CN101094954A - Retention improving composition - Google Patents
Retention improving composition Download PDFInfo
- Publication number
- CN101094954A CN101094954A CN 200580045343 CN200580045343A CN101094954A CN 101094954 A CN101094954 A CN 101094954A CN 200580045343 CN200580045343 CN 200580045343 CN 200580045343 A CN200580045343 A CN 200580045343A CN 101094954 A CN101094954 A CN 101094954A
- Authority
- CN
- China
- Prior art keywords
- component
- monomer
- retention
- composition
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
A novel retention aid is provided, which can realizes not only high retention but also excellent paper formation and is easy to use, in various papermaking processes. A composition for improving retention is provided, which comprises (A) a cationic water-soluble polymer and (B) an amphoteric water-soluble polymer. The component (A) preferably is a copolymer having a cation equivalent of 0.05 to 4.00 meq/g or one having a 0.5% salted viscosity of 30 to 200 mPa.s. The component (B) preferably is either a copolymer comprising a cationic radical-polymerizable monomer unit, an anionic radical-polymerizable monomer unit, and a nonionic radical-polymerizable monomer unit, or an amphoteric water-soluble polymer obtained by polymerizing a cationic radical-polymerizable monomer with an anionic radical-polymerizable monomer in the presence of a polysaccharide. From the standpoint of attaining excellent formation, the component (B) preferably has a molar proportion of the cationic radical-polymerizable monomer unit to the anionic radical-polymerizable monomer unit (hereinafter referred to as Ca/An) satisfying Ca/An < 1.2.
Description
Technical field
The present invention relates to be used to improve the composition of retention, it comprises cationic water-soluble polymer and amphoteric water-soluble polymer.Composition according to the present invention is particularly useful as retention agent with in the paper industry technical field.
Background technology
Usually, in paper technology, when the raw material that will contain filler is diluted to the ultimate density that is suitable for importing paper machine or afterwards, to wherein adding retention agent so that stop paper pulp and filler to flow to the plain boiled water, thereby improve retention from paper machine.
As retention agent, use water-soluble polymer such as water soluble polymer amount polyethylene glycol oxide and cationic-type polyacrylamide usually.
Yet in order to improve retention, the retention agent that contains these water miscible polymer must be with relatively large use.As a result, they are debatable, because produce huge Soft flocks (flocs), thereby paper evenness are worsened.
In order to address this problem, notice so-called dual system recently, wherein combine and use cationic polymer with anionic compound or polymer.Their representative instance comprises: wherein add anionic inorganic compound such as bentonitic method (patent document 1) and wherein adding the method (patent document 2) of adding the anion colloidal silica after the cationic polymer after the interpolation cationic polymer.
Patent document 1: Japanese patent unexamined open (Kokai) number 04-281095 (claim).
Patent document 2: Japanese Patent No. 2945761 (claim).
Disclosure of the Invention
Treat problem by the present invention's solution
Though better aspect the balance of retention agent between retention and paper evenness of describing in patent document 1 and 2, improved degree is still not enough.In addition, these retention agents comprise two kinds of liquid that must combine use, so they are disadvantageous, because they must use in paper technology by the mode of complexity, for example, consider when and where add various liquid, and how many various liquid are combined.
In order to address the above problem, the inventor has advised comprising a kind of retention agent of composition, and described composition contains two kinds of amphiphilic polymers (patent document 3) that the ion equivalent differs from one another.
This retention agent shows that excellent performance to address the above problem, is inadequate in the application that is used for retention that need be more excellent still sometimes.Especially, depend on the type of raw material to be used, it is being inadequate aspect retention and the paper evenness sometimes.
Can to obtain high retention in order finding out, can to guarantee excellent paper evenness and be used for the novel retention agent of various papermaking systems easily, the inventor has carried out deep research.
Patent document 3: Japanese patent unexamined open (Kokai) number 2003-175302 (claim).
The means of dealing with problems
The inventor has carried out various researchs, found that the composition that comprises cationic water-soluble polymer and amphoteric water-soluble polymer is effective.Therefore, finished the present invention.
The present invention will be described in detail belows.
In this manual, acrylate or methacrylate are expressed as (methyl) acrylate; Acrylic or methacrylic acid is expressed as (methyl) acrylic acid; Acrylamide or Methacrylamide are expressed as (methyl) acrylamide.
1. improve the composition of retention
The present invention relates to improve the composition of retention, it comprises (A) cationic water-soluble polymer (hereinafter to be referred as component (A)) and (B) amphoteric water-soluble polymer (hereinafter to be referred as component (B)).Hereinafter, every kind of component will be described.
1-1. component (A)
As the cationic water-soluble polymer of the component of using among the present invention (A), can use various polymer, as long as they are cationic.
Preferably, component (A) is the copolymer that comprises radical cation polymerisable monomer (abbreviating cationic monomer hereinafter as) unit and nonionic free radical polymerization monomer (hereinafter to be referred as non-ionic monomer) unit.
1-1-1. cationic monomer
As cationic monomer, can use all cpds, as long as they have the free radical polymerizability.The example of cationic monomer comprises uncle's salt, as hydrochloride and the sulfate of (methyl) propenoic acid dialkyl aminoalkyl ester as (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid lignocaine ethyl ester, (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid diethylamino-2-hydroxypropyl acrylate and (methyl) acrylic acid dimethylamino propyl ester; Uncle's salt is as dialkyl aminoalkyl (methyl) the acrylamide for example hydrochloride and the sulfate of dimethylaminoethyl (methyl) acrylamide; Quaternary salt, as the alkyl halide adduct for example methyl chloride adduct and aryl halide adduct as the benzyl chloride adduct of the amino alkane ester of (methyl) propenoic acid dialkyl; And quaternary salt, as the alkyl halide adduct benzyl chloride adduct of methyl chloride adduct and aryl halide adduct such as dialkyl aminoalkyl (methyl) acrylamide for example.
Among these compounds, the quaternary salt of the amino alkane ester of (methyl) propenoic acid dialkyl is preferred; The alkyl halide adduct of (methyl) propenoic acid dialkyl aminoalkyl ester is preferred.
1-1-2. non-ionic monomer and other monomer
Non-ionic monomer comprises methoxyl group (methyl) acrylate of (methyl) acrylamide, dimethyl (methyl) acrylamide, diethyl (methyl) acrylamide, (methyl) hydroxy-ethyl acrylate, ethylene oxide addition and (methyl) allyl ether of ethylene oxide addition.
Among these, (methyl) acrylamide is preferred.
As required, can use monomer except that above-mentioned monomer in combination.Other monomer comprises, for example, and (methyl) acrylic acid methoxyl group ethyl ester, (methyl) acrylic acid butoxy ethyl ester, (methyl) acrylic acid ethyl carbitol ester, (methyl) methyl acrylate, (methyl) ethyl acrylate and vinyl acetate.
1-1-3. preparation method
The preparation method of component (A) is not particularly limited, and can adopt general polymerization.For example, as for aqueous polymerization, can adopt and wherein use potassium peroxydisulfate, ammonium persulfate, 2,2 '-two (2-amidine propane) dihydrochlorides of azo, redox polymerization initator etc. carry out the hot radical polymerization as polymerization initiator, or use benzoin or acetophenone base photo-induced polymerization initiator to carry out method based on the photic radical polymerization of UV radiation.In addition, as for inverse emulsion polymerization, except above-mentioned polymerization initiator, can also use water-insoluble initator such as azodiisobutyronitrile and benzoyl peroxide to carry out polymerization.
By method as known in the art the polymer that is gel form that is obtained is cut or cuts off then.Utilize drier such as band drier, whizzer, far-infrared dryer and Vibratingfluidbeddrier that the polymer that is cut off is dry under about 60-150 ℃ of temperature, utilize grind into powder polymer such as three-stage roll mill, and carry out size Control and handle.
When in fact using the component (A) that obtains by water-in-oil type (anti-phase) emulsion polymerisation, following is emulsion oil-in-water with its phase inversion: add hydrophilic surfactant active and dilute with water with higher HLB.
As component (A), the preferred component that is powder type of using.
The cation equivalent that preferably has 0.05-4.00meq/g according to component of the present invention (A).When cation equivalent during, can damage paper evenness usually less than 0.05meq/g.When cation equivalent during greater than 4.00meq/g, retention reduces usually.
Cation equivalent among the present invention is meant the value of measuring by colloid titration method.
Can comprise described cationic monomer by the amount that is enough to reach above-mentioned preferred cation equivalent according to component of the present invention (A), and preferably comprise the described cationic monomer of 0.5-55.0 mole %.
Component (A) preferably has the 30-200mPas as the molecular weight index, more preferably 30-120mPas, the especially preferably 0.5% salinization viscosity of 30-90mPas.When described salinization viscosity during less than 30mPas, retention reduces usually.When described salinization viscosity during greater than 200mPas, evenness suffers damage usually.
Simultaneously, " 0.5% salinization viscosity " among the present invention is meant the value of following acquisition: polymer is dissolved in 4% the sodium-chloride water solution obtaining the 0.5wt% sample solution of described polymer, and uses the Brookfield viscometers with 1 or No. 2 rotor under 60rpm it to be measured down at 25 ℃.
1-2. component (B)
As the amphoteric water-soluble polymer of the component of using among the present invention (B), can use various polymer.Preferably, component (B) is the copolymer that comprises cationic monomer unit and radical anion polymerisable monomer (abbreviating anionic monomer hereinafter as) unit.
1-2-1. cationic monomer
As cationic monomer, can use aforesaid monomer.
Among those monomers, the quaternary salt of (methyl) propenoic acid dialkyl aminoalkyl ester is preferred, and the alkyl halide adduct of (methyl) propenoic acid dialkyl aminoalkyl ester is preferred.
1-2-2. anionic monomer
As anionic monomer, can use all cpds, as long as they have the free radical polymerizability.The example of anionic monomer comprises that unsaturated carboxylic acid is as (methyl) acrylic acid, crotonic acid, itaconic acid and maleic acid and their salt.The example of described salt comprises the salt of ammonium salt and alkali metal such as sodium and potassium.
Among these, (methyl) acrylic acid is preferred.
1-2-3. other monomer
In the present invention, component (B) comprises described cationic monomer and the anionic monomer as requisite component, and can further comprise non-ionic monomer as required.
As non-ionic monomer, can use above-mentioned monomer.
Among those monomers, (methyl) acrylamide is preferred.
As required, can use monomer except that above-mentioned monomer in combination.The example of these monomers comprises above-mentioned those.
Bond as preferred monomer among the present invention, can mention: (1) comprises uncle's salt of propenoic acid dialkyl aminoalkyl ester or quaternary salt as cationic monomer, acrylates is as anionic monomer, with the copolymer of acrylamide as non-ionic monomer, (2) comprise uncle's salt of methacrylic acid dialkyl aminoalkyl ester or quaternary salt as cationic monomer, acrylates is as anionic monomer, with the copolymer of acrylamide as non-ionic monomer, (3) comprise uncle's salt of uncle's salt of methacrylic acid dialkyl aminoalkyl ester or quaternary salt and propenoic acid dialkyl aminoalkyl ester or quaternary salt as cationic monomer, acrylates is as anionic monomer and the acrylamide copolymer as non-ionic monomer.
The component here (B) can be according to aforesaid preparation method's preparation.
The amphoteric water-soluble polymer of component (B) is the polymer (hereinafter to be referred as polysaccharide-modified amphiphilic polymers) by described cationic monomer and anionic monomer polymerization are obtained preferably, because this kind polymer is realized high retention and high evenness simultaneously.
Hereinafter, will the respective components and the preparation method of polysaccharide-modified amphiphilic polymers be described.
1-2-4. polysaccharide-modified amphiphilic polymers
1) polysaccharide
In the present invention, can use various polysaccharide.
For instance, the polysaccharide that derives from the natural source material comprises starch.The instantiation of starch comprises farina, wax shape farina, sweet potato starch, corn starch, high side chain cornstarch, wheaten starch, rice starch, tapioca, sago starch, mannosan (glumannan) and galactan; With starch raw material such as wheat flour, corn flour, through cutting and dry sweet potato with through cutting and dry cassava.
The example of the polysaccharide except that starch comprises cellulose such as methylcellulose, ethyl cellulose, hydroxyethylcellulose and carboxymethyl cellulose, Na-alginate, Arabic gum, dextran, gelatin, casein, collagen, chitin and poly glucosamine.
Preferred polysaccharide is a starch, specifically comprises above-mentioned starch such as farina, wax shape farina, sweet potato starch, corn starch, high polysaccharide cornstarch, wheaten starch, rice starch, tapioca, sago starch, mannosan and galactan.
Described starch can be the producing starch that obtains by chemistry or enzymatic modification.Processing method comprises, for example, and oxidation, esterification, etherificate and acid treatment.
The polysaccharide that uses among the present invention is preferably above-mentioned to make its polysaccharide that becomes cationic or both sexes by commonsense method, excellent with the copolymerizable property monomer of describing later and have excellent flocculating property because they have.
Can make the polysaccharide cationization by commonsense method.
The cationization method comprises with cationic agent handles the starch raw material.The instantiation of cationic agent comprises tertiary amine such as diethyllaminoethyl chlorine and quaternary ammonium salt such as chlorination 3-chloro-2-hydroxypropyl trimethyl ammonium and chlorination glycidyl trimethyl ammonium.
The polysaccharide of cationization preferably has 0.01-0.06wt/wt%, more preferably the CATION substitution value of pressing the nitrogen-atoms conversion of 0.02-0.06wt/wt%.
Polysaccharide can be for example, to have experienced those of known response after cationization.For instance, they can be the amphoteric polysaccharides that has experienced the anionization reaction.The instantiation of anionization reaction comprises: the phosphorylation of use inorganic phosphate etc.; The urea phosphorylation and the oxidation of use hypohalite etc.; Use the carboxy methylation of chloroacetic acid; And sulphation.
Polysaccharide preferably uses with the glue form, and therefore preferably lives through the boiling processing those.Here " boiling " is meant polysaccharide is heated to their gelatinization temperature or higher processing.At this, according to the type of starch to be used, can set heating-up temperature according to circumstances, but preferably 70 ℃ or higher.The boiling of starch can be undertaken by discontinuous method or continuation method.
Can after above-mentioned cationization or in above-mentioned cationization, carry out boiling.
Preferably, under the solids content of 25 ℃ and 10-40wt%, use the viscosity of the starch glue to be used of Brookfield viscometer mensuration to be 100-10,000mPas.
Preferred dilute with water of polysaccharide glue that uses among the present invention and the slurry of making 3-10wt%.
When the polysaccharide glue aging solidify or the dispersibility in water variation the time, preferably before using, it is carried out boiling and handles.In this case, boiling method can be with above-mentioned identical.
2) monomer
As cationic monomer, anionic monomer and other monomer, can use above-mentioned those.As preferred monomer, also can use above-mentioned those.
3) preparation method
Polysaccharide-modified amphiphilic polymers is the polymer by cationic monomer and anionic monomer polymerization are obtained.
This preparation method comprises, for example, wherein in the presence of polymerization initiator and polysaccharide according to the method for commonsense method with cationic monomer and anionic monomer polymerization.
Hereinafter, will respective components to be used, polymerization etc. be described.
(1) ratio of polysaccharide and monomer and combination
As for the polysaccharide of polysaccharide-modified amphiphilic polymers of the present invention and the ratio of monomer, based on the total amount of described polysaccharide and all monomers, the ratio of monomer is preferably 50wt% or more, more preferably 50-99wt%.
When the ratio of monomer during less than 50wt%, it is water insoluble that the polymer of gained becomes sometimes, or the heavy polymer as flocculant can be provided.
Bond as preferred monomer among the present invention, can mention: (1) comprises uncle's salt of propenoic acid dialkyl aminoalkyl ester or quaternary salt as cationic monomer, acrylates is as anionic monomer, with the copolymer of acrylamide as non-ionic monomer, (2) comprise uncle's salt of methacrylic acid dialkyl aminoalkyl ester or quaternary salt as cationic monomer, acrylates is as anionic monomer, with the copolymer of acrylamide as non-ionic monomer, (3) comprise uncle's salt of uncle's salt of methacrylic acid dialkyl aminoalkyl ester or quaternary salt and propenoic acid dialkyl aminoalkyl ester or quaternary salt as cationic monomer, acrylates is as anionic monomer and the acrylamide copolymer as non-ionic monomer.
(2) polymerization initiator
Polymerization initiator comprises azo polymerization initiator, redox polymerization initator, photo-induced polymerization initiator etc.
Hereinafter, every kind of polymerization initiator will be described.
Zero azo polymerization initiator
All cpds can be used as azo polymerization initiator, and their instantiation comprise 4,4 '-two (4-cyanovaleric acid) (the 10 hours half life temperatures: 69 ℃ of azo; The temperature in bracket that describes below is represented same meaning); 2,2 '-azodiisobutyronitrile (65 ℃); 2,2 '-two (2-methylbutyronitrile) (67 ℃) of azo; 2,2 '-azo two [2-methyl-N-(2-ethoxy) propionamide] (86 ℃); 2,2 '-two (2-amidine propane) hydrochlorides (56 ℃) of azo; With 2,2 '-two [2-(2-imidazoline-2-yl) propane] hydrochlorides (44 ℃) of azo.
Azo polymerization initiator can use individually or two or morely combine use.
Among above-mentioned azo polymerization initiator, preferred compound is that 10 hours half life temperatures are 50 ℃ or more, more preferably 50-90 ℃, even more preferably 50-70 ℃ azo polymerization initiator, reason is that they have the high solubility in water, produce the polysaccharide-modified amphiphilic polymers that does not contain or contain hardly insoluble substance, produce the polysaccharide-modified amphiphilic polymers that has the polysaccharide-modified amphiphilic polymers of high molecular and the unreacted monomer that comprises the reduction amount is provided.
Based on the total amount of polysaccharide and monomer, the ratio of azo polymerization initiator to be used is preferably 50-5,000ppm, more preferably 100-3,000ppm, even more preferably 300-1,000ppm.Azo polymerization initiator ratio less than 50ppm causes incomplete polymerization, produces the residual monomer of recruitment; Greater than 5,000ppm provides the water-soluble polymer of lower molecular weight.
Zero redox polymerization initator
The redox polymerization initator is the bond of Oxidizing and Reducing Agents.
Oxidant is peroxide preferably because it to polysaccharide have hydrogen extraction effect and successfully with monomer-grafted to polysaccharide.The example of peroxide comprises persulfate such as sodium peroxydisulfate, potassium peroxydisulfate and ammonium persulfate, organic peroxide such as benzoyl peroxide, t-butyl hydroperoxide and succinic acid peroxide, hydrogen peroxide, and sodium bromate.Among these peroxide, persulfate is preferred, even because they also are being excellent aspect the hydrogen extraction effect under low temperature when polymerization begins.
The example of reductant comprises sulphite such as sodium sulfite, bisulfites such as sodium hydrogensulfite, ascorbic acid or its salt, rongalite, hydrosulfurous acid or its salt, triethanolamine and cuprous sulfate.
The example of the preferred bond of peroxide and reductant comprises persulfate and sulphite and persulfate and bisulfites.
Based on the total amount of polysaccharide and monomer, the ratio of oxidant is preferably 10-1,000ppm, more preferably 20-500ppm, especially preferably 40-200ppm.Ratio less than 10ppm may cause inadequate hydrogen to extract; Greater than 1,000ppm may make the molecular weight of polysaccharide-modified amphiphilic polymers become low and can not show sufficient performance.
Based on the total amount of polysaccharide and monomer, the ratio of reductant is preferably 10-1,000ppm, more preferably 20-500ppm.
When using the redox polymerization initator, its preferred addition has polymerization accelerant, for example, and based on polymerization accelerant such as the copper chloride and the frerrous chloride of inorganic metal.
Zero photo-induced polymerization initiator
Preferred photo-induced polymerization initiator comprises ketal class photo-induced polymerization initiator and acetophenones photo-induced polymerization initiator because they to polysaccharide have hydrogen extraction effect and successfully with monomer-grafted to polysaccharide.In this case, the optics cracking taking place and has produced the benzoyl of hydrogen extractant effect.
The example of ketal class photo-induced polymerization initiator comprises 2,2-dimethoxy-1,2-diphenyl second-1-ketone and benzyl dimethyl ketal.
The example of acetophenones photo-induced polymerization initiator comprises diethoxy acetophenone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxy-cyclohexyl-benzophenone, 2-methyl-2-morpholino (4-sulphomethyl phenyl) third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane, 2-hydroxy-2-methyl-1-phenyl third-1-ketone and 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] and these oligomer.
Except above-claimed cpd, photo-induced polymerization initiator can be benzoin class photo-induced polymerization initiator, thioxanthene ketone photo-induced polymerization initiator or as the open described photo-induced polymerization initiator that contains polyalkylene oxide groups of (Kokai) number 2002-097236 of Japanese Patent Laid.
Based on the total amount of polysaccharide and monomer, the ratio of photo-induced polymerization initiator is preferably 10-1,000ppm, more preferably 20-500ppm, even more preferably 40-200ppm.May cause the increase of the amount of inadequate hydrogen extraction or residual monomer less than the ratio of 10ppm; Greater than 1,000ppm may make the molecular weight of polysaccharide-modified amphiphilic polymers become low and can not show sufficient performance.
When using photo-induced polymerization initiator, can also comprise triethanolamine and methyl diethanolamine in conjunction with photosensitizer such as amido photosensitizer.
(3) polymerization methods
Polymerization methods comprises aqueous polymerization, inverse suspension polymerization and inverse emulsion polymerization; Preferred water phase-polymerization and inverse emulsion polymerization are because their easy operations.
For example, when adopting aqueous polymerization, with polysaccharide and monomer dissolving or be dispersed in the aqueous medium with in polymerization in the presence of polymerization initiator under 10-100 ℃.To or be dispersed in the water as raw-material polysaccharide and monomer dissolving, when using them, add in the aqueous medium then.
When adopting inverse emulsion polymerization, for example, use this kind method, the aqueous solution that wherein will comprise polysaccharide and monomer stirs and is that the organic dispersion medium of the hydrophobic surfactant of 3-6 mixes to carry out emulsification with comprising HLB, then in the presence of polymerization initiator 10-100 ℃ of following polymerization with generation water-in-oil type (anti-phase) polymer emulsion.The example of organic dispersion medium comprises high boiling hydrocarbon solvent such as solvent naphtha.
The ratio of polysaccharide and monomer can be set according to circumstances according to purpose in aqueous medium or organic dispersion medium, and is preferably 20-70wt%.
According to the type of polymerization initiator to be used, polymerization can be photo polymerization, redox polymerization etc.
Particularly, polymerization can be undertaken by polymerization initiator being added in the aqueous solution that comprises polysaccharide and monomer or the reversed-phase emulsion.
Polymerization also can be the combination of photo polymerization and redox polymerization.
When the control molecular weight, can use chain-transferring agent.The example of chain-transferring agent comprises mercaptan compound such as mercaptoethanol and mercaptopropionic acid and reducing inorganic salt such as sodium sulfite, sodium hydrogensulfite and sodium hypophosphite.
In the present invention, aqueous polymerization is preferred.In this case, preferably carry out polymerization under light radiation, reason is short polymerization time and excellent productivity.
When the polymerization carried out under light radiation, can use ultraviolet light and/or visible light as radiant light; Ultraviolet light is preferred.
The intensity of light radiation is determined according to the molecular weight of the type of type, photo-induced polymerization initiator and/or the photosensitizer of monomer or concentration, the polysaccharide-modified amphiphilic polymers studied, polymerization time etc., generally speaking, is preferably 0.5-1,000W/m
2, more preferably 5-400W/m
2
Light source can be, for example, and fluorescence chemical lamp, fluorescent blue lamp, metal halide lamp or high-voltage mercury lamp.
In the polymerisation under the light radiation, the temperature of the aqueous solution of monomer is not particularly limited, but is preferably 5-100 ℃ usually, more preferably 10-95 ℃, carries out under temperate condition to allow photo polymerization reacting balance ground.Temperature when polymerization begins is preferably 5-15 ℃, because obtain the polysaccharide-modified amphiphilic polymers of high molecular and remove at an easy rate and reduce phlegm and internal heat.
The polymerisation of the aqueous solution of monomer under light radiation can be undertaken by discontinuous method or continuation method.
(4) preferred polymerization
The preparation method of polysaccharide-modified amphiphilic polymers preferably wherein in the presence of polysaccharide, azo polymerization initiator and hydrogen extractant with the method for cationic monomer and anionic monomer polymerization, because this permission is grafted to heavy polymer on the polysaccharide, reduces the amount of residual monomer and the polysaccharide-modified amphiphilic polymers that shows the flocculating property of various excellences when as flocculant is provided.
Azo polymerization initiator comprise aforesaid those.
The example of hydrogen extractant comprises redox hydrogen extractant (hereinafter to be referred as the RD extractant) and photo-induced polymerization initiator hydrogen-like extractant (hereinafter to be referred as the PT extractant).RD extractant and PT extractant not only extract hydrogen from polysaccharide, and play the polymerization initiator effect of monomer.
The RD extractant is oxidant etc. preferably, the example of described oxidant comprise aforesaid those.In this case, it preferably combines use with reductant.
The PT extractant is ketal class photo-induced polymerization initiator or acetophenones photo-induced polymerization initiator preferably, their example comprise aforesaid those.
Polysaccharide-modified amphiphilic polymers should comprise and wherein monomer-graftedly is aggregated to graft copolymer on the polysaccharide as main component, comes from described monomer but is not grafted onto polymer on the described polysaccharide but also can comprise.
1-2-5. the processing of the component that is obtained (B)
By aforesaid mode will cut or prescind by the component (B) (it is gel form usually) that aqueous solution polymerization obtains, drying and grind into powder polymer, and carry out size Control and handle, randomly add additive etc., use then.
When in fact using the component (B) that obtains by water-in-oil type (anti-phase) emulsion polymerisation, become emulsion oil-in-water to follow dilute with water its phase inversion according to said method.
As component (B), the preferred component that is powder type of using.
Component (B) preferably has the 0.5% salinization viscosity of 10-100Pas.In order to obtain high retention and high evenness, described viscosity is 10-80mPas more preferably, preferred especially 10-50mPas.Viscosity is the evenness of the component in the scope of 10-100mPas (B) ordinary loss paper not.
In component (B), the mol ratio Ca/An of cationic monomer and anionic monomer can suitably determine according to purpose.
When need be aspect evenness during the paper of excellence, component (B) preferably satisfies Ca/An＜1.2, more preferably has the Ca/An of 0.5-0.9.
On the other hand, when need be aspect retention during the paper of excellence, component (B) preferably satisfies Ca/An＞5, more preferably has the Ca/An of 5-15.
This kind component (B) obtains by making described cationic monomer and anionic monomer satisfy described monomer ratio combined polymerization.
1-3. preparation of compositions method
Comprise component (A) and component (B) in combination according to composition of the present invention.
Can be according to composition of the present invention by component (A) and component (B) mixing are prepared.Perhaps, add every kind of component individually in the papermaking process that can will describe in the back.
Component (A) and component (B) can each self-contained a kind of components, or two or more components.Yet, because conveniently, preferably use the bond of a kind of component (A) and a kind of component (B).
Component (A) and the ratio of component (B) in composition can suitably be determined according to purpose.Yet composition preferably is made of 40-90wt% component (A) and 10-60wt% component (B).
The polymer of composition of the present invention preferably is powder type or reversed-phase emulsion form, more preferably is powder type.
In the use of reality, when polymer is powder that this powder is water-soluble, and as aqueous solution use, or when polymer was reversed-phase emulsion, water diluted its so that phase inversion, and use with the emulsion oil-in-water form.Under two kinds of situations, solids content is preferably 0.01-0.5wt%, more preferably 0.01-0.1wt%.
When powder is water-soluble and when using as the aqueous solution, the described aqueous solution preferably has the pH value of 4-6.
2. papermaking process
Use the papermaking process of the present composition can be according to conventional methods, and can followingly carry out: the present composition is added in the raw material, carry out papermaking then.
Adding the method for retention agent can carry out according to conventional methods in the following manner, for example, adds described auxiliary agent or interpolation after this dilution when raw material being diluted to the ultimate density that is used to import paper machine.
The raw material that retention agent is applied to wherein comprises those that are used for general papermaking process, and comprises at least paper pulp and filler and randomly usually, and the additive except that filler is particularly including sizing agent, fixer, paper reinforcing agent, colouring agent etc.
Retention agent of the present invention is preferably applied to the paper pulp that is made of waste paper that accounts for whole paper pulp higher proportion such as deinked waste paper.In addition, retention agent of the present invention can be preferably applied to the papermaking systems of high filler content, neutral papermaking systems and high speed papermaking systems.
The example of filler comprises clay, kaolin, agalite, talcum, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, zinc oxide, titanium oxide etc.The example of sizing agent comprises acrylic acid-styrol copolymer etc.; The example of fixer comprises aluminum sulfate, cationic starch, alkyl ketene dimer etc.; The example of paper reinforcing agent comprises starch, CATION or amphiprotic polyacrylamide etc.
With respect to the dry pulp weight in the raw material, the ratio of retention agent to be added is preferably 50 to 500ppm, more preferably 100-500ppm.
PH value with raw material after adding described retention agent is maintained to preferred 5-10, more preferably 5-8.After adding retention agent, immediately raw material is imported paper machine.
The invention effect
Composition of the present invention can be as the retention agent of a component form, and formation of sheet and retention that it is not subjected to when and where to add its influence and make papermaking process in the papermaking process process become balanced.
Preferred forms of the present invention
The invention provides the retention improving composition that comprises component (A) and component (B).
Component (A) preferably comprises the copolymer of cationic monomer unit and non-ionic monomer unit, and preferably has 0.05 to 4.00meq/g cation equivalent, also preferably has the 0.5% salinization viscosity of 30-200mPas.
Described component (B) preferably comprises the copolymer of radical cation polymerisable monomer unit, radical anion polymerisable monomer unit and nonionic free radical polymerization monomer unit; Or amphoteric water-soluble polymer by radical cation polymerisable monomer and the polymerization of radical anion polymerisable monomer are obtained.
When preparing when having the paper of excellent evenness, component (B) preferably satisfies Ca/An＜1.2.When preparing when having the paper of excellent retention, component (B) preferably satisfies Ca/An＞5 on the other hand.
And component (B) preferably has the 0.5% salinization viscosity of 10-100mPas.
Can be preferably applied to wherein to add in the above-mentioned composition any to carry out papermaking in the raw material then papermaking process according to composition of the present invention.
Embodiment
With reference to embodiment and comparative example the present invention is described more specifically below.
In the following description, " % " is meant wt%, and " part " is meant weight portion.
Zero preparation embodiment 1 (preparation of cationic polymer)
In the stainless steel reaction bottle, put into total amount and be the aqueous solution of dimethylaminoethyl acrylate methyl chloride quaternary salt (hereinafter to be referred as " DAC ") of 760g and the aqueous solution of acrylamide (hereinafter to be referred as " AM "), satisfying provides 10/90 DAC/AM mol ratio (the DAC/AM weight ratio of 23.2/76.8) and 28% solids content.
Subsequently, solution is adjusted to 10 ℃ temperature nitrogen blowing 60 minutes in described solution simultaneously.Then, solid weight based on all monomers and starch, respectively with 1, the concentration of 000ppm, 0.3ppm, 30ppm and 30ppm is added the two amidine propane hydrochlorides (hereinafter to be referred as V-50) of azo, copper chloride, ammonium persulfate and sodium hydrogensulfite, then is arranged on 100W black light on the reaction bulb at 6.0mW/cm by use
2Radiation intensity under radiation carried out polymerization in 60 minutes to obtain to be the cationic polymer of aqueous gel form.
From bottle, take out the cationic polymer that obtained and dry and grind to obtain the powder amphiphilic polymers.This cationic polymer is called C-1.
Measure the 0.5% salinization viscosity (abbreviating salinization viscosity hereinafter as) of the polymer that is obtained.The result is shown in the table 1.
Below abbreviation in the table 1 was represented, 0.5% salinization viscosity abbreviated salinization viscosity as.
DAC: the methyl chloride quaternary salt of dimethylaminoethyl acrylate
AA: acrylic acid
AM: acrylamide
Table 1
| Be called for short | Monomer (mol%) | Polymer | |||||
| DAC | AA | AM | Cation equivalent (meq/g) | Ca/An | Salinization viscosity (mPas) | ||
| Cationic polymer | C-1 | 10 | 0 | 90 | 1.2 | 65 | |
| Amphiphilic polymers | CR-1 | 42 | 5 | 53 | 8.4 | 28 | |
| AR-1 | 30 | 35 | 35 | 0.9 | 20 | ||
| CO-1 | 23 | 2 | 75 | 11.5 | 43 | ||
| CO-2 | 15 | 8.6 | 76.4 | 1.7 | 45 | ||
| CO-3 | 15.8 | 1 | 83.2 | 15.8 | 44 | ||
Zero preparation embodiment 2 (preparation of amphiphilic polymers)
With preparing the powdery amphoteric polymer with embodiment 1 the same method, the maximum temperature when difference is component to be used and ratio changed into those and the solids content shown in the table 1 and satisfy in polymerization through regulating becomes 85-90 ℃.
Measure the salinization viscosity of the amphiphilic polymers that is obtained.The result is shown in the table 1.
Zero preparation embodiment 3 (preparation of polysaccharide-modified amphiphilic polymers)
In the stainless steel reaction bottle, adding total amount is the aqueous solution of the DAC of 760g, the aqueous solution of AA and the aqueous solution of AM, and the mol ratio that satisfies DAC/AA/AM is the solids content of 42/5/53 (weight ratio of DAC/AA/AM is 66.3/3.0/30.7) and 56%.
With ion exchange water the starch size of amphoterisation (is derived from Oji Cornstarch Co., the Ace KT-245 of Ltd.; Solids content: 22% or littler; Hereinafter to be referred as " KT-245 ") be diluted to 5% solids content and heat further under 80 ℃ that to handle 30 minutes with boiling be 6% amphoterisation starch size to obtain solids content.Add the amphoterisation starch size that is obtained with the amount of 213g, 3% of the total amount that described amount is represented according to their solids content corresponding to monomer and starch.In addition, add the 20g ion exchange water and be adjusted to 43%, their gross weight is adjusted to 1.0kg, then stir and disperse with solids content with all monomers and starch.
Subsequently, solution is adjusted to 10 ℃ temperature nitrogen blowing 60 minutes in described solution simultaneously.Then, solid weight based on all monomers and starch, respectively with 1, the concentration of 000ppm, 0.3ppm, 30ppm and 30ppm is added V-50, copper chloride, ammonium persulfate and sodium hydrogensulfite, then is arranged on 100W black light on the reaction bulb at 6.0mW/cm by use
2Radiation intensity under radiation carried out polymerization in 60 minutes to obtain to be the water-soluble bisexual copolymer of aqueous gel form.
From bottle, take out the amphiphilic polymers that obtained and dry and grind to obtain the powdery amphoteric polymer.This amphiphilic polymers is called SCR-1.
Measure the salinization viscosity of the polymer that is obtained.The result is shown in the table 2.
Table 2
| Preparation embodiment | Be called for short | Starch | Monomer (mol%) | Polymer | |||
| KT-245 (％) 1) | DAC | AA | AM | Ca/An | Salinization viscosity (mPas) | ||
| 3 | SCR-1 | 3 | 42 | 5 | 53 | 8.4 | 23 |
| 4 | SAR-1 | 3 | 30 | 35 | 35 | 0.9 | 18 |
| 5 | SCR-2 | 3 | 20 | 2 | 78 | 10.0 | 30 |
1) with respect to the ratio of the total amount of starch and monomer
Zero preparation embodiment 4 and 5
With with prepare embodiment 3 the same methods and prepare polymer, difference is to change component to be used and ratio into shown in the table 2 those.
Measure the salinization viscosity of the polymer that is obtained.The result is shown in the table 2.
Zero embodiment 1 and 2
According to the ratio shown in the table 3 component (A) shown in the following table 3 and component (B) are mixed with the preparation composition.As retention agent, use the aqueous solution of the following composition that comprises 0.05wt%.
Table 3
| Composition | Polymer to be used (part) | After Ca/An mixes | |
| (A) | (B) | ||
| BL-1 | C-1(50) | CR-1(50) | 11.5 |
| BL-2 | C-1(70) | AR-1(30) | 1.7 |
The pulp material (hereinafter to be referred as raw pulp) of 1% solids content that employing constitutes by deinked waste paper (50SS%) with from the kraft pulp (50SS%) of broad leaf tree (with described deinked waste paper and kraft pulp chopping and beat).At this on the one hand, according to the canadian standard freeness (hereinafter being called CSF) that JIS P 8121 shreds 350ml with described deinked waste paper and paper pulp, difference is to use 1% sample.
1, under the stirring of 000rpm, in described raw pulp, add following component (1)-(5) in order with 10 seconds intervals, utilize dynamic drainage cylinder method to measure total retention.The following evaluation of paper evenness: adopt and derive from Kumagai Riki Kogyo Co., the bronze silk screen of the square type of Ltd. is used for carrying out papermaking with the paper pulp that has wherein added retention agent, to obtain 60g/m before the thin slice forcing press compacting of using square type
2Basic weight.Then, with the paper of gained in automatic drier after 100 ℃ of following dryings, measure the evenness index (this index is big more, and evenness is good more) of paper with the evenness exerciser.
The result who is obtained is shown in the table 4.The final pH value of paper pulp is 7.9.
(1) precipitated calcium carbonate: 20% (with respect to the ratio of paper pulp solids content in the paper pulp, hereinafter to be referred as " with respect to paper pulp ")
(2) cationic starch: 0.3% (with respect to paper pulp)
(3) aluminum sulfate: 1.7% (with respect to paper pulp)
(4) paper reinforcing agent (15% aqueous solution of the copolymer of making by DAC/AA/AM=20/10/70 (mol ratio)); Viscosity: 3,500mPa.s): 0.5%
(5) retention agent: 150ppm (with respect to paper pulp)
Table 4
| Retention agent | Addition (ppm) | Total retention (%) | Evenness | |
| Embodiment 1 | BL-1 | 150 | 87.8 | 60 |
| Embodiment 2 | BL-2 | 150 | 88.9 | 68 |
| The comparative example 1 | CO-1 | 150 | 84.5 | 50 |
| The comparative example 2 | CO-2 | 150 | 84.1 | 59 |
| The comparative example 3 | C-1 | 150 | 87.1 | 40 |
Zero comparative example 1-3
Estimate the performance of retention agent with the method the same with embodiment 1, difference is the CO-1 shown in the table 1, CO-2 and C-1 as retention agent.The result who is obtained is shown in the table 4.
Zero discusses
Result in the table 4 shows that retention agent of the present invention all is being excellent aspect total retention and the evenness two.On the other hand, be of inferior quality aspect the balance of comparative example 1 and 2 (the wherein amphiphilic polymers that use has and the embodiment same monomer is formed individually) between retention and evenness.In addition, the comparative example 3 who wherein uses component (A) individually aspect retention better but the evenness aspect is of inferior quality.
Zero embodiment 3-5
According to the ratio shown in the table 5 component (A) shown in the following table 5 and component (B) are mixed with the preparation composition.As retention agent, use the aqueous solution that comprises the following composition of 0.05wt%.
Table 5
| Composition | Polymer to be used (part) | After Ca/An mixes | |
| (A) | (B) | ||
| BL-3 | C-1(50) | SCR-1(50) | 11.5 |
| BL-4 | C-1(70) | SAR-1(30) | 1.7 |
| BL-5 | C-1(50) | SCR-2(50) | 15.8 |
As raw pulp, use the pulp material (with described deinked waste paper and kraft pulp chopping and beat) of 1% solids content that constitutes by deinked waste paper (70SS%) with from the kraft pulp (30SS%) of broad leaf tree.
With under the stirring of 1000rpm, said components (1)-(5) being added in the described raw pulp with embodiment 1 the same method.Then, measure total retention.
The result who is obtained is shown in the table 6.The final pH value of paper pulp is 7.9.
Table 6
| Retention agent | Addition (ppm) | Total retention (%) | Evenness | |
| Embodiment 3 | BL-3 | 150 | 85.5 | 80 |
| Embodiment 4 | BL-4 | 150 | 85.6 | 95 |
| Embodiment 5 | BL-5 | 150 | 86.8 | 81 |
| The comparative example 4 | CO-1 | 150 | 82.1 | 40 |
| The comparative example 5 | CO-2 | 150 | 82.6 | 45 |
| The comparative example 6 | CO-3 | 150 | 84.0 | 45 |
| The comparative example 7 | C-1 | 150 | 85.5 | 30 |
Zero comparative example 4-7
Estimate the performance of retention agent with the methods the same with embodiment 3, difference is that shown in the employing table 6 those are as retention agent.The result who is obtained is shown in the table 6.
Zero discusses
According to the result in the table 6, comprising polysaccharide-modified amphiphilic polymers is being excellent as the retention agent of component (B) aspect total retention and the evenness two.
On the other hand, comparative example 4-6 (wherein use and have the single amphiphilic polymers of forming with embodiment 3-5 same monomer) shows inadequate total retention and the evenness of being on duty mutually.In addition, only the comparative example 7 who is made of component (A) shows good total retention, but evenness is on duty mutually.
Industrial applicability
Can be preferably used as retention agent according to composition of the present invention, and be used for paper industry.
Claims (8)
1. be used to improve the composition of retention, it comprises (A) cationic water-soluble polymer and (B) amphoteric water-soluble polymer.
2. according to the composition that is used to improve retention of claim 1, wherein said component (A) is the copolymer that comprises radical cation polymerisable monomer unit and nonionic free radical polymerization monomer unit, and has the cation equivalent of 0.05-4.00meq/g.
3. according to the composition that is used to improve retention of claim 1 or 2, wherein said component (A) has the 0.5% salinization viscosity of 30-200mPas.
4. according to each the composition that is used to improve retention among the claim 1-3, wherein said component (B) is the copolymer that comprises radical cation polymerisable monomer unit, radical anion polymerisable monomer unit and nonionic free radical polymerization monomer unit.
5. according to each the composition that is used to improve retention among the claim 1-3, wherein said component (B) is the amphoteric water-soluble polymer by radical cation polymerisable monomer and the polymerization of radical anion polymerisable monomer are obtained.
6. according to each the composition that is used to improve retention among the claim 1-5, the molar ratio (hereinafter to be referred as Ca/An) of radical cation polymerisable monomer unit that wherein said component (B) has and radical anion polymerisable monomer unit satisfies Ca/An＜1.2.
7. comprise the composition that is used to improve retention according to each composition among the claim 1-6, wherein said component (B) has the 0.5% salinization viscosity of 10-100mPas.
8. papermaking process comprises: with adding raw material to according to each the composition that is used for improving retention among the claim 1-7, carry out papermaking then.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004381092 | 2004-12-28 | ||
| JP381099/2004 | 2004-12-28 | ||
| JP381092/2004 | 2004-12-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101094954A true CN101094954A (en) | 2007-12-26 |
Family
ID=38992561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580045343 Pending CN101094954A (en) | 2004-12-28 | 2005-12-28 | Retention improving composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101094954A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107001521A (en) * | 2014-11-17 | 2017-08-01 | 凯米罗总公司 | The method of the cationic water gelatin polymer product dry for preparing, polymer product and application thereof |
| CN109072557A (en) * | 2016-03-22 | 2018-12-21 | 凯米罗总公司 | System and method for manufacturing paper, cardboard or the like |
-
2005
- 2005-12-28 CN CN 200580045343 patent/CN101094954A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107001521A (en) * | 2014-11-17 | 2017-08-01 | 凯米罗总公司 | The method of the cationic water gelatin polymer product dry for preparing, polymer product and application thereof |
| CN109072557A (en) * | 2016-03-22 | 2018-12-21 | 凯米罗总公司 | System and method for manufacturing paper, cardboard or the like |
| CN109072557B (en) * | 2016-03-22 | 2021-12-21 | 凯米罗总公司 | System and method for producing paper, board or the like |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4940952B2 (en) | Yield improver composition | |
| JP4894264B2 (en) | Composition comprising amphoteric water-soluble polymer | |
| JPWO2006070853A6 (en) | Yield improver composition | |
| CN100500720C (en) | Process for producing water-soluble polymer | |
| TWI415997B (en) | Composition and method for paper processing | |
| JP4742861B2 (en) | Composition | |
| JP2005205409A (en) | Amphoteric polymer coagulant | |
| US20060289139A1 (en) | Retention and drainage in the manufacture of paper | |
| CN101094954A (en) | Retention improving composition | |
| JPH11241294A (en) | Paper-strengthening agent for paper making and production of strengthened paper | |
| JP6593642B2 (en) | Papermaking additive and paper obtained using the same | |
| JP7173677B2 (en) | Method for enhancing drainage performance of pulp slurry during manufacture of paper products and products produced therefrom | |
| CN101208479A (en) | Improved retention and drainage in the manufacture of paper | |
| JP2001295196A (en) | Method for improving yield | |
| JP2009022840A (en) | Polymer flocculant and its application | |
| JP2004225208A (en) | Papermaking additive and papermaking method using the same | |
| JPH03174092A (en) | Sizing agent composed of cationic rosin emulsion and production thereof | |
| JPH05287693A (en) | Production of additive for paper production | |
| JPH08113894A (en) | Additive for production of paper | |
| JP2005042270A (en) | Fluorescence retarder and method for retarding fluorescence |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20071226 |