WO2011075633A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2011075633A3 | World Intellectual Property Organization (WIPO) | A3 | |
| TW201137200A | Taiwan Province of China | A | |
| AU2010330791A1 | Australia | A1 | |
| MX2012006279A | Mexico | A | |
| CN102656317A | China | A | |
| KR20120102706A | Republic of Korea | A | |
| EP2513373A2 | European Patent Office (EPO) | A2 | |
| JP2013515176A | Japan | A | |
| EP2513373B1 | European Patent Office (EPO) | B1 | |
| ES2432239T3 | Spain | T3 | |
| PT2513373E | Portugal | E | |
| US8632659B2 | United States of America | B2 | |
| RU2012130159A | Russian Federation | A | |
| PL2513373T3 | Poland | T3 | |
| US2014090791A1 | United States of America | A1 | |
| JP5680670B2 | Japan | B2 | |
| US9028650B2 | United States of America | B2 | |
| TWI493087B | Taiwan Province of China | B | |
| RU2564817C2 | Russian Federation | C2 | |
| AU2010330791B2 | Australia | B2 | |
| CN102656317B | China | B | |
| BR112012014455A2 | Brazil | A2 | |
| KR101753436B1 | Republic of Korea | B1 | |
| CA2784322C | Canada | C | |
| MX369909BThis record | Mexico | B | |
| BR112012014455B1 | Brazil | B1 |
Numbers
- Publication
- 369909
- Publication, DOCDB
- 369909
- Publication, EPODOC
- MX369909
- Application
- 2014008977
- Application, DOCDB
- 2014008977
- Application, EPODOC
- MX20140008977
Titles2
- English
- PAPER SIZING COMPOSITION.
- Spanish
- COMPOSICION DE ENCOLADO DE PAPEL.
Classification
- CPC, 6
- D21H17/17
- D21H21/16
- D21H19/10
- D21H17/45
- D21H17/56
- D21H21/14
- IPC, 3
- D21H17 17
- D21H19 10
- D21H21 16