CN1262710C - Paper sizing composition - Google Patents

Paper sizing composition Download PDF

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Publication number
CN1262710C
CN1262710C CNB008196435A CN00819643A CN1262710C CN 1262710 C CN1262710 C CN 1262710C CN B008196435 A CNB008196435 A CN B008196435A CN 00819643 A CN00819643 A CN 00819643A CN 1262710 C CN1262710 C CN 1262710C
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Prior art keywords
weight
composition
aluminium
acid
sizing agent
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CNB008196435A
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CN1454274A (en
Inventor
林庭东
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Suo Li Cisco skill Cayman company
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Hercules LLC
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D21H17/15—Polycarboxylic acids, e.g. maleic acid
    • D21H17/16—Addition products thereof with hydrocarbons
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/17—Ketenes, e.g. ketene dimers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/23—Lignins
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/66—Salts, e.g. alums

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention discloses a paper sizing composition which comprises cellulose activity sizing agent (a), a dispersion system (b) containing negative ion main dispersing agent and subsidiary dispersing agent selected from cation and/or non-ion dispersing agent and inorganic salt (c).

Description

Paper glueing composition
Technical field
The present invention relates to paper glueing composition, comprise: a) sizing agent, b) dispersion, and c) inorganic salts; In addition, the invention still further relates to and utilize the method for described composition paper sizing, and the product that utilizes described glueing composition to make.
Background technology
The cellulolytic activity sizing agent, be widely used in the paper industry as the component of alkyl ketene dimer (AKD) as the size dispersions prescription.The serviceability of described sizing agent derives from it and directly is bonded to ability on the plain component hydroxyl of paper fibre.Frequently, in these applying glue prescriptions, sizing agent for example AKD mixes with the dispersion that comprises cationic starch and/or lignin sulphonyl sodium.The example of described dispersion can be at US4, and 861,376 (Edwards) and US3 find among 223,544 (Savina).At this these two pieces of documents are incorporated herein by reference.
Inorganic salts such as alum or contain the salt of aluminium, the serviceability in paper-making process has also been known a period of time.In fact, by increasing dehydration, these salt have improved the production capacity of paper machine widely.Usually, the concentration of salt is high more, water separation capability is just strong more.
Therefore, the mixture of organic sizing agent such as AKD dispersion and inorganic salts such as alum is valuable mixture, and it not only provides glue blending function but also water separation capability is provided.The example of described mixture is listed in US5, and 145,522 (people such as Nakagawa) and US5 among 627,224 (people such as Lyrmalm), are introduced into as a reference at this.Yet the problem that this mixture ran into is: organic sizing agent is often incompatible especially with inorganic salts, if the concentration of inorganic salts becomes too high in organic size dispersions liquid phase, will isolate.
Thereby this area needs a kind of dispersion compatible with organic sizing agent with inorganic salts.Many dispersions have been described in the literature.For example, US5, in 627,224, with amphiphilic polymers as unique dispersant, so that the polymeric aluminum compound is introduced in the dispersion of AKD.Yet it is elusive making the composition that comprises organic sizing agent and inorganic salts obtain good stable always.Therefore, this area needs a kind of composition that addresses the above problem.
Summary of the invention
According to noted earlier, the purpose of this invention is to provide and have the size dispersions that improves stability.
Another object of the present invention provides the size dispersions that strengthens water separation capability.
Another object of the present invention provides size dispersions, and described dispersion comprises the inorganic salts of organic sizing agent and variable concentrations, comprising high inorganic salt concentration.
In addition, the invention still further relates to and comprise (a) cellulolytic activity sizing agent, (b) and comprise the dispersion of main dispersant and auxilliary dispersant and (c) composition of inorganic salts; With described composition manufacturing method and using method; And the product that comprises described composition.
By providing a kind of Aquo-composition to realize the present invention, said composition comprises the cellulolytic activity sizing agent, comprises the dispersion and at least a salt that is equal to or greater than about 5.5% weight aluminium element in cellulolytic activity sizing agent weight of anionic dispersing agents and at least a cation dispersing agent or non-ionic dispersing agent.In preferred embodiments, the cellulolytic activity sizing agent comprises at least a in ketene dimer and the ketenes polymer; More preferably, ketene dimer comprises at least a in thiazolinyl ketene dimer and the alkyl ketene dimer.In another embodiment preferred, the cellulolytic activity sizing agent comprises at least a in enetutanedioic acid anhydride and the stearic anhydride.
The cellulolytic activity sizing agent can comprise: contain about 12 organic epoxides to about 22 carbon atoms, contain about 12 acyl halides to about 22 carbon atoms, contain about 12 to the fatty acid anhydride of about 22 carbon atoms or contain about 12 organic isocyanates to about 22 carbon atoms.
Preferably, described composition comprises ketene dimer or the ketenes polymer of structural formula I:
N is the integer of 0-about 20 in the formula, R and R 2Identical or different and be to have about 6 to about 24 carbon atoms, saturated or undersaturated alkyl, and R 1For having about 2 to about 40 carbon atoms, saturated or undersaturated alkyl.Preferably, n from 0 to about 6; More preferably, n from 0 to about 3; And most preferably, wherein n is 0.R has about 10-20 carbon atom, saturated or undersaturated alkyl; Preferably R has about 14-16 carbon atom, saturated or undersaturated alkyl.R 2Be preferably and have about 10-20 carbon atom, saturated or undersaturated alkyl; More preferably, R 2For having about 14-16 carbon atom, saturated or undersaturated alkyl.Preferential is R 1For having about 4 to about 40 carbon atoms, saturated or undersaturated alkyl.
Described anionic dispersing agents can comprise: the polymeric dispersant of sulfur-bearing hydrochlorate or sulfonate.Described anionic dispersing agents comprises the formaldehyde condensation products of sodium naphthalene sulfonate, the formaldehyde condensation products of Negel, the formaldehyde condensation products of sodium phenolsulfonate, the formaldehyde condensation products and the lignosulphonates of phenol sodium sulphate, and described lignosulphonates preferably comprise sodium lignosulfonate.Preferably, sodium lignosulfonate comprises: in the sodium lignosulfonate gross weight, contain be less than about 5.9% weight, preferably be less than about 5% weight, more preferably less than about 4.5% weight, more preferably less than about 4% weight and most preferably be less than the sodium lignosulfonate of about 3.6% weight sulfonate sulphur.
The content of anionic dispersing agents can for cellulolytic activity sizing agent weight about 0.02 to about 20% weight, more preferably from about 0.4 to about 7% weight, most preferably from about 0.9 to about 3% weight.
Preferred compositions comprises cation dispersing agent, the preferably cation-modified starch of described cation dispersing agent, cation-modified guar gum or low electric charge cationic polymer.Preferably, composition comprises cation-modified starch, its content be cellulolytic activity sizing agent weight about 0.4 to about 400% weight, more preferably from about 2 to about 100% weight, most preferably from 10 to about 30% weight.
Described salt can comprise the metal that is selected from I, II, III, IV, V family and transition elements, with and the combination.Preferably, described salt comprises aluminium, magnesium, calcium or barium.Preferably, described composition comprises formula Al x(SO 4) y(H 2O) zAluminium salt, x is 1-3 in the formula, y is 1-4, z is 0-20.Preferably, aluminium salt is aluminum sulfate.Aluminium salt also can have formula Al n(OH) mX 3n-m, X is an anion in the formula, and n and m are the integer greater than zero, and 3n-m is greater than zero.In described salt, anion preferably comprises chloride or acetate and described aluminium salt and comprises aluminium polychloride.
In one aspect of the invention, the content of described salt is equivalent to about 5.5% weight aluminium to about 10% weight aluminium in cellulolytic activity sizing agent weight; More preferably, its content is equivalent to about 6% weight aluminium to about 8% weight aluminium in cellulolytic activity sizing agent weight.
In addition, by being provided, a kind of Aquo-composition realized the present invention, described composition comprises the cellulolytic activity sizing agent, the dispersion and at least a salt that is equal to or greater than about 0.2% weight aluminium element in cellulolytic activity sizing agent weight that contains that one of comprise in the sodium lignosulfonate of modification and cation dispersing agent, non-ionic dispersing agent and its combination at least.In described composition, in cellulolytic activity sizing agent weight, the content of described salt is equivalent to or greater than the aluminium of about 0.4% weight.Preferably, in cellulolytic activity sizing agent weight, the content of described salt be equivalent to or greater than about 1.5% weight, more preferably be equivalent to or greater than about 3% weight, more preferably be equivalent to or greater than about 4.4% weight, more preferably be equivalent to or greater than about 5.5% weight, most preferably be equivalent to or greater than the aluminium of about 6% weight.
Composition can comprise salt, in cellulolytic activity sizing agent weight, its content be equivalent to or be less than about 40% weight, more preferably be equivalent to or be less than about 30% weight, more preferably be equivalent to or be less than about 20% weight, more preferably be equivalent to or be less than about 15% weight, more preferably be equivalent to or be less than about 12% weight, more preferably be equivalent to or be less than about 10% weight, most preferably be equivalent to or be less than the aluminium of about 8% weight.
Composition can comprise salt, in cellulolytic activity sizing agent weight, its content be equivalent to from about 0.2 to about 40% weight, more preferably from about 0.4 to about 30% weight, more preferably from about 1.5 to about 20% weight, more preferably from about 3 to about 15% weight, more preferably from about 4.4 to about 12% weight, more preferably from about 5.5 to about 10% weight, most preferably from about 6 aluminium to about 8% weight.
In addition, also realized the present invention by a kind of Aquo-composition is provided, said composition comprise in ketene dimer and the ketenes polymer one of at least, comprise the dispersion and the aluminum sulfate of modified lignin sodium sulfonate and cationic modified starch.
In addition, by a kind of Aquo-composition that is used for the paper product applying glue is provided, also realized the present invention, by with the cellulolytic activity sizing agent, comprise the dispersion one of at least in anionic dispersing agents and cation dispersing agent and the non-ionic dispersing agent and comprise at least a salt more than or equal to about 5.5% weight aluminium element and mix and produce described composition in cellulolytic activity sizing agent weight.
In addition, by the method for cellulose based product applying glue is realized the present invention, described method comprises: cellulolytic activity sizing agent, the dispersion that one of comprises in anionic dispersing agents and cation dispersing agent and the non-ionic dispersing agent at least and at least a salt that comprises more than or equal to about 5.5% weight aluminium element in cellulolytic activity sizing agent weight are added in the cellulosic material.In preferred embodiments, cellulosic material can comprise the surface of paper pulp or paper product.
In addition, by providing a kind of composition to the cellulose based product applying glue (kit) to realize the present invention, described composition comprises: cellulolytic activity sizing agent, the dispersion that one of comprises in anionic dispersing agents and cation dispersing agent and the non-ionic dispersing agent at least and comprise at least a salt more than or equal to about 5.5% weight aluminium element in cellulolytic activity sizing agent weight.
Detailed Description Of The Invention
The invention provides the paper glueing composition that comprises inorganic salts, dispersion and cellulolytic activity sizing agent such as ketene dimer.Glueing composition of the present invention even under high inorganic salt concentration environment, also be stable.The glueing composition that comprises inorganic salts and dispersant will promote the effect of reactive gluing agents and the glue efficient of improvement will be provided during papermaking.
Except as otherwise noted, all percentages of pointing out in the present invention, umber, ratio etc. are all by weight.In addition, except as otherwise noted, all percentage values are that calculate on the basis to provide 100% of sample weight all in this application.Therefore, for example 30% expression: 30 weight portions in per 100 weight portion samples.
Except as otherwise noted, the standard of compound or component comprises compound or component itself, and with the combination of other compound or component, as the mixture of compound.For example, term cellulolytic activity sizing agent means as used herein: comprise the cellulolytic activity sizing agent, and/or the mixture of cellulolytic activity sizing agent, and the term inorganic salts mean: the mixture that comprises inorganic salts and/or inorganic salts.
Term " alkyl " should be understood to as used herein: comprise " aliphatic series ", " cyclic aliphatic " and " aromatics ".Alkyl should be understood to: comprise alkyl, thiazolinyl, alkynyl, cycloalkyl, aryl, aralkyl and alkaryl.In addition, " alkyl " should be understood to comprise: unsubstituted alkyl and the alkyl that replaces, the latter refers to beyond de-carbon and the hydrogen, also has the auxilliary substituent hydrocarbon part that adds.
Term " stable " means satisfied at least three conditions of composition required for protection as used herein: not gelling when 1) described composition carries out wearing out at least two weeks; 2) described Aquo-composition viscosity when carrying out wearing out at least two weeks is lower than 5000 centipoises; And 3) between at least two all aging periods, Aquo-composition is not separated into independently phase.Below each condition will be described.
First condition is not have gelling.Mean at this employed gel or gelling: composition demonstrates solid shape performance under mechanical force.Following gelling is tested: behind the preparation composition, immediately two samples are placed the bottle of 100 grams respectively.First bottle carries out the gelling test immediately.By the gelling test that Dou to 15 ° the sample of inclining is at leisure observed to carry out sample.If this sample does not flow, just think by gelling.Second bottle is carried out the gelling test after 32 ℃ of two weeks of storage.In indoor temperature measurement gelatification.
Second condition is viscosity.Preferably, the viscosity of sample is lower than 5000, more preferably is lower than 4000, more preferably is lower than 3000, more preferably is lower than 1000, more preferably is lower than 500, more preferably is lower than 300, most preferably is lower than 200 centipoises.Viscosity is measured by utilizing Brookfield DV-II viscosimeter.The selection of spindle and speed can easily be determined by those skilled in the art.The following viscosity test that carries out: behind the preparation composition, immediately the sample of two 100 grams is placed the bottle of 100 grams respectively.First bottle is carried out viscosity test immediately.Second bottle is carried out viscosity test after 32 ℃ of two weeks of storage.Before test, should make each sample bottle reduce to room temperature.
The 3rd condition is to separate, and it is to measure according to the bottom total solid of Aquo-composition.In the time in 25 ℃ of aging two weeks, the variation of bottom total solid (BTS%) should not surpass 20%.More preferably, the bottom total solid changes and should not surpass 15%, more preferably be no more than 10%, most preferably be no more than 5%.
The bottom total solid is answered following the measurement: the bottle that immediately sample of two part of 100 gram is placed 100 grams after the preparation composition respectively.First bottle to its bottom total solid measure immediately.After 25 ℃ of aging two weeks, its bottom total solid is measured for second bottle.Utilize pipette that " bottom " of each sample taken a sample and measure the bottom total solid.Preferably, with the bottom of pipette contact 100 gram sample bottles and take out about 2 gram samples and carry out this sampling procedure.According to the sample of these about 2 grams, 1.5 grams are placed on the aluminium weighing pan.This 1.5 gram is inhaled the sample that moves to be heated in 150 ℃ baking oven about 45 minutes.The percentage of nonvolatile matter is determined by the quality of measuring dry back residuals in the dispersion.The residue percentage of the sample that obtains bottom 100 gram sample bottles is referred to as " bottom total solid " BTS%.Calculate percentage change between aging period by comparing with the bottom total solid of unaged sample by the bottom total solid of aging sample.
In the above stated specification of stability condition, be considered to the digestion period in two weeks preferred.More preferably, after at least one month, this condition will be gratifying, and more preferably, after three months, this condition will be gratifying.Most preferably, after six months, composition still satisfies described stability condition.
Composition of the present invention comprises: (a) cellulolytic activity sizing agent, (b) comprise the dispersion of main anionic dispersing agents and auxilliary dispersant, and described auxilliary dispersant comprises one of at least and (c) inorganic salts that are selected from CATION or the non-ionic dispersing agent.Component (a), details (b) and (c) will be described below.
The cellulolytic activity sizing agent
Be applicable to that cellulolytic activity sizing agent of the present invention preferably includes: it is believed that can be by forming the sizing agent of covalent chemical bond with cellulosic hydroxyl reaction.Be applicable to that cellulolytic activity sizing agent of the present invention is preferably hydrophobic, in final products, can play water-repelling agent.
Preferred cellulolytic activity sizing agent is including, but not limited to ketene dimer and polymer, as alkyl ketene dimer (AKD) and thiazolinyl ketene dimer; Enetutanedioic acid anhydride (ASA); Stearic anhydride; Contain about 12 organic epoxides to about 22 carbon atoms; Contain about 12 acyl halides to about 22 carbon atoms; Contain about 12 fatty acid anhydrides to the aliphatic acid of about 22 carbon atoms; With contain 12 organic isocyanates to about 22 carbon atoms.
Ketene dimer used according to the invention and polymer preferably have structural formula I:
Figure C0081964300111
N is 0-20 or bigger integer in the formula, preferably from 0-6, more preferably from 0-3, most preferably is 0.R and R 2Can be identical or different, they are saturated or undersaturated alkyl, have about 6 to about 24 carbon atoms, preferred about 10 to about 20 carbon atoms, 14-16 carbon atom more preferably from about.R 1Be saturated or undersaturated alkyl, have about 2 to about 40 carbon atoms, preferred about 4 to about 20 carbon atoms.Preferably, R and R 2Be undersaturated at least about 25%.
Preferably, ketene dimer comprises (a) octyl group, decyl, dodecyl, myristyl, cetyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl, betanaphthyl, ketene dimer with cyclohexyl, and/or the ketene dimer that (b) makes: motanic acid by one or more following organic acids, naphthenic acids, 9, the 10-decylenic acid, 9, the 10-dodecenoic acid, gaidic acid, oleic acid, ricinoleic acid, linoleic acid, eleostearic acid, at coconut oil, babassu oil, palm-kernel oil, olive oil, peanut oil, rape oil, butter, lard, the naturally occurring mixture of the aliphatic acid of finding in the blubber, and any mixture of above-mentioned aliphatic acid.Most preferred ketene dimer is selected from: the ketene dimer of octyl group, decyl, dodecyl, myristyl, cetyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl, betanaphthyl and cyclohexyl.
Alkyl ketene dimer uses for many years industrial, and by preparing by two polymerizations of the alkyl ketene saturated, that the straight chain fat acyl chloride makes; The most widely used is the alkyl ketene dimer that is made by palmitic acid and/or stearic acid.The aqueous dispersion of these materials can Hercon The paper sizing agent derive from Hercules Incorporated (Wilmington, DE).
The ketenes polymer that uses for the inventive method has said structure formula I, and wherein, n is at least 1 integer, R and R 2Can be identical or different, they are saturated or undersaturated, straight or branched alkyl, it has 6-24 carbon atom, preferred 10-20 carbon atom, more preferably 14-16 carbon atom; And R 1Be saturated or undersaturated, straight or branched alkylidene, it has 2-40 carbon atom, preferably has 4-8 or 28-40 carbon atom.
The ketenes polymer is described in: EP-A-0,629,741Al, US5,685,815 and PCT International Application No. WO 97/30218 in, at this all these documents are incorporated herein by reference.
The ketene dimer and the polymer that use for the present invention comprise: solid shape or be not those materials of solid (be not crystal, semi-crystal or waxy solid in essence, do not having the situation current downflow of heat of fusion when being them in heating) at 25 ℃.
Ketene dimer and polymer can be the mixtures of said structure formula I compound, wherein, n preferably from 0-6, more preferably from 0-3, most preferably be 0; R and R 2Can be identical or different, they are to have alkyl 6-24 carbon atom, saturated or undersaturated, straight or branched; R 1Be saturated or undersaturated, straight or branched alkylidene, it has 2-40 carbon atom, preferably has a 4-32 carbon atom; And in the mixture of compound, R and R 2At least 25% be undersaturated.
Ketene dimer and polymer can comprise the mixture of ketene dimer or polymer compounds, and they are the product that comprise the reactant mixture of unsaturated mono carboxylic aliphatic acid.Described reactant mixture can comprise saturated mono carboxylic aliphatic acid and dicarboxylic acids in addition.Preferably, the described reactant mixture that is used to prepare dimer and polymer compounds comprises the unsaturated mono carboxylic aliphatic acid of at least 25% weight, the more preferably unsaturated mono carboxylic aliphatic acid of at least 70% weight.
Be included in unsaturated mono carboxylic aliphatic acid in the reactant mixture preferably have 10-26 carbon atom, more preferably have 14-22 carbon atom, most preferably have a 16-18 carbon atom.These acid for example comprise: oleic acid, linoleic acid, dodecenoic acid, tetradecenoic acid (myristoleic acid), gaidic acid (palmitoleic acid), octadecenoic acid (linolelaidic acid), 18 trienic acids (linolenic acid), eicosenoic acid (gadoleic acid), nervonic acid (arachidonic acid), cis-13-docosenoic acid (erucic acid), anti--13 docosenoic acids (brassidic acid) and docosapentaenoic acid (clupanodonic acid) and their acyl halide, preferably acid chloride.Can use one or more monocarboxylic acids.Preferred unsaturated mono carboxylic aliphatic acid is oleic acid, linoleic acid and palmitoleic acid and their acyl halide.Most preferred unsaturated mono carboxylic aliphatic acid is oleic acid and linoleic acid, and their acyl halide.
Preferably, be used for preparing in the present invention the ketene dimer that uses and polymeric saturated mono carboxylic fatty acids have 10-26 carbon atom, more preferably have 14-22 carbon atom, most preferably have a 16-18 carbon atom.These acid for example comprise: stearic acid, isostearic acid, myristic acid, palmitic acid, heptadecanoic acid, pentadecanoic acid, capric acid, undecanoic acid, dodecoic acid, tridecanoic acid, nonadecanoic acid, arachidic acid and docosanoic acid and their halide, preferred chloride.Can use one or more saturated mono carboxylic aliphatic acid.Preferred acid is palmitic acid and stearic acid.
The alkyl dicarboxylic aid who is used for preparing the ketenes polymer compounds that uses for the present invention preferably has 6-44 carbon atom, more preferably has 9-10,22 or 36 carbon atoms.Described dicarboxylic acids for example comprises: decanedioic acid, azelaic acid, 1,10-dodecanedioic acid, suberic acid, brazilic acid, docosandioic acid and C 36Dimer acids for example derives from Henkel-Emery (Cincinnati, EMPOL 1008 Ohio), and their halide, preferably chloride.Can use one or more described these dicarboxylic acids.The dicarboxylic acids that has 9-10 carbon atom is more preferred.Most preferred dicarboxylic acids is decanedioic acid and azelaic acid.
When dicarboxylic acids being used for the polymeric preparation of using for the present invention of ketenes, the maximum mol ratio of dicarboxylic acids and monocarboxylic acid (saturated and unsaturated summation) preferably is about 5, preferred maximum is about 4, most preferred maximum is about 2.The mixture of dimer and polymer compounds can utilize the known method of preparation standard ketene dimer to prepare.In first step, utilize PCI 3Or other halogenating agent, be preferably chlorinating agent, form acyl halide, acid chloride preferably by aliphatic acid or fatty acid mixt and dicarboxylic acids.Then, in the presence of tertiary amine (comprising trialkylamine and Cycloalkyl amine), preferred triethylamine, acyl halide is changed into ketenes.Make two polymerizations of ketenes part to form the compound of wishing then.
Ketene dimer and polymer are disclosed in US5,685,815 and the open WO97/30218 of pct international patent in, be introduced into as a reference at this.Ketene dimer can be Precis Sizing agent also derives from Hercules Incorporated.
According to the present invention, enetutanedioic acid anhydride (ASA) preferably is made up of the aliphatic unsaturated hydrocarbon that comprises the succinic anhydride side group.They are set about, are prepared with two-step method by alpha-olefin usually.At first make isomerisation of olefin by put randomly mobile two keys by alpha-position.In second step, make the reaction of isomerized alkene and maleic anhydride, to obtain having the final ASA of structural formula II:
Figure C0081964300141
Be used for comprising: contain about 8 thiazolinyls, cycloalkenyl group and arylalkenyl compound to about 22 carbon atoms with the typical alkene of maleic anhydride reaction.Concrete example is different octadecylene base succinic anhydride, positive octadecylene base succinic anhydride, n-hexadecene base succinic anhydride, dodecyl succinic anhydride, different dodecenyl succinic succinic anhydride, positive dodecenyl succinic succinic anhydride and positive octenyl succinic anhydride.
Enetutanedioic acid anhydride is disclosed in US4, in 040,900, be introduced into as a reference at this, (second edition is edited by W.F.Reynolds also to be disclosed in the The Sizing of Paper of C.E.Farley and R.B.Wasser, Tappi Press, 1989, the 51-62 pages or leaves) in.Multiple enetutanedioic acid anhydride can derive from Albemarle Corporation (Baton Rouge, Louisiana).Preferably, the enetutanedioic acid anhydride that uses for the present invention is a liquid at 25 ℃.More preferably, they are liquid in the time of 20 ℃.
The consumption of cellulolytic activity sizing agent is preferably the amount that is enough to provide glue blending function to composition.Lower limit is, in the composition consumption of cellulolytic activity sizing agent be preferably greater than Aquo-composition weight about 1%, more preferably greater than Aquo-composition weight about 5%, most preferably greater than about 7% of about Aquo-composition weight.The upper limit is, the consumption of cellulolytic activity sizing agent preferably less than Aquo-composition weight about 50%, more preferably less than Aquo-composition weight about 30%, most preferably less than about 15% of Aquo-composition weight.When representing with scope, the consumption of cellulolytic activity sizing agent in composition be preferably Aquo-composition weight about 1 to about 50%, more preferably from Aquo-composition weight about 5 to about 30%, most preferably from about 7 to about 15% of Aquo-composition weight.
Dispersion
Described composition also comprises: the preferred dispersion that makes composition stable that rises.Described dispersion comprises main dispersant and auxilliary dispersant.Term " master " and " assisting " just for reference to convenient, are in no case thought to limit as used herein.Main dispersant comprises at least a anionic dispersing agents.Suitable anionic dispersing agents including, but not limited to: contain sulfonate and sulfate polymeric dispersant as its functional group.The example of described anionic dispersing agents comprises the sodium lignosulfonate of sodium lignosulfonate and modification including, but not limited to the formaldehyde condensation products of the formaldehyde condensation products of sodium naphthalene sulfonate, the formaldehyde condensation products of Negel, sodium phenolsulfonate, the formaldehyde condensation products and the lignosulphonates of phenol sodium sulphate.
Especially preferred anionic dispersing agents is: even in the presence of a large amount of inorganic salts, still provide stable those to composition.Preferably, anionic dispersing agents comprises at least a lignosulphonates.Preferably, lignosulphonates comprise: demonstrating with respect to common lignosulphonates increases hydrophobic lignosulphonates, as Norlig 12F (lignotech, USA Inc., WI), therefore and when compare, has the more hydrophilic-lipophilic balance (HLB) (HLB) that moves of hydrophobic value of court with unmodified lignosulphonates.Therefore, preferred lignosulphonates are hydrophobic lignosulphonates.The hydrophobic increase of lignosulphonates can realize in many ways, but preferably recently realize by the weight percent that reduces sulfonate sulphur in the lignosulphonates.General remark to the lignosulphonates method of modifying, the general remark that particularly reduces the method for sulfonate sulphur concentration is described in (Reed Inc. in " AWorking Chemist ' s Guide to the Chemistry of Lignosulphonates " 1-12 page or leaf, Chemical Division (Quebec, Canada)), at this its full content is incorporated herein by reference.
Preferred lignosulphonates are sodium lignosulfonates, in the sodium lignosulfonate gross weight, its comprise be lower than about 5.9% weight, more preferably less than about 5% weight, more preferably less than about 4.5% weight, more preferably less than about 4% weight, the sulfonate sulphur of 3.6% weight most preferably from about.Preferably, in the gross weight of sodium lignosulfonate, described sodium lignosulfonate comprises greater than about 0.5% weight, more preferably greater than about 1.5% weight, most preferably greater than the sulfonate sulphur of about 2.5% weight.In the gross weight of sodium lignosulfonate, preferred sodium lignosulfonate comprise from about 0.5% to about 5.9% weight, more preferably from about 1.5% to about 5% weight, most preferably from about 2.5% sulfonate sulphur to about 4% weight.
Preferably, the molecular weight of suitable sodium lignosulfonate is greater than about 2000 gram/moles, more preferably greater than about 5000 gram/moles, most preferably greater than about 10000 gram/moles.Its molecular weight of suitable sodium lignosulfonate preferably be lower than about 150000 gram/moles, more preferably be lower than 120000 gram/moles, most preferably be lower than about 80000 gram/moles.The molecular weight ranges of preferred sodium lignosulfonate is from about 2000 to about 150000 gram/moles, most preferably from about 10000 to about 80000 gram/moles.
Preferably, in Aquo-composition weight, the consumption of anionic dispersing agents is greater than about 0.01% weight, more preferably greater than about 0.05% weight, most preferably greater than about 0.1% weight.Preferably, in the weight of Aquo-composition, the consumption of anionic dispersing agents is lower than about 10% weight, more preferably less than 5% weight, most preferably be lower than 3%.Preferably, in Aquo-composition weight, the consumption of anionic dispersing agents from about 0.01% to about 10% weight, more preferably from about 0.05% to about 5% weight, most preferably from about 0.1% to about 3% weight.
The consumption of anionic dispersing agents can be represented with the percetage by weight of cellulolytic activity sizing agent.Preferably, the consumption of anionic dispersing agents be sizing agent weight about 0.02% to about 20% weight, more preferably for cellulolytic activity sizing agent weight about 0.4 to about 7% weight, most preferably for cellulolytic activity sizing agent weight about 0.90 to about 3% weight.
Example with suitable sodium lignosulfonate of high hydrophobicity is DynasperseLCD (Lignotech USA, Inc.m WI), the example of sodium lignosulfonate is Norlig12F (Lignotech, USA Inc., WI).
In addition, described dispersion also comprises auxilliary dispersant, and it can play function of stabilizer.Auxilliary dispersant suitably comprises the material that is not anionic dispersing agents, promptly is CATION and/or non-ionic dispersing agent.Cation dispersing agent is those dispersants with clean cationic charge.Cation dispersing agent is including, but not limited to cation-modified starch and guar gum or low electric charge cationic polymer.Low electric charge cationic polymer preferably includes: have in the polymer of band cationic charge and be less than 51% repetitive and have positive charge, and all the other repetitive neutrals or band anionic charge, precondition is that the net charge on polymer is a cationic charge.The example of low electric charge cationic polymer comprises: Kymene 557H, LX, and ULX (HerculesIncorporated, Wilmington, DE), they be poly-amino polyamide-epichlorohydrin resins and Merquat 550 (Calgon Corporation, Pittsburgh, PA).Poly-amino polyamide-epichlorohydrin resins is described in US4,470,742 people such as () Bull, US5, and 714,552 (Bower), US5,171,795 people such as () Miller and US5,614,597 (Bower) are incorporated herein by reference all these documents at this.The application of cationic polymer in glueing composition is described in the US4 that all is issued to Dumas, 243,481 usually; 4,240,935; 4.279,794; 4,295,931; In 4,317,756 and 4,522,686, all these documents are incorporated herein by reference at this.Non-ionic dispersing agent is including, but not limited to any water-soluble nonionic polymer, as starch and polyethylene glycol oxide.Auxilliary dispersant preferably comprises cation-modified starch.
In Aquo-composition weight, described auxilliary dispersant is preferably greater than about 0.2% weight, more preferably greater than about 0.5% weight, most preferably use greater than the consumption of about 1% weight; Preferably, auxilliary dispersant be lower than 20% weight, more preferably to be lower than 5% weight, most preferably to use with the consumption that is lower than 3.5% weight; Preferably, the amount ranges of auxilliary dispersant from about 0.2% to about 20% weight, more preferably from about 0.5% to about 5%, most preferably from about 1% to about 3.5% weight.
The consumption of auxilliary dispersant can be represented with the percentage of the weight of used cellulolytic activity sizing agent.Preferably, the consumption of auxilliary dispersant be cellulolytic activity sizing agent weight about 0.4% to about 400% weight, more preferably from about 2% to about 100% weight, most preferably from about 10% to about 30% weight.
Preferred auxilliary dispersant comprises various starch, and they are including, but not limited to any water-soluble cationic starch.Preferred starch comprises: have uncle's amino or season amino as the CATION waxy corn starch of Charge Source.The preferred range of viscosities of starch from low viscosity to medium-viscosity.
By at 95 ℃, under the pH of 4.5-6, solution infusion 30 minutes in water can obtain the viscosity of starch solution.Refer at this employed medium-viscosity: utilize 10% weight starch solution, by the #2 spindle of 100rpm and 38 ℃ measure from about 101 Brookfield viscosity to about 2000 centipoises.Refer in this employed low viscosity: utilize 10% weight starch solution, by the #2 spindle of 100rpm and 38 ℃ measure from about 1 Brookfield viscosity to about 100 centipoises.The example of preferred starch is Sta lok 140, make by StaleyManufacturing Company (Illinois).
Inorganic salts
Composition of the present invention comprises salt, preferably inorganic salts.Preferably, described salt is the compound that improves dewatering.Preferred inorganic salts will be finished such effect, but inorganic salts can also be finished other effect in composition.For example, described one or more inorganic salts also can work to improve the sizing agent retention.
Preferably, inorganic salts comprise slaine, and it can be alkaline-earth metal (periodic table II family) salt, alkali metal (periodic table I family) salt or the salt that is formed by transition metal (periodic table) or the salt that formed by the metal of III, IV and V (periodic table).Can use multiple salt about this, comprise the salt of magnesium, barium, aluminium and calcium, but preferably, be selected from aluminium salt and calcium salt.Suitable aluminium salt is including, but not limited to the aluminum sulfate of following structural formula, Al x(SO 4) y(H 2O) z, x is from 1-3 in the formula, and y is from 1-4, and z is from 0-20.Be referred to as aluminum sulfate alum, suitable can obtain from market (General Chemical Corporation, NJ).Other aluminium salt comprises: the polymeric aluminum compound of following formula, Al n(OH) mX 3n-m, X is anion such as chloride or acetate in the formula, and n and m be the integer greater than zero, to cause (3n-m) greater than zero.When X was chloride, described salt was aluminium polychloride (PAC).Be applicable to that calcium salt of the present invention preferably has formula CaY n, Y is an anion in the formula, as chloride, acetate or nitrate, and n is 1-2.Also can use the mixture of salt in addition.
When using aluminium salt, its consumption is in Aquo-composition weight, preferably provide from about 0.02 to the aluminium element of about 2% weight, more preferably from about 0.04% to about 1.5%, most preferably from about 0.08% aluminium element to about 0.8% weight.When using calcium salt, its consumption is in Aquo-composition weight, preferably provide from 0.04% to the calcium constituent of about 4.4% weight, more preferably from about 0.1% to the calcium constituent of about 3.3% weight, most preferably from about 0.2% calcium constituent to about 2% weight.
When existing, the amount of aluminium element can be represented with the percentage of used cellulolytic activity sizing agent weight.Preferably, in cellulolytic activity sizing agent weight, the content of aluminium element is greater than about 0.2% weight, more preferably greater than about 0.4% weight, more preferably greater than about 1.5% weight, more preferably greater than about 3% weight, more preferably greater than about 4.4% weight, more preferably greater than about 5.5% weight, most preferably greater than about 6% weight.Preferably, in cellulolytic activity sizing agent weight, the content of aluminium element less than about 40% weight, be more preferably less than about 30% weight, be more preferably less than about 20% weight, be more preferably less than about 15% weight, be more preferably less than about 12% weight, be more preferably less than about 10% weight, most preferably less than about 8% weight.When representing with scope, in cellulolytic activity sizing agent weight, the content of aluminium element from about 0.2 to about 40% weight, more preferably from 0.4 to about 30% weight, more preferably from about 1.5 to about 20% weight, more preferably from about 3 to about 15% weight, more preferably from about 4.4 to about 12% weight, more preferably from about 5.5 to about 10% weight, most preferably from about 6 to about 8% weight.
The consumption of slaine used according to the invention can be determined by the equivalent of its aluminium.For the application,, can determine the equivalent of aluminium by the atomic mass of metallic element and the ratio of electric charge in the calculating salt.For example, the atomic mass of aluminium is 27, and electric charge is 3 +, the ratio that converts atomic mass and electric charge to is 9 (27/3).The atomic mass of calcium is 40, and electric charge is 2 +, so the ratio of atomic mass and electric charge is 20.Be to determine the equivalent of calcium with respect to aluminium, with the ratio of the atomic mass of calcium and electric charge, promptly 20, divided by the ratio of the atomic mass of aluminium and electric charge, promptly 9, the result is 2.2.The numerical value that obtains 2.2 is the multiplier of the calcium weight of determining to be equivalent to aluminium weight.Therefore, a gram aluminium, so if desired, the gram number of suitable calcium is 2.2 grams.As other example, the multiplier of magnesium (24/2=12) is 1.3 (12/9); Sodium (23/1=23) is 2.6 (23/9); Beryllium (9/2=4.5) is 0.50 (4.5/9); And lithium (6.9/1=6.9) is 0.77 (6.9/9).These conversions can be applicable to any metal.By utilizing this equivalent formula, can be with any amount of different inorganic salts combination, to obtain desirable effect.
As an example, can consider following embodiment 1: with alum solution (aluminum sulfate, the Al of 445.6 grams 48.5% 2(SO 4) 314H 2O MW594) is added in the sample of 222.8 gram AKD (cellulolytic activity sizing agent).The alum of described consumption comprises 19.6 gram aluminium (445.6 * .485=216.116; 216.116 gram aluminum sulfate * 54 gram aluminium/594 gram aluminum sulfate=19.6 gram aluminium).Conversion shown in above using, this content of aluminium are equivalent to 43.2 gram calcium (19.6 * 2.2), 25.5 gram magnesium (19.6 * 1.3), 9.8 gram berylliums (19.6 * 0.5) and 15.1 gram lithiums (19.6 * 0.77).Therefore, can easily replace another kind of inorganic salts, perhaps with different salt combinations, almost without any difficulty with a kind of inorganic salts.For example, in aluminum sulfate, the ratio of sulfate atomic mass and electric charge is not considered.
Therefore, as used herein, " quite " in the amount of the element of aluminium amount is: utilize that aforementioned conversion Calculation goes out, suitable amount.For example, utilize aforementioned conversion, can determine to be equivalent to the amount of calcium, magnesium or the barium of X% aluminium weight.Briefly, must determine the gram number of aluminium in the X% weight aluminium.According to the gram number of aluminium, simply change, so that determine to be equivalent to the amount of calcium, magnesium or the barium of X% aluminium weight.
Certainly, the amount that is equivalent to the aluminium of aluminium amount is same amount.Therefore, " the aluminium amount that is equivalent to 6% weight aluminium " is exactly 6% weight aluminium.This conspicuous fact is just listed at this in order to know.
This simple conversion regime also is applicable to the amount that relates to the aluminium amount.Example as used in this " greater than " or " less than " the amount of element, the amount of aluminium is exactly to utilize amount aforementioned conversion, that be greater than or less than.For example, utilize aforementioned conversion, determine amount greater than calcium, magnesium or the barium of X% weight aluminium.Briefly, must determine the gram number of aluminium in X% weight aluminium.According to the gram number of aluminium, simply change, so that determine amount greater than calcium, magnesium or the barium of X% aluminium weight.
Other is usually used in composition such as biocide, clay, calcium carbonate, titanium dioxide, non-ionic surface active agent, optical brightener, retention agent and filter aid or the like of field of papermaking, also can use by its normal consumption, and discovery or expection and above-mentioned composition are compatible.Water is used for making total composition to become 100%.
The present invention can be used for: wherein size dispersions is added into the internal sizing of paper pulp at the wet end of paper-making process; Or the top sizing that applies at squeezer or coating machine place of size dispersions wherein.In addition, the present invention can also be used in the component or two components of bi-component applying glue system.For example a component can internally be mixed with wood pulp and second component applies when size press, and this is often to use in papermaking.
Do not have further detailed content, it is believed that and utilize above stated specification, those skilled in the art can use the present invention in fullest ground.Therefore, below preferred specific embodiment be illustrative, in no case be limiting the scope of the invention.Except as otherwise noted, all percentages all by weight.
Above and below all patents of quoting as proof and the full content of publication, all be incorporated herein by reference at this.
Embodiment 1
The preparation of size dispersions
Be prepared as follows the AKD size dispersions.Unmodified sodium lignosulfonate (the Norlig 12F that 5.6 grams is comprised about 6% sulfonate sulphur Lignotech, USA Inc., WI) and 1269.2 the gram water be added in the jet boiling vessel.Stir, until Norlig 12F Fully till the dissolving.With 55.8 gram cationic starch (Sta Lok 169 , A.E.Staley Mfg.Co. IL) is added in the described boiling vessel.Boiling was heated 60 minutes and in boiling vessel, stirring during the boiling at 95 ℃ with steam.Formed mixture is the dispersant system that mixes.Then, this mixture is cooled to 70 ℃, and (Aquapel 364 to add 222.8 gram AKD , HerculesIncorporated, DE) (AMA 424 with 1.2 gram biocides , Vinings Indus, GA).Stirred 5 minutes at 70 ℃.Then at 211kg/cm 2Pressure under, (Gaulin Corporation MA) makes the mixture homogenising, is cooled to 25 ℃ then rapidly by 15M GaulinLaboratory Homogenizer.After the cooling, when stirring, the alum solution by adding 445.6 grams 48.5% (General Chemical Co., NJ) and preparation AKD size dispersions (I).
Embodiment 2
The preparation of a series of size dispersions
Similarly, be prepared as follows a series of AKD size dispersions that make by the sodium lignosulfonate that demonstrates relative high hydrophobicity of the present invention.Sodium lignosulfonate (the Dynasperse LCD that 5.6 grams is comprised about 3.6% sulfonate sulphur , Lignotech, USA Incorporated, inWisconsin) and 1269.2 the gram water be added in the jet boiling vessel.Stir, until Dynasperse LCD Fully till the dissolving.With 55.8 gram cationic starch (Sta Lok 169 , A.E.Staley Mfg.Co. IL) is added in the described boiling vessel.Boiling was heated 60 minutes and in boiling vessel, stirring during the boiling at 95 ℃ with steam.Formed mixture is the dispersant system that mixes.Then, this mixture is cooled to 70 ℃, and (Aquapel 364 to add 222.8 gram AKD , Hercules Incorporated is DE) with 1.2 gram biocide (AMA424 , Vinings Indus, GA).Stirred 5 minutes at 70 ℃.Then at 211kg/cm 2Pressure under, (GaulinCorporation MA) makes the mixture homogenising, is cooled to 25 ℃ then rapidly by 15M Gaulin Laboratory Homogenizer.After the cooling, when stirring, (sell by GeneralChemical Corp., NJ) prepare AKD size dispersions (II) by the alum solution that adds 445.6 grams 48.5%.Similarly, prepare AKD size dispersions (III), prepare size dispersions (IV) by adding 89.1 gram alum solutions by adding 222.8 gram alum solutions.Prepare size dispersions (V) similarly with dispersion (II), different is not add Dynasperse LCD Prepare size dispersions (VI) similarly with dispersion (II), different is not add cationic starch.
Embodiment 3
The dispersion that makes in embodiment 1 and 2 is used for carrying out the viscosity stability test.Described viscosity is to utilize the Brookfield DV-II viscosimeter of band #1 spindle, measures at 60RPM.The viscosity of dispersion is measured after making dispersion immediately.Then, after 32 ℃ of aging two weeks, measure viscosity once more.The result is summarized in the table 1.For the sample I-IV that uses the mixed dispersant system, its viscosity is stable; And for cationic starch or Dynasperse LCD Be used as the sample V and the VI of unique dispersant independently, dispersant or generation gelling or separation.
Table 1
The dispersion sequence number Viscosity (initial cp) Viscosity (two weeks, cp)
I 40 61
II 31 27
III 49 61
IV 41 85
V 32 Gelling
VI 11 Separate
Embodiment 4
The dispersion that embodiment 1 and 2 is made is used for carrying out the layering stability test.Typically, 1.5 gram dispersions are placed on the aluminium dish and 150 ℃ stove heating 45 minutes.Percentage by non-volatile content in the dispersion of such heating means measurement is referred to as " bottom total solid % " (BTS%).After making dispersion, measure the BTS% of described dispersion immediately.Then 100 gram dispersions are placed the vial of 100 grams.After 25 ℃ are carried out wearing out in two weeks, measure the BTS% that derives from bottle bottom sample once more.If the difference between two BTS% is less, think that so this dispersion is stable for layering.The result is summarized in the table 2.The dispersion I that makes by the mixed dispersant system of unmodified sodium lignosulfonate and cationic starch, in two weeks aging after, the very layering of high level will be arranged.Yet,, be stable for layering by the sample II-IV that the mixed dispersant system of hydrophobic sodium lignosulfonate and cationic starch makes.As the dispersion V that unique dispersant makes, have the layering of low degree by cationic starch, but as shown in table 1, it does not but have viscosity stability.To separate as the dispersion VI that unique dispersant makes by hydrophobic sodium lignosulfonate.
Table 2
The dispersion sequence number Viscosity (initial cp) Viscosity (two weeks, cp)
I 20.5 18.7
II 20.5 20.0
III 18.7 18.6
IV 16.6 16.4
V 17.0 16.9
VI 16.2 Separate
Embodiment 5
With the dispersion II, the III that make among the embodiment 2 and IV and the control sample Hercon 70 that makes by HercluesIncorporation (Delaware) Paper size dispersions is used for carrying out the drainage efficiency test.According to the method for describing among the SCAN-C21:65, utilize Canadian Standard Freeness (CSF) tester to carry out described test.The paper pulp that is refined to the reuse old corrugated container (OCC) of 400CSF is sneaked in the water, to prepare 0.2% slurries.Count 0.04%AKD with dry pulp weight and add size dispersions.In addition, also with 0.50% Sta lok 400 Starch (A.E.Staley Manufacturing Co., IL) and 0.025% Reten-1523H (Hercules Incorporated DE) is added in the described slurries.PH regulator to 7.0 with slurries.Measure the freedom (CSF) of mixture and the result is summarized in the table 3.With contrast Hercon 70 Compare, dispersion II-IV has demonstrated tangible improvement aspect drainage.
Table 3
The dispersion sequence number CSF(ml)
II 510
III 465
IV 500
Hercon 70 420
Embodiment 6
Aqueous dispersion II, III and the IV of embodiment 2 are with control sample Hercon 70 Be used on middle test paper machine, preparing internal sizing paper together.The paper that will be made by the paper pulp of reuse old corrugated container (OCC) is beaten the Canadian freedom to 350, and to form at pH7.0 quantitatively be 40 Rim/3000 foot 2Page.Water content at the spool place with paper page drying position to 5%.Just before dilute at the mixing pump place, size dispersions is added in the underflow.Addition in dried paper weight from 0.0225% to 0.068%AKD.In addition, also with 38.0% sodium sulphate (Haviland Chemical Co., MI), 0.15% alum (General Chemical Corp, NJ), and 0.025%Reten-1523H (Hercules Incorporated) is used for papermaking.Water content at the spool place with paper page drying position to 5%.Utilize Hercules Size Test (HST) to carry out the applying glue test.In HST test, the paper of applying glue is placed under the ink solutions that comprises 1% formic acid and 1.2% naphthol green B.Reverse side at this solution is measured the reflectivity of paper at the very start, and monitoring is because the decline due to the ink penetration then.The HST time (second) is: the time of changing expense when reflectivity drops to its initial value 80%.Table 4 has been summarized sizing results.Result by table 4 shows: during not only at high AKD addition but also at few additive, dispersion II-IV has comparison than Hercon 70 Obvious stronger glue blending function.
Table 4
The dispersion sequence number ADK％ HST(s)
II 0.0225 71
III 0.0225 99
IV 0.0225 81
Hercon 70 0.0225 48
II 0.045 1089
III 0.045 1182
IV 0.045 1348
Hercon 70 0.045 704
According to the front explanation, those skilled in the art can easily determine principal character of the present invention, and without departing from the spirit and scope of the present invention, can make various changes and improvements to the present invention, to make it to adapt to different purposes and condition.

Claims (10)

1. Aquo-composition comprises:
The cellulolytic activity sizing agent;
Dispersion, contain in the sodium lignosulfonate gross weight be lower than 5.9% weight sulfonate sulphur sodium lignosulfonate and be selected from cation dispersing agent and non-ionic dispersing agent in one of at least; With
At least a inorganic salts that contain one or more metallic elements that are selected from periodic table of elements I, II, III, IV and V family metal and transition metal.
2. the Aquo-composition of claim 1, wherein, sodium lignosulfonate comprises and is lower than 5% sulfonate sulphur in the sodium lignosulfonate gross weight.
3. the Aquo-composition of claim 2, wherein, sodium lignosulfonate comprises and is lower than 4.5% sulfonate sulphur in the sodium lignosulfonate gross weight.
4. the Aquo-composition of claim 3, wherein, sodium lignosulfonate comprises and is lower than 4% sulfonate sulphur in the sodium lignosulfonate gross weight.
5. the Aquo-composition of claim 4, wherein, sodium lignosulfonate comprises counts 3.6% sulfonate sulphur with the sodium lignosulfonate gross weight.
6. the Aquo-composition of claim 1, wherein, the amount of described salt is in the weight of cellulolytic activity sizing agent, makes the equivalent of described at least a metallic element equal the equivalent of the aluminium of from 3 to 15% weight.
7. the Aquo-composition of claim 6, wherein, the amount of described salt is in the weight of cellulolytic activity sizing agent, makes the equivalent of described at least a metallic element equal the equivalent of the aluminium of from 4.4 to 12% weight.
8. the Aquo-composition of claim 7, wherein, the amount of described salt is in the weight of cellulolytic activity sizing agent, makes the equivalent of described at least a metallic element equal the equivalent of the aluminium of from 5.5 to 10% weight.
9. the Aquo-composition of claim 8, wherein, the amount of described salt is in the weight of cellulolytic activity sizing agent, makes the equivalent of described at least a metallic element equal the equivalent of the aluminium of from 6 to 8% weight.
According to each described Aquo-composition of claim 1-9 in the purposes of cellulose based product being carried out in the applying glue.
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HUP0400410A2 (en) * 2004-02-11 2006-02-28 Technofill Kereskedelmi Es Szo Surface finishing method of strength-increase of corrugated papers
AT503093B1 (en) * 2005-12-23 2008-02-15 Kemira Chemie Ges Mbh Papermaking emulsion, process for its preparation and its use
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EP2014829A1 (en) * 2007-07-13 2009-01-14 Sugar Industry Innovation Pty Ltd A method for coating a paper product
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