CN1784458A - Aqueous systems containing additive pre-mixes and processes forming the same - Google Patents

Aqueous systems containing additive pre-mixes and processes forming the same Download PDF

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CN1784458A
CN1784458A CN 200480011927 CN200480011927A CN1784458A CN 1784458 A CN1784458 A CN 1784458A CN 200480011927 CN200480011927 CN 200480011927 CN 200480011927 A CN200480011927 A CN 200480011927A CN 1784458 A CN1784458 A CN 1784458A
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polymkeric substance
composition
total
cationic polymers
particle
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克莱门特·L.·布兰加德特
查尔斯·L.·伯迪克
勒妮·M.·加瓦斯
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Hercules LLC
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Hercules LLC
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Abstract

The present invention relates to an additive for pigmented aqueous systems comprising a mixture of a cationic polymer and a high surface area anionic inorganic particle, methods for making and using the additive, methods of forming an aqueous paper coating color as well as cellulose matrix coated therewith; and a process for preparing stabilized pre-mixes.

Description

The method that contains the water-based system of additive pre-composition and be used to form this water-based system
The application requires the rights and interests of U.S. Provisional Application of submitting on May 2nd, 2,003 60/467,802 and the U.S. Provisional Application of submitting on May 15th, 2,003 60/470,762, at this content of each application is all introduced with as a reference.
Technical field
In general, the present invention relates to the method that contains the water-based system of additive pre-composition and form this water-based system, the additive that wherein is used for painted water-based system comprises the mixture of cationic polymers and anion particle, relates to the method that forms water-based paper coating colorant (coating color) and with its coated fibres element matrix; And the method for preparing stable pre-composition.
Background technology
100 for many years, and pigmented coating has been used to improve the optical property and the impressionability of paper.Opacity, brightness, ink receptivity and gloss that pigment in the coating and their formed holes (pore space) have increased paper have been known.Have higher gloss by rolling the formed smooth surface of described coating paper than coarse relatively uncoated substrate, and easier printing thereon.
It is known that cationic polymers and cationic pigment are used for that the paper coating uses in this area.For example, article is LePoutre for example, and P. exists Progress in Organic Coating17, " the The structure of paper coatings:an update " of 89-106 page or leaf (1989), and Lepoutre, P. wait Science at the Journal of in September, 1989 Pulp and Paper, 15, #5 has described in the 183-185 page or leaf " The light-scattering efficiency of microvoids in papercoatings and filled papers " on its surface and has used cationic polymers, amphiphilic polymers is controlled the coating solid with the latex that contains amphiphilic polymers and is fixed and increase the space of dry paint (void) mark.These cationic additives and negatively charged ion coating colorant interacts consumingly, produces the more effectively vesicular structure of scattered light, and has than the paper coating of standard and more to many pigment surface area of exposure.Increase opacity and brightness that scattering of light can promote coating.Increase pigment surface area and can increase absorbency.Yet pigment concussion problem (forming gel and hard aggregate) has hindered the commercial use of cationic polymers additive in paper coating is used.
In using, papermaking use cationic pigment and cationic polymers in a lot of articles and patent, to discuss, for example, and United States Patent (USP) 2,795,545 (Gluesenkamp); United States Patent (USP) 3,804,656 (Kaliski etc.); United States Patent (USP) 5,718,756 (Mohler); United States Patent (USP) 4,738,726 (Pratt); Von Raven A., Scritmatter, G., Weigl, J. is at " the Cationic coating colors-a new coatingsystem " of in December, 1998 TAPPI Journal 141-148 page or leaf; United States Patent (USP) 4,874,466 (Savino); United States Patent (USP) 4,964,955 (Lamar); With United States Patent (USP) 5,169, be described among 441 (Lauzon).These articles and Patent Office are limited to direct interpolation cationic polymers, perhaps handle most water-based paint with the cationic polymers of relative few additive, next carry out high shear mixing, and this will cause the formation of luming.
The present invention is after considered the needs in the industry and relevant method is provided, and employed in the method additive, and this can cause the pigment concussion that reduces, easier use and better operational suitability.
Summary of the invention
The present invention relates to comprise the embodiment of the painted water-based system of additive pre-composition, wherein said additive pre-composition comprises cationic polymers and anion particle (for example inorganic mineral or the synthetic particle and/or their mixture of high surface area, band anionic charge).
The invention still further relates to the method that forms water-based system (for example, water-based paper is coated with colorant), it comprises:
(1) mixed anion particle and cationic polymers; Wherein form the additive pre-composition,
(2) randomly filter this additive pre-composition;
(3) randomly in this additive pre-composition, add stablizer;
(4) randomly this additive pre-composition is joined and be coated with in the slurry body (starch);
(5) randomly in this additive pre-composition, add biocide; With
(6) this additive pre-composition is added in the water-based system.
Further, the present invention includes according to above-described method and come the coating cellulose matrix, and the cellulosic matrix of described coating, it further may further comprise the steps:
(7) coating cellulose matrix; With
(8) dry this cellulosic matrix.
Further, the present invention relates to prepare the embodiment of the method for stable pre-composition, it comprises:
(a) form the pre-composition that comprises anion particle and cationic polymers;
(b) in this pre-composition, add stablizer, wherein formed stable pre-composition; With
(c) randomly in stable pre-composition, add biocide.
In addition, the present invention relates to use the stable pre-composition of aforesaid method production.
Description of drawings
Fig. 1 has described the concentration of cationic polymers and the relation between the pigment concussion.
Fig. 2 has described the relation between dope viscosity and the pre-composition interpolation concentration.
Fig. 3 has described the relation between coating wt and the opaqueness.
Fig. 4 has described the relation between coating wt and the brightness.
Fig. 5 has described the relation between pre-composition interpolation concentration and the opaqueness.
Fig. 6 has described the relation of adding between concentration and the brightness.
Fig. 7 has described the dilution churning time in later stage and the relation between the pigment concussion.
Fig. 8 has described pre-composition addition and the solid relation between fixing.
Embodiment
At this, the full content of all reference, the especially United States Patent (USP) quoted in this specification sheets is all introduced with as a reference.
Unless otherwise stated, concerning the place of quoting numerical range herein, this scope meaning comprises its end points, and all integers and mark in this scope.When a definition scope time, the scope of each embodiment of the present invention is not intended to be limited to the occurrence narrated.In addition, all scopes of being set forth in this article all mean and not only comprise described concrete scope, but also are included in the arbitrary combination that wherein comprises described minimum value and peaked numerical value.
Embodiment of the present invention can be used for for the purpose that promotes dry back structurizing effect, need carry out in the cation-modified application pigment such as the void volume that increases.Thereby embodiment of the present invention are suitable for including but not limited in the industrial application such as paper coating, paper sizing pressurization coating, paper wet end pigment retention, tackiness agent, drilling mud.
In general, the method that the present invention relates to contain the water-based system of additive pre-composition and be used for forming this water-based system, wherein said additive comprises with anion particle blended cationic polymers, form the method for the water-based system (for example, water-based paper coating colorant) contain this additive and with its coated fibres element matrix; And relate to the method for the stable pre-composition of preparation, wherein said anion particle has relaxed the interaction between cationic polymers and the anion aqueous pigment, and has reduced or eliminated the pigment caking significantly.
Term used herein " system " or its derivative include but not limited to paper coating, the paint mixture that contains pigment, paper green end pigment retention, tackiness agent, drilling mud, paper sizing pressurization coating etc.
Term used herein " anion particle " comprises the inorganic mineral of high surface area, band anionic charge, and/or the synthesizing inorganic particle of high surface area, band anionic charge, and/or their mixture.
It is before one of cationic polymers or anion particle are joined water-based system that term used herein " adds " what describe indirectly, and cationic polymers and anion particle are mixed, thereby forms pre-composition.
It is that cationic polymers is joined in the water-based system that term used herein " directly adds " what describe, so do not form pre-composition.
Term used herein " (being total to) polymkeric substance " not only comprises homopolymer but also comprise multipolymer.
The present invention relates to a kind of painted water-based system, it comprises:
(i) comprise cationic polymers and anion particle (for example, high surface area, the band anionic charge inorganic mineral or synthetic particle) the additive pre-composition.
The type and the utilizable various amount that are used for the pigment of this water-based system can change in wide range, yet these aspects it is well known to those having skill in the art that.
The addition that joins the pre-composition in the painted water-based system preferably in the scope of per 100 parts of pigment 0.01-2.0 dry parts, more preferably per 100 parts of pigment 0.05-1.0 parts, most preferably per 100 parts of pigment 0.1-0.5 parts.Yet the addition of pre-composition can change according to the electric density of polymkeric substance.
Typically, the solid content of this pre-composition is about 40% based on about 5%-of this pre-composition gross weight, preferred 15%-about 30%.
In addition, in making described additive pre-composition, cationic polymers can be joined in the anion particle solution, wherein this cationic polymers can add soon, thereby forms the solution than low-solid content.But what also wish is to add anion particle in cationic polymer solution, and this causes the solution of the high solid that can dilute and stir before using.
Be used for cationic polymers of the present invention and can be linear or side chain and should have to a certain degree water-soluble.Water-soluble meaning shows that this cationic polymers can be dissolved in the concentration of effective use or be scattered in the pigment pre-composition.
Cationic polymers can contain the polarity link units, for example (methyl) acrylamide, vinyl cyanide etc., and the nonionic link units that perhaps polarity is lower, (methyl) acrylic acid lower alkyl esters for example is as (methyl) acrylic acid C 1-4Alkyl ester is not as long as this hydrophobicity and this low unitary density of polarity chain link exceedingly reduce the water-soluble of cationic polymers under the working concentration.
Typical cationic polymers comprises that weight-average molecular weight is about 5, and about 3,000,000 dalton of 000-is preferred about 10, and about 1,000,000 dalton of 000-is more preferably about 20,000-about 500,000 daltonian those cationic polymerss.
Need not be limited by theory, believe that the effect of cationic polymers increases along with the increase of electric density usually.The cationic charge density of cationic polymers of the present invention preferably should be higher relatively.The electric density of described cationic polymers is preferably about 0.1 milligramequivalent/Ke-Yue 8 milligramequivalent/grams, more preferably from about 1 milligramequivalent/Ke-Yue 8 milligramequivalent/grams, most preferably from about 2.0 milligramequivalents/Ke-Yue 6.5 milligramequivalent/grams.Electric density can be determined according to those conventional electric charge titration methods as known in the art.
Suitable cationic polymers comprises and is used for those polymkeric substance that water treatment or papermaking are used, and it comprises and being incorporated herein and United States Patent (USP) as a reference 4,753,710; 5,246,548; 5,256,252 and 6,100, those cationic polymerss described in 322.For example, at United States Patent (USP) 5,256, the representative cationic polymers of describing in 252 comprises the quaternary ammonium salt of (methyl) acrylic acid aminoalkyl ester (being total to) polymkeric substance that (1) N-alkyl replaces, comprise for example poly-(diethylamino ethyl propylene acid esters) acetate, poly-(diethylamino ethyl-methacrylate), poly-(dimethyl aminoethyl methacrylate) (as " DMAEM.MC Q " of alkyl chloride quaternary ammonium salt) etc.; (2) polyamine with for example by the quaternary ammonium salt of the reaction product of the acrylate type compound of methyl acrylate and quadrol preparation; (3) (being total to) polymkeric substance of (methacryloyl oxygen ethyl) trimethyl ammonium chloride; (4) (being total to) polymkeric substance of acrylamide and quaternary ammonium compound such as acrylamide and diallyl methyl (β-propionamido-) ammonium chloride, acrylamide (Beta-methyl acryl oxygen ethyl) trimethylammonium methylsulfuric acid ammonium etc.; (5) quaternised vinyl lactam-acrylamide (being total to) polymkeric substance; (6) quaternary ammonium salt of the unsaturated carboxylic acid polyester of hydroxyl, for example poly--2-hydroxyl-3-(methacryloxy) oxypropyl trimethyl ammonium chloride; (7) as the reaction product of phenylethylene-maleic anhydride (being total to) polymkeric substance and 3-dimethylamino propylamine and the quaternary ammonium salt of the polyimide-amine for preparing; (8) quaternised polyamine; (9) the quaternised reaction product of amine and polyester; (10) quaternary ammonium salt of the condensation of polyvinylamine and ethylene dichloride (being total to) polymkeric substance; (11) the halid quaternized condensation product of polyalkylene-polyamines and epoxy; (12) the quaternized condensation product of alkylidene group-polyamines and multifunctional halohydrin, for example (being total to) polymkeric substance (" EPI-DMA ") of Epicholorohydrin/dimethyl amine; (13) the quaternized condensation product of alkylidene group-polyamines and halohydrin; (14) (being total to) polymkeric substance of the quaternized condensation of ammonia and halohydrin; (15) quaternary ammonium salt of polyvinyl benzyl trialkylamine, for example polyvinyl benzyl trimethyl ammonium chloride; (16) has the quaternary ammonium salt of (being total to) polymkeric substance of the vinyl-heterocyclic monomer of nitrogen in the ring, for example poly-(1,2-dimethyl-5-vinyl pyridine Methylsulfate), poly-(chlorination-2-vinyl-2-tetrahydroglyoxaline) etc.; (17) comprise the poly dialkyl diallyl ammonium salt of diallyl dimethyl ammoniumchloride (" polyDADMAC "); (18) (being total to) polymkeric substance of vinyl unsaturated acid, its ester and acid amides and diallyldialkylammonihalide salt comprises poly-(vinylformic acid-diallyldimethylammonium chloride-hydroxypropyl acrylate) (" polyAA-DADMAC-HPA "); (19) PMAm base oxypropyl trimethyl ammonium chloride (" polyMAPTAC "); (20) quaternary ammonium salt of ammonia-ethylene dichloride condensation (being total to) polymkeric substance; And the quaternary ammonium salt of (21) epoxy halogenide (being total to) polymkeric substance, for example Polyglycol 166-450 Methochloride, Polyglycol 166-450 Methylsulfate etc.Can also utilize and comprise above-mentioned two or more mixture of polymers.
The preferred cation polymkeric substance comprises diallyldialkylammonihalide salt (being total to) polymkeric substance, (being total to) polymkeric substance of diallyl amine, (being total to) polymkeric substance of diallyl alkylamine, polymine, (being total to) polymkeric substance of dialkylamine/Epicholorohydrin, (being total to) polymkeric substance of polyamines/Epicholorohydrin, (being total to) polymkeric substance of multiamide/Epicholorohydrin, (being total to) polymkeric substance of multiamide amine, (being total to) polymkeric substance of multiamide amine/Epicholorohydrin, (being total to) polymkeric substance of dialkyl aminoalkyl acrylamide and Methacrylamide and quaternised (being total to) polymkeric substance, (being total to) polymkeric substance of dialkyl aminoalkyl acrylate and methacrylic ester and quaternised (being total to) polymkeric substance.Preferred cationic polymers comprises (being total to) polymkeric substance, the polymine of diallyl dimethyl ammonium salt (being total to) polymkeric substance, polyamines/Epicholorohydrin, (being total to) polymkeric substance and multiamide amine/Epicholorohydrin (being total to) polymkeric substance of dimethylamine/Epicholorohydrin.Most preferred cationic polymers comprises (being total to) polymkeric substance of diallyl dimethyl ammonium salt (being total to) polymkeric substance and dimethylamine/Epicholorohydrin.Can also utilize and comprise above-mentioned two or more mixture of polymers.
When joining cationic polymers in the water-based system, preferably its concentration in pre-composition is for being less than 2.5%, and more preferably 1.5% or still less, most preferably 1.0% or still less.
Usually, this cationic polymers can make according to any ordinary method known in the art.
Usually, as noted above, the anion particle that is used for the present invention comprises the inorganic mineral of the band anionic charge of high surface area, and/or the synthesizing inorganic particle of the band anionic charge of high surface area, and/or their mixture.
The inorganic mineral and the synthesizing inorganic particulate embodiment of suitable band anionic charge of the present invention generally include swelling clay, if you would take off soil for instance, and silica base particle (for example, silica reaches the particle based on silico-aluminate (alumino-silicate)).
Operable polynite is known in paper retention aid field, and comprises swelling clay and synthetic or semisynthetic equivalent.
Suitable polynite includes but not limited at this description and the United States Patent (USP) 4 that is incorporated herein by reference, 753, described in 710 those, also comprise in the dioctahedron polynite group for example the member (for example, montmorillonite (montmorillonite), wilkinite, polynite (montmorillinite), beidellite and nontronite) and the trioctahedron group in member's (for example, hectorite and saponite), sepolite, sepiolite (sepialite) and attapulgite.
Suitable wilkinite and hectorite are disclosed in United States Patent (USP) 4,305,781 respectively; 4,753,710; 5,501,774; 5,876,563; Also with United States Patent (USP) 4,753, and among the 710 disclosed EP 0235893 (for example, wilkinite can be the negatively charged ion swelling clay, as sepiolite, attapulgite, and perhaps preferred polynite.The wide in range United States Patent (USP) 4,305 that is described in, the wilkinite in 781 is suitable.Suitable montmorillonite comprises Wyoming bentonite or Fuller's earth.These clays can be chemical modifications, for example by alkaline purification calcium-base bentonite are transformed into alkali metal bentonite, also can not be); And also with United States Patent (USP) 5,071, described in the 512 disclosed EP 0446205, be incorporated herein these patents as a reference.
Preferred described swelling clay is a colloid,, has about 1 millimicron (1 nanometer) to the interior granularity of about 1 little (1 micron) scope that is.In addition, preferably this swelling clay surface-area is 50m at least 2/ g, more preferably surface-area is at least 100m 2/ g, most preferably 200m at least 2/ g.For example, the surface-area of wilkinite after expanding is preferably 400m at least 2/ g.Typical coating clay and lime carbonate surface-area are 1-12m 2/ g.
Preferred swelling clay, most preferably wilkinite has at least 60% below 50 microns, more preferably at least 90% below 100 microns, most preferably at least 98% in the dry granularity below 100 microns (dry size).
According to the present invention, operable silica base particle is included in United States Patent (USP) 5,167,766 and 5,274, described in 055 those, for example, colloided silica, (such compound is also referred to as aluminium silicate polymer (polyaluminosilicate) and aluminium silicate polymer microgel for colloidal aluminium modified silica or pure aluminium silicate, they all are contained in the silica and pure aluminium silicate of this employed term colloidal aluminium modification), and their mixture, use separately or be combined and used in known in the art as the anionic inorganic particle of retention aid etc. with other type.In addition, suitable silica and silicoaluminate alkali particle comprise and are disclosed in United States Patent (USP) 4,388,150; 4,954,220; 4,961,825; 4,927,498; 4,980,025; 5,127,994; 5,176,891; 5,368,833; 5,447,604; 5,470,435; 6,100,322; Also be disclosed as United States Patent (USP) 5,603, those among 805 EP0656872 and the WO 95/23021 are incorporated herein these all patents with as a reference.
The granularity of suitable silica base particle be preferably be lower than about 50 nanometers, more preferably less than about 20 nanometers, about 10 nanometers of 1-most preferably from about.Suitable silica base particle specific surface area is 50m at least 2/ g, preferably 100m at least 2/ g, and preferred 200m at least 2/ g.Specific surface area can be according to Sears at Analytical Chemistry 28 (1956): 12, and the method described in the 1981-1983 is measured with the NaOH titration.
Also can use the mixture of silica and swelling clay (for example polynite, preferred natural sodium bentonite) in the present invention.
Usually, anion particle and the cationic polymers ratio in the additive pre-composition can be about 95: 5 to about 10: 80 (cationic polymers of about 95 weight % to the anion particle of about 10 weight % and about 5 weight % to about 80 weight %), preferred about 90: 10 to about 20: 80 (cationic polymers of about 90 weight %) to the anion particle of about 20 weight % and about 10 weight % to about 80 weight %, more preferably 90: 10 to about 40: 60 (cationic polymers of about 90 weight %) to the anion particle of about 40 weight % and about 10 weight % to about 60 weight %, most preferably 85: 15 to about 60: 40 (cationic polymers of about 85 weight %) to the anion particle of about 60 weight % and about 15 weight % to about 40 weight %.Yet this ratio depends on employed polymkeric substance, and for example, when using the mixture of wilkinite and poly-DADMAC, the ratio of wilkinite: poly-DADMAC is preferably at about 92.5: 7.5 to 60: 40, more preferably at about 70: 30 to about 85: 15 scope.
The invention further relates to and form water-based system (for example, water-based paper coating colorant), it comprises:
(1) mixed anion particle and cationic polymers; Wherein formed the additive pre-composition,
(2) randomly filter this additive pre-composition;
(3) randomly in this additive pre-composition, add stablizer;
(4) randomly this additive pre-composition is joined and be coated with in the slurry body;
(5) randomly in this additive pre-composition, add biocide; With
(6) this additive pre-composition is joined in the water-based system.
Further, the present invention includes according to above-described method coating cellulose matrix, and the matrix of described coating, it further may further comprise the steps:
(7) coating cellulose matrix; With
(8) dry this cellulosic matrix (for example, paper).
This additive pre-composition can join in the water-based system in the arbitrfary point in the preparation coating process.Yet, preferably, pre-composition joined be coated with in the slurry body or last the adding.This is coated with the compound that slurry body is a lot of coating compositions, wherein is in order to dilute pre-composition pre-composition to be joined to be coated with in the slurry body.This is coated with the water that slurry body typically contains high percentage ratio (for example with respect to solids content be about 70% water), thereby makes it possible to dilute this pre-composition and do not need to introduce the water of amount in addition to whole water-based system.Yet under each situation, this additive pre-composition all is to add indirectly, and wherein as mentioned above, described additive pre-composition formed before joining water-based system.Can use those anion particles described above and cationic polymers here.
Usually, when using the non-expansibility anion particle, the order by merging in the step (1) is unimportant to performance, but normally anion particle " same as before " is joined in the polymers soln.But when producing the pre-composition (＞5% solid) of high solid, the order of step is important in the described method.If use swelling clay (for example wilkinite etc.), then for swelling clay being added to the water, adding then this polymkeric substance, be preferably anion particle is joined in a certain amount of water that contains cationic polymers.
As shown in step (2), use those methods as known in the art, for example use Ronningen-Petter DCF-800 strainer with 100 microns sieve apertures, can randomly filter pre-composition to remove formed any coarse grain, wherein this strainer is cleared away this sieve automatically to prevent the sieve obstruction.
Introducing can add optional stablizer in pre-composition in step (3), to reduce any precipitation or the layering of anion particle in pre-composition.This stablizer can be high molecular or middle molecular weight, can be cationic or non-ionic.Nonionic stabiliser comprises the methylol Natvosol, the Natvosol of butylglycidyl ether modification, hydroxypropylcellulose, methyl hydroxyethylcellulose, methylhydroxypropylcellulose, methylcellulose gum, ethyl cellulose, the poly-N-vinyl pyrrolidone, polyvinyl alcohol, polyethylene oxide, poly(propylene oxide), polyacrylamide, starch ethers (for example hydroxyethyl starch), starch ester (for example starch of alkyl succinic acid anhydride modification), Sumstar 190, guar gum, pectin, carrageenan, Viscogum BE, xanthan gum, water soluble protein (for example soya bean) and lyophobic association type thickener for paints.The cationic stabilized agent comprise cationic starch and Galactosol cation guar gum (Hercules Inc., Wilmington, Delaware).Preferred described stablizer is a non-ionic type.Most preferably described stablizer is hydroxypropylguar gum or Natvosol.
Usually, use viscosity that the amount of stablizer causes water-based system to be 1000cps (Brookfield under the 100RPM) at least, preferably 2000cps, more preferably 3000cps at least at least.Most preferred viscosity is in the scope of the about 3500cps of about 2000-.
Typically, the addition of stablizer is about 5% based on about 0.1%-of described pre-composition gross weight, and still, this amount depends on the type of stablizer and the solid content of pre-composition.For example, for Natvosol and hydroxypropylguar gum, preferred described amount be based on the gross weight of pre-composition about 0.2% to about 1.0%, more preferably 0.3% to about 0.7%.The adding speed of stablizer and be stirred in known in the art, should be adjusted mixture to obtain to mix well.
For instance, prevent that bacterium from consuming specific polymkeric substance such as guar gum and when the peculiar smell that causes, layering and shortage package stability, use the optional biocide in the step (5) usually in hope.Water-based system can not use this biocide and make, yet, because the disadvantageous effect of bacterium, need refrigeration, vacuum-packed or in short duration, use usually.The embodiment of suitable antimicrobial agents in order for example comprise the AMA-35D-P biocide (Kemira ChemicalCo.Marietta, Georgia) and Proxel GXL (AveciaInc., Wilmington DE).
For step (6), pre-composition normally aspirates or is poured in the water-based system, to the speed of its method or adding without any special restriction.As mentioned above, when joining it in water-based system, the concentration of preferred cationic polymkeric substance in this pre-composition is for being less than 2.5%, more has preferred 1.5% or still less, and most preferably 1.0% or still less.
The coating of cellulosic matrix can be carried out according to the currently known methods of this area, for example, by Fapet Oy (2000) publish, Lehtinen, described in the Pigment Coating and SurfaceSizing of Paper 415-594 page or leaf of Esa like that.
The drying of cellulosic matrix can be carried out according to the currently known methods of this area, for example, publish by Fapet Oy (2000), Lehtinen, described in the Pigment Coating and SurfaceSizing of Paper 415-594 page or leaf of Esa like that.
The invention further relates to the stable method that is suitable for the pre-composition that after one period storage period, uses that preparation is made of polymkeric substance and anion particle.More specifically, preparing the stable anion particle/polymkeric substance pre-composition and the method for stablizer comprises:
(a) formation comprises the pre-composition that is preferably bentonitic anion particle and cationic polymers;
(b) in this pre-composition, add stablizer (neutral or cationic), wherein formed stable pre-composition; With
(c) randomly in pre-composition, add biocide.
Except described above, suitable bentonitic embodiment comprises for example commercially available composition such as sodium bentonite (Wyoming or western part), and it has high turgidity in water.
Cationic polymers component of the present invention can be any cationic polymers that uses in the conventional paper technology, for example described above those.Similarly, anion particle described above and stablizer also can use at this.
Usually, as mentioned above, it is 1000cps (brookfield viscosity under the 100rpm) at least that the consumption of stablizer should cause viscosity, preferred 2000cps at least, more preferably 3000cps at least.Most preferably this viscosity is in the scope of the about 3500cps of about 2000-.In addition, stablizer adds with the about 0.2%-about 5% based on the pre-composition gross weight usually, but this amount depends on the kind of stablizer and the solid content of pre-composition.For example, for Natvosol and hydroxypropylguar gum, preferred described amount is about 1.0% based on about 0.2%-of pre-composition gross weight, and more preferably 0.3%-about 0.7%.
The invention further relates to the formed stable pre-composition of above-mentioned method.
Embodiment
In the following embodiments, describe the present invention further in detail, wherein all parts and percentage ratio are by weight.Should be appreciated that the embodiment of these expression preferred embodiment of the invention just illustrates for example and provides.From top discussion and these embodiment, under without departing from the spirit and scope of the present invention, those skilled in the art can determine principal character of the present invention, and the present invention is made various changes and modification, so that it is suitable for various application and condition.
Embodiment 1-85: 15 wilkinites: the preparation of poly-DADMAC pre-composition
Make and prepare 85: 15 wilkinites of 5% solid in the following method: the poly-DADMAC pre-composition.106.25g wilkinite (coming from Southern Clay Products, Gonzalez, the Bentolite H of Texas) and 2346.88g water are packed in the 5L beaker, use overhead stirrer to mix 1-2 minute then up to obtaining uniform pre-composition (500rpm).Under agitation in 1-2 minute time, drip then 46.88g PRP-4440 poly-DADMAC (the diallyldimethylammonium chloride polymkeric substance, 40% solid can be available from Pearl River Polymers, Riceboro, Georgia).In the adition process of poly-DADMAC, described mixture expansion and retrogradation, and then disperse.After finishing adding, stirred pre-composition in addition 2 hours, supersound process is 10 minutes on the #2 of Branson ultrasonoscope 450 device, removes by filter any coarse grain by 200 purpose sieves then.If necessary, the H of use 15% 2SO 4The pH that finishes pre-composition is at last adjusted to pH 7-8.
Embodiment 2-silica: the preparation of Reten 203 pre-compositions
Make preparation 5% solid silica: Reten 203 cationic polymers pre-compositions on the proportional range shown in the table 1 in the following method.Silica (Ludox FM, Grace-Davison, Columbia with requirement; Maryland) and water pack in the beaker of 100mL, use overhead stirrer (500rpm) to mix then 15 minutes.Then vigorous stirring (form good good vortex) drip down requirement Reten 203 (the diallyldimethylammonium chloride polymkeric substance, Mn=2-300,000,20% solid, available from Hercules Incorporated, Wilmington, DE).Stirred this pre-composition then 2.5 hours, and on the #8 of Branson ultrasonoscope 450 device supersound process 3 minutes.Filter to remove any coarse grain by 200 purpose sieves again.If necessary, the H of use 15% 2SO 4This pre-composition is adjusted to pH 7-8.
Table 1
Final total solids % 5 The TS% of silica solution 16.02
Final pH 7-8 The TS% of Reten solution 20.41
Final volume 25
Ratio
Silica Reten Silica % G. silica Reten％ g.Reten G. water
100 1 4.95 7.73 0.05 0.06 17.21
100 10 4.55 7.09 0.45 0.56 17.35
100 50 3.33 5.20 1.67 2.04 17.76
100 100 2.50 3.90 2.50 3.06 18.04
50 100 1.67 2.60 3.33 4.08 18.32
10 100 0.45 0.71 4.55 5.57 18.72
1 100 0.05 0.08 4.95 6.06 18.86
The preparation of embodiment 3-kaolin/calcium carbonate coating colorant
Make the coating colorant for preparing kaolin/calcium carbonate-base in the following method.In table 2, provided the detailed description of compound.The dilution water and the dispersion agent (DispexN40V, Ciba Specialty Chemicals, Sufolk VA) that at first add requirement.Add Hydrafine  #1 kaolin (can be, Edison, NJ buys) under the Cowles agitator vigorous stirring lentamente using then from J.M.HuberCorporation.In the whole process that clay adds, remain good vortex.After clay dispersion was good, (Omya was available from Pleuss-Staufer Incorporated, VT) and RPSTiO to add the water-ground limestone of Hydrocarb  90 in vigorous stirring lentamente 2Slurries (available from E.I.duPont de Nemours and Company, Wilmington, DE).Use the Cowles agitator to continue to stir slurries 30 minutes then.
In the preparation pigment slurry, use steam-jacketed kettle under 95-100 ℃, Penford 290 starch (available from Penford Products Co.Cedar Rapids, Iowa) to be boiled 45 minutes.The concentration (30%) of adjusting starch in the process of boiling is with the compensation moisture loss.Then, in vigorous stirring, hot starch solution (with 65 ℃ of storages) is joined in the pigment mucilage.After coating cools down from starch adds, and the adding styrene butadiene latices (Dow 620, Latex CP620NA, and Dow U.S.A.Midland Michigan) also fully is mixed in the coating colorant.In vigorous stirring, one after the other add Calsan  65 lubricants (BAS F, North Mount Olive, NJ), Sequarez  755 insolubilizers (Omnova SolutionsCorporation, Fairlawn is OH) with Proxel GXL sanitas (Avecia Inc.).After these additives were scattered, the pH that will be coated with colorant with ammonium hydroxide adjusted to 8.0.Before particle/cationic polymers mixture adds, water will be coated with the solid of colorant and adjust to 68%.
Pre-composition with wilkinite/poly-DADMAC (embodiment 1) and silica/poly-DADMAC (embodiment 2) is added in the coating colorant of clay/carbonate.Particle/cationic polymers the pre-composition of requirement is added drop-wise in the coating colorant sample (68% solid) that stirs.Except as otherwise noted, the pre-composition of wilkinite and silica adds with 5% of total solids.In the whole interpolation process of particle pre-composition, keep good vortex.The water that adds requirement then is diluted to 62% total solids will be coated with colorant, except as otherwise noted.Before test, with the sample restir of handling 15-30 minute (500rpm).
Table 2
Clay/carbonate compound
Additive Describe Umber Exsiccant gram number Solid % The wet gram number that adds
#1 kaolin Hydrafine 58 1740 100％ 1740
GCC Hydrocarb 90 41 1230 100％ 1230
TiO2 The RPS slurries 1 30 71％ 42.3
Latex Dow 620 9 270 50％ 540
Starch Penford 290 3 90 30.36％ 296.4
Lubricant Calsan 65 0.3 9 50％ 18
Dispersion agent Dispedx N-40 0.1 3 40％ 7.50
Insolubilizer Sequarez 755 0.21 6.3 55％ 11
Sanitas Proxel GXL 0.1 3 100％ 3
Alkali Ammonium hydroxide On demand
Total exsiccant gram number 3378.3
Total wet gram number 3885.65
Total solids 68％
The gram number that is added to the water 1082.44
Final gross weight 4968.09
Embodiment 4-wilkinite/poly-DADMAC pre-composition
With 663g water and 108.4g PRP-4440 poly-DADMAC (the diallyldimethylammonium chloride polymkeric substance, 40% solid, Pearl River Polymers, Riceboro Georgia) packs in the stainless steel beaker and stirred 5 minutes with 500rpm.In 5 minutes time, sneak into 228.3g wilkinite (what obtained contains 92.7% solid, derives from Southern Clay Products, Gonzalez, the Bentolite H of Texas) then.After interpolation is finished, stirred pre-composition 2 hours with 500rpm.In whole process, make the temperature of pre-composition remain on 20 ℃.Filter this pre-composition by 200 mesh sieves then and assemble formed any coarse grain to remove by negatively charged ion wilkinite and cationic polymers.The coarse grain of about 0.5g is separated (total solids 0.2%) by sieve.
After finishing filtration, when continue stirring with 1.2g biocide (AMA-35D-P biocide, Kemira Chemical Co.Marietta, Georgia) and subsequently hydroxypropylguar gum (the HPG of 6.0g, Galactasol 40H4FD 1-Hercules, Wilmington Delaware) is sprayed onto in the pre-composition.Restir this pre-composition 3 hours (500rpm) after adding is finished.In whole process, make the temperature of pre-composition remain on 20 ℃.The viscosity of pre-composition increases sharply in begin after adding hydroxypropylguar gum 30-60 minute.Final product has 7.9 pH and the Brookfield RV viscosity (100rpm, #5 axle) of 3000cps.
Embodiment 5-pre-composition solid and HPG addition are to stratified influence
Carry out shaker test to determine the solid of the highest wilkinite/poly-DADMAC pre-composition, this shaker test can be carried out in the other method described in the embodiment 4 by use.As shown in table 3, the fluid pre-composition is to make with the total solids up to 40%.The Brookfield RV viscosity of pre-composition increases (100rpm) along with the increase of solid %.
Table 3
Solid % Brookfield viscosity
21％ 34cps
24％ 42cps
27％ 50cps
30％ 64cps
35％ 120cps
40％ 260cps
Measure under 21%, 24%, the 27% and 30% pre-composition solid HPG then to the influence of settling stability.Method described in the use embodiment 4 prepares pre-composition.The addition of HPG is selected to prepare the pre-composition viscosity in the 500cps-3500cps scope for each solid %.The acceptable settling stability is defined as and is less than 5% solid layering from top to the bottom of pre-composition and does not have lump to form.
As shown in table 4, the stability of pre-composition usually increases along with the increase of the addition of solid %, HPG and pre-composition viscosity.All 16 pre-compositions all show 1 day good settling stability.(Brookfield RV, pre-composition 100rpm) have obtained the acceptable stability in storage at least 1 week to all initial viscosities for 1500cps at least.All initial viscosities all can not pass through stability test less than the pre-composition of 1500cps after storing for 1 week.And the pre-composition that all initial viscosities are at least 3000cps does not demonstrate the formation of stratified sign or lump after storing for 8 week.To passed through 4 week and 8 week stability test pre-composition test show that when testing with the coating compound described in the embodiment 3, they have provided the increase of dope viscosity expection and have not had the pigment concussion.Pre-composition is diluted to 5% total solids and in joining coating before stirred 30 minutes.200g handled is coated with material samples and remains in the standard of measurement that coarse-grained amount on 200 mesh sieve is used as the pigment concussion.
The preparation of the wilkinite that embodiment 6-is stable/poly-DADMAC pre-composition
255g wilkinite (wilkinite H can buy from Southem Clay Products) and 1632.5g water are packed into the stainless steel beaker, mixed (500rpm) 1-2 minute with overhead stirrer then.In vigorous stirring, and the PRP-4440 poly-DADMAC of dropping 112.5g in 1-2 minute time period (the diallyldimethylammonium chloride polymkeric substance, 40% solid can be available from Pearl River Polymers, Riceboro, GA).In the adition process of PRP-4440, this mixture expansion and retrogradation, and then be separated into the fluid pre-composition.In case after finishing adding, just continue to stir this mixture 90 minutes, then supersound process 15 minutes on the #2 of Branson Sonifier 450 device.
Then the aliquots containig of 200mL cationic bentonite pre-composition is packed in the glass beaker.When using the overhead stirrer vigorous stirring, the Natrosol 250H4BR of 1.0g (Natvosol can be from Hercules, Wilmington, DE buys) is added in the pre-composition lentamente.In case this adding is finished, just continue to stir this mixture 30 minutes, use BransonSonifier 450 supersound process 6 minutes on the #2 device then.After fortnight at room temperature, not observing pre-composition has precipitation or stratified sign.
The dilution of embodiment 7-pre-composition is to the influence of pigment concussion
Under 0.75% and 2.25% strength of solution, measure and (be equal to PRP-4440 from Pearl River Polymers by direct adding PC-1193, the diallyldimethylammonium chloride polymkeric substance is called PRP-4440 hereinafter) and the pigment oscillation degree that causes.These strength of solution are respectively corresponding to 85: 15 wilkinite under 5% and 15% total solids: the PRP-4440 pre-composition.This wilkinite pre-composition is to use the method described in the embodiment 6 to prepare.Evaluation is carried out in the clay described in the embodiment 3/carbonate coating colorant.200g handled is coated with the standard of measurement that material samples the coarse-grained amount on 200 mesh sieve of retaining in is used as the pigment concussion.
As shown in Figure 1, by the concentration of PRP-4440 is reduced to 0.75% from 2.25%, reduced the pigment oscillation degree in clay/carbonate coating colorant significantly.The mixture concentration of wilkinite with 85: 15: PRP-4440 is reduced to 5% (0.75% PRP-4440) from the total solids of 15% (2.25% PRP-4440) also can reduce the pigment concussion.Directly add PRP-4440 and add the relatively demonstration of 85: 15 the caused pigment oscillation degree of wilkinite mixture with 15% solid (also be 2.25% PRP-4440) with 2.25% solid, the pre-composition that contains wilkinite PRP-4440 makes pigment concussion minimizing 85-90%.The similar contrast of the wilkinite mixture concentration of PRP-4440 strength of solution with 0.75% and 5% total solids (also being 0.75%PRP-4440) shows, pre-mixing PRP-4440 and wilkinite make pigment shake to have reduced 98-99%.85: 15 wilkinite mixture of 5% solid has provided with the coating of not handling similar in the same old way pigment has been shaken.
Embodiment 8-wilkinite/poly-DADMAC dilution is to the influence of dope viscosity
Prepare 85: 15 the wilkinite of total solid concentration in the 2.5%-20% scope with dilution by the 25% solid pre-composition that method described in the embodiment 4 prepares: the PRP-4440 pre-composition.Test of the influence of each pre-composition then to the kaolin/calcium carbonate coating compound brookfield viscosity described in the embodiment 3.Test is a pre-composition addition in benchmark 0.35-0.55 part scope with coating pigment.Under given pre-composition addition, (Brookfield LVT 60r.p.m.) adds the reduction of concentration and increases (referring to Fig. 2) along with pre-composition the brookfield viscosity of coating.
The influence of embodiment 9-poly-DADMAC/ wilkinite ratio
Use high molecular (Mn=2-300,000, Reten 203, Hercules, Wilmington, DE) and lower molecular weight (Mn=30,000, PRP-4440, Pearl River Polymers, Riceboro, diallyldimethylammonium chloride polymkeric substance (poly-DADMAC) preparation wilkinite/poly-DADMAC pre-composition Georgia).Use the anion particle of the wilkinite (Bentolite H, Southern Clay Products) of high surface area as pre-composition.The cationic polymers content of described pre-composition is the 5-50% (referring to table 5 and 6, the wilkinite of 95%-50%) of total solids.This pre-composition uses the method preparation described in the embodiment 1.
Then, every kind of wilkinite/poly-DADMAC pre-composition of test is to the kaolin/water-ground limestone base coating brookfield viscosity described in the embodiment 3 and the influence of pigment concussion.The interpolation concentration of cationic polymers can have remarkable influence (embodiment 7 and 8) to its performance.Therefore, the interpolation concentration of every kind of pre-composition is selected, added concentration (0.75%) in whole wilkinite/poly-DADMAC proportional range, to obtain identical cationic polymers.As shown in table 5 and table 6, the % total solids of every kind of pre-composition and interpolation concentration thereof change with poly-DADMAC and bentonitic ratio.Usually, the increase of the dope viscosity that is obtained under given cationic polymers addition increases along with the increase of cationic polymers percentage ratio in pre-composition.Therefore, adjust the addition of every kind of pre-composition to obtain identical dope viscosity (about 2000cps, Brookfield RV, 100rpm, #4 or #5 axle).Test undressed coating (coating self) in contrast.Also direct adding high molecular and lower molecular weight poly-DADMAC cationic polymers are measured, to quantize to form in advance the benefit of described pre-composition.The concentration of cationic polymers is fixed on 0.75% solid, and this is identical with the interpolation concentration of cationic polymers in wilkinite/poly-DADMAC pre-composition.
Detect the pigment concussion of each coating of handling (coating that contains the additive pre-composition) then.Described in embodiment 7,200g is coated with material samples retains in the standard of measurement that the coarse-grained amount on 200 mesh sieve is shaken as pigment.The results are shown in table 5 and the table 6.Directly add and appoint any positively charged ion poly-DADMAC polymkeric substance all to produce significant pigment concussion.For the pigment concussion of high molecular and lower molecular weight poly-DADMAC, the pre-composition for preparing between 15%-30% (wilkinite of 85%-70%) with poly-DADMAC concentration has provided optimal results.The pre-composition that makes in this scope poly-DADMAC addition is compared with the corresponding cationic polymers of direct adding and has been obtained the bigger dope viscosity increase and the pigment concussion of much less.Poly-DADMAC low and higher concentration causes the reduction of performance in the wilkinite pre-composition.The pre-composition for preparing under poly-DADMAC addition between 7.5% and 15% and the poly-DADMAC addition 40% has caused very big dope viscosity to increase and the pigment of medium level shakes.The pre-composition for preparing under 5% and 50% poly-DADMAC pre-composition addition causes and directly adds the similar pigment concussion of corresponding poly-DADMAC cationic polymers.
Based on these results, wilkinite/poly-DADMAC the pre-composition that contains 7.5%-40%poly-DADMAC (wilkinite of 92.5%-60%) is for more excellent, and the wilkinite/poly-DADMAC pre-composition that contains 15%-30%poly-DADMAC (wilkinite of 85%-70%) is for more preferably.
The tentative coating machine evaluation of embodiment 10-kaolin/calcium carbonate coating
Go up 85: 15 wilkinite of evaluation at the cylinder shape test coating machine (CLC) of Western Michigan University: the coating performance of PRP-4440 pre-composition.Described pre-composition is that the method described in the employing embodiment 1 prepares with 5% total solids.The coating colorant of clay/carbonate and addition means then use described in the embodiment 3.With the interpolation concentration fixed of pre-composition at 5% total solids.Use uncoated wood pulp substrate as substrate (38g/m 2).Surface covered is fixed on 925 meters/minute.Wilkinite/PRP-4440 the pre-composition of evaluation under 0.45 part and 0.65 part of addition.Test undressed coating in contrast.Adjust the gap length between substrate and the coating blade, be used for each of the coating handled for reference sample and wilkinite: PRP-4440 to wear 3-8g/m 2Glue spread.Before the test under 65 ℃ and 1000 pounds/linear inch this White Board of calendering 3 times.
Shown among Fig. 3 and 4 opaqueness of CLC White Board and the test result of brightness.When in whole coating weight scope, comparing, the coating of handling through wilkinite: PRP-4440 than undressed to have obviously higher opaqueness and brightness in the same old way.
Embodiment 11-wilkinite/poly-DADMAC adds the influence of concentration
25% solid pre-composition by method preparation described in the dilution use embodiment 4 prepares the wilkinite/poly-DADMAC pre-composition of total solid concentration in the 2.5%-20% scope.Test of the influence of every kind of pre-composition then to coating opaqueness and brightness.This research is to go up, use the 62% solid clay/carbonate coating compound described in the embodiment 3 at Western Michigan University cylinder shape test coating machine (CLC) and adopt the method described in the embodiment 10 to carry out.As shown in Fig. 5 and 6 (best data regression fit), by adding the 0.5 part of wilkinite/opaqueness that the poly-DADMAC pre-composition obtains and the increase of brightness along with decline is stablized in the increase of adding concentration.Do not wish to be limited by theory, these result's hints are relevant with the increase of viewed brookfield viscosity with the increase of opaqueness by wilkinite/brightness that the poly-DADMAC pre-composition obtains.Based on these results, the interpolation concentration of 10% total solids is preferred.The pre-composition that is less than 8% total solids adds concentration for more preferably.
The influence of embodiment 12-wilkinite/poly-DADMAC churning time
Amount by the pigment that wilkinite/the poly-DADMAC pre-composition the forms concussion (Hard Roll in the coating) described in the adding embodiment 4 is measured in 10,15,20,25 and 30 minutes after 25% total solids is diluted to 5% total solids.Use clay/carbonate coating compound of describing among the embodiment 3 to estimate (64% solid).As shown in Figure 7, after dilution, stir stable decline in 25 minutes that begin by the amount that in described coating, adds the pigment concussion that wilkinite/the poly-DADMAC pre-composition forms.Longer churning time does not have wholesome effect for the amount of formed pigment concussion in the paper coating.Based on these results, at least 25 minutes churning time is for preferred after the high solid pre-composition is diluted.This research is at room temperature carried out.Time short under comparatively high temps may be just enough.
Embodiment 13-coating solid is fixed
Coating solid fixing fast (with fixing as the dry thing of coating under the low % solid) is relevant with the coating brightness and the opaqueness that increase.Measured the stable wilkinite of HPG described in the embodiment 4 in the scope of pre-composition addition: the poly-DADMAC pre-composition influences coating solid fixed.Clay described in the embodiment 3/carbonate coating is used to the research.Pre-composition is diluted to 5% solid, before it is added the coating compound, stirred 25 minutes then.In each case, after pre-composition adds, the coating solid is adjusted to 64%.As shown in Figure 8, the point of fixity of coating stably reduces along with the increase of pre-composition addition.These results show, wilkinite: the poly-DADMAC pre-composition can be used to control the coating solid and fixes.
Embodiment 14-wilkinite: poly-DADMAC pre-composition and clay/carbonate after treatment The ζDian Shi of coating
Use Malvern ζ Sizer and test a series of wilkinites: the ζDian Shi of PRP-4440poly-DADMAC pre-composition by the described method of Lauzon (introduce in this article with as a reference United States Patent (USP) 5,169,441).Described pre-composition uses the method preparation described in the embodiment 1.As shown in table 7, the particle in all four kinds of pre-compositions all carries positive ζDian Shi.The ζDian Shi that well-known undressed swelling soil zone is negative.Measured positive ζDian Shi has confirmed combining closely of positively charged ion poly-DADMAC polymkeric substance and bentonite clay particle in this research.
The analysis that undressed clay/carbonate described in embodiment 3 is coated with the granules of pigments in the material samples shows that these particles have-25 to-28 millivolts negative ζDian Shi.At 85: 15 wilkinites with 0.75 part: after the poly-DADMAC pre-composition was handled described coating, the granules of pigments in clay/carbonate coating still had negative ζDian Shi (24.8 millivolts).These results confirm wilkinite: the adding of poly-DADMAC pre-composition does not generate as prior art described " positively charged ion " coating.
Table 7
Pre-composition ζDian Shi
95: 5 wilkinite: PRP-4440 + 30.0 millivolts
85: 15 wilkinite: PRP-4440 + 54.7 millivolts
75: 25 wilkinite: PRP-4440 + 64.7 millivolts
65: 35 wilkinite: PRP-4440 + 65.0 millivolts
The scope of embodiment 15-cationic polymers
Use the cationic polymers of wide range to prepare the wilkinite pre-composition.The cationic polymers of being tested comprises: Perform 1279 (Hercules, the dimethylamine/quadrol of branching/epichlorohydrin polymers, M wThe positive charge of=500,000,5.8 milligramequivalent/gram), the lower molecular weight (M that can buy from Aldrich wThe positive charge of=75,000,5.8 milligramequivalent/gram) dimethylamine/quadrol/epichlorohydrin polymers, Kymene 557 (Hercules is described in United States Patent (USP) 2,926, multiamide amine Epicholorohydrin wet method enhanced resin in 154 is to have the positive charge of 2.2 milligramequivalent/grams at 8 o'clock at pH), (Hercules is described in United States Patent (USP) 3 to Kymene  736,655,506,3,248,353 and 2,595, hexamethylene-diamine/epichlorohydrin copolymer in 935 is to have the positive charge of 4.0 milligramequivalent/grams at 8 o'clock at pH), polymine (PEI, M w=50,000, can buy from Aldrich, be to have the positive charge of about 8 milligramequivalent/grams at 8 o'clock at pH) and acrylamide/diallyldimethylammonium chloride multipolymer (can buy from Aldrich, have the positive charge of about 3 milligramequivalent/grams).Every kind of situation, the wilkinite pre-composition all is to make with very wide cationic polymers addition scope, and the wilkinite of high surface area (Bentolite H, Southern Clay Products) is used as the anion particle of pre-composition.Pre-composition adopts the method preparation described in the embodiment 1.Before this pre-composition of preparation, the HCl with 10% is with the polymine sample pH8 that neutralizes.After supersound process, pre-composition is not filtered.
Test of the influence of every kind of wilkinite/cationic polymers pre-composition then to kaolin/water-ground limestone base coating brookfield viscosity described in the embodiment 3 and pigment concussion.The various cationic polymerss of direct adding have also been tested in test, to quantize to form in advance the benefit of described pre-composition.Test undressed coating as reference.Described in embodiment 7 and 8, the interpolation concentration of cationic polymers can have remarkable influence to its performance.For direct adding cationic polymers, its strength of solution is fixed on 0.75% solid.Every kind of pre-composition is added concentration all select, add concentration (0.75%) in whole wilkinites/cationic polymers proportional range, to obtain identical cationic polymers.Therefore, the % total solids of various pre-compositions changes (referring to table 8-11) along with the ratio of wilkinite and cationic polymers.Usually, the increase of the dope viscosity that under given cationic polymers addition, obtains along with pre-composition in cationic polymers percentage ratio increase and increase.Therefore, adjust the addition of various pre-compositions to obtain being equal to or higher than the dope viscosity that obtains viscosity by the corresponding cationic polymers of direct adding.Use the method for describing among the embodiment 7 to determine the pigment concussion amount of the coating that each was handled by measuring the coarse-grained amount that on 200 mesh sieve, remains.Result to every kind of cationic polymers obtained is below described.
The pre-composition of Perform 1279 dimethylamine/quadrol/epichlorohydrin copolymer
Prepare wilkinite/cationic polymers pre-composition (referring to table 8, the wilkinite of 90%-30%) with 1279 additions of the Perform in the 10%-70% scope.
Produce very heavy pigment concussion when directly adding Perform 1279 cationic polymerss.When comparing with identical dope viscosity, all wilkinite/Perform 1279 pre-compositions have all obtained than directly adding Perform 1279 pigment concussion still less.The pre-composition that contains the Perform 1279 of 10%-20% has produced optimum balance between viscosity that increases and the concussion of low-level pigment.Based on these results, the pre-composition that contains 10%-70%Perform 1279 (wilkinite of 90%-30%) is for preferred.The pre-composition that contains 10%-20%Perform 1279 (wilkinite of 80%-90%) is for more preferably.
The pre-composition of dimethylamine/quadrol/epichlorohydrin copolymer (DMA-epi)
Same dimethylamine/quadrol/epichlorohydrin copolymer (the M that uses the branching of lower molecular weight w=75,000 dalton, Aldrich, Milwaukee, WI, about 5.8 milligramequivalent/grams) prepare the wilkinite pre-composition.As shown in table 9, wilkinite/cationic polymers pre-composition is that the DMA-epi addition (wilkinite of 90%-10%) with 10%-90% makes.
Produce very heavy pigment concussion when directly adding lower molecular weight DMA-epi cationic polymers.When comparing with identical dope viscosity, all wilkinites/DMA-epi pre-composition has all obtained than directly adding cationic polymers pigment concussion still less.The pre-composition that contains the lower molecular weight DMA-epi cationic polymers of 20%-60% has produced optimum balance between viscosity that increases and the concussion of low-level pigment.
Based on these results, the pre-composition that contains 10%-90%DMA-epi (wilkinite of 90%-10%) is for preferred.The pre-composition that contains 20%-60%DMA-epi (wilkinite of 80%-40%) is for more preferably.
Should also be noted that low-molecular-weight DMA-epi cationic polymers has produced bigger dope viscosity than Perform 1279 (high-molecular weight DMA-epi cationic polymers) and increased and the concussion of littler pigment.Based on these results and result that lower molecular weight and high-molecular weight poly-DADMAC (PRP-4440 and Reten 203) are obtained, molecular weight is about 10, and 000-is about, and 1,000,000 daltonian cationic polymers is preferred.Molecular weight is about 20, and 000-about 500,000 daltonian cationic polymerss are for more preferably.
Kymene 557 multiamides amine/Epicholorohydrin pre-composition
As shown in table 10, wilkinite/cationic polymers pre-composition is that the Kymene 557 (90%to 10% wilkinite) with the 10%-90% addition prepares.
By the time heavy pigment concussion during directly adding Kymene 557 has produced in coating.Pigment concussion degree increases along with the increase of Kymene 557 additions.When contrasting with identical dope viscosity, the pre-composition that Kymene 557 additions (wilkinite of 50%-30%) of 50%-70% make has obtained optimum.The viscosity that the pre-composition that makes in polymkeric substance addition scope has obtained being obtained with direct adding Kymene 557 increases similar dope viscosity to be increased, and has the pigment concussion of much less.When with the contrast of identical dope viscosity level, the pre-composition that makes under low and higher Kymene 557 additions has produced than directly adding the less slightly pigment concussion of Kymene 557.
Based on these results, the pre-composition that contains 50%-70%Kymene 557 (wilkinite of 50%-30%) is for preferred.The addition scope of this Kymene 557 is more much higher than Lauzon institute preferred range (wilkinite is 7.6% Kymene 557).At last, should be noted that Kymene 557 cationic polymerss with relative low charge density increase dope viscosity so effectively not as poly-DADMAC and the DMA-epi polymkeric substance with higher charge density.
Polyamines Epicholorohydrin (Kymene 736) cationic polymers/wilkinite pre-composition
As shown in table 11, wilkinite/cationic polymers pre-composition is to prepare with the addition of 10%-90%Kymene 736 (wilkinite of 90%-10%).Directly in coating, add Kymene 736 and produce heavy pigment concussion.Pre-composition with the preparation of Kymene 736 concentration (wilkinite of 70%-30%) of 30%-70% has provided optimum.The viscosity that the pre-composition that makes in the scope of this polymkeric substance addition has obtained being obtained with direct adding Kymene 736 increases similar dope viscosity to be increased, and has the pigment concussion of much less.The pre-composition that makes under lower Kymene 736 additions has provided low pigment concussion level, but more very different than the pre-composition that makes with 30-70%Kymene 736 for increasing dope viscosity.The Kymene 736/ wilkinite pre-composition that makes with 80-90%Kymene 736 has big dope viscosity to increase and less pigment concussion than directly adding Kymene 736.
Based on these results, the pre-composition that contains 10%-90%Kymene 736 (wilkinite of 90%-10%) is for preferred.The pre-composition that contains 10%-70%Kymene 736 (wilkinite of 90%-30%) is for more preferably.The pre-composition that contains 30%-70%Kymene 736 (70%-30% wilkinite) is for most preferably.
At last, should be noted that the Kymene 736 with relative high charge density has obtained bigger dope viscosity increase than the Kymene 557 that has than low charge density.
Acrylamide/DADMAC multipolymer and PEI/ wilkinite pre-composition
PEI addition (wilkinite of 90%-10%) preparation cationic polymers/wilkinite pre-composition with acrylamide/DADMAC multipolymer and 10%-90%.There is not a kind of result who provides expectation in these pre-compositions.Described acrylamide/DADMAC multipolymer has produced the pre-composition that coagulates wadding that causes serious pigment concussion.Also there is not at present to understand the reason that causes PEI pre-composition poor performance.Perhaps the molecular weight that polymkeric substance is lower, less branching or the form of chemical modification can produce desirable result.Described at embodiment 17, obtained better result when substituting wilkinite as anion particle with the silica of high surface area.
Embodiment 16-anionic inorganic particulate scope
Use the silica of silica or aluminium modification to prepare a series of pre-composition as anion particle.These pre-compositions use the method described in the embodiment 2 to prepare.Employed silica is: (granularity is 22nm to Ludox TM, 135m 2/ g), (granularity is 12nm to Ludox HS, 220m 2/ g) (granularity is 5nm, 420m with Ludox FM 2/ g).Three kinds of silicas of all this can (Columbia Maryland) buys from Grace-Davison.The silica of employed aluminium modification is: (granularity is 22nm to Ludox TMA, 140m 2/ g) (granularity is 12nm, 220m with Ludox AM 2/ g).These two kinds can (Columbia Maryland) buys from Grace-Davison.In each case, all with the cationic polymers component of PRP-4440poly-DADMAC as pre-composition.Described pre-composition is that the 10%-90% of total solids prepares with the addition of PRP-4440.
As show as shown in the 12-16, test of the influence of every kind of pre-composition to kaolin/water-ground limestone base coating brookfield viscosity described in the embodiment 3 and pigment concussion.Tested viscosity is that (Brookfield RV, undressed coating 100rpm) in contrast for 450-500cps.Also direct adding PRP-4440 poly-DADMAC is tested, to quantize to form in advance the benefit of described pre-composition.
Described in embodiment 7 and 8, the interpolation concentration of cationic polymers can have remarkable influence to its performance.For direct adding, the PRP-4440 strength of solution is fixed on 0.75% solid.Interpolation concentration to every kind of pre-composition is all selected, and adds concentration (0.75%) to provide identical PRP-4440 poly-DADMAC in whole anion particle/poly-DADMAC ratio ranges.Therefore, the % total solids of every kind of pre-composition changes (referring to table 12-16) with the ratio of anion particle and cationic polymers.As viewed among the embodiment in front, the increase of the dope viscosity that is obtained under given cationic polymers addition increases along with the increase of cationic polymers percentage ratio in pre-composition.Therefore, the addition of adjusting every kind of pre-composition is to obtain and directly to add the viscosity that PRP-4440 was obtained and equate or higher dope viscosity (1500-200cps is referring to showing 12-16).By using method measurements of describing among the embodiment 7 to remain in coarse-grained amount on 200 mesh sieve, determine the amount that the pigment of every kind of undressed coating shakes.The coarse grain (referring to table 12-16) that directly adds 0.075 part the common every 200g coating 5-15mg of generation of PRP-4440.The result that each obtained by silica and aluminium modified silica anion particle is described below.
Ludox TM silica/PRP-4440 pre-composition
Produced the result of expectation with the Ludox TM pre-composition (referring to table 12, the Ludox TM of 90%-50%) of the PRP-4440 addition of 10%-50% preparation.The pre-composition that makes with the addition of this scope has big dope viscosity to increase and the pigment concussion of much less than directly adding PRP-4440.PRP-4440 addition with 15%-50% (the Ludox TM of 85%-50%) has obtained optimum.These pre-compositions have increased dope viscosity effectively and seldom have been with or without the pigment concussion.Higher PRP-4440 addition causes heavy pigment concussion in Ludox TM pre-composition.
Based on these results, the Ludox TM pre-composition that contains 10%-50%PRP-4440 (the Ludox TM of 90%-50%) is for preferred.The Ludox TM pre-composition that contains 15%-50%PRP-4440 (85%-50%Ludox TM) is for more preferably.
Ludox HS silica/PRP-4440 pre-composition
Produced the result of expectation with the Ludox HS pre-composition (referring to table 13, the Ludox HS of 85%-10%) of the PRP-4440 addition of 15%-90% preparation.The pre-composition that makes with the addition of this scope has big dope viscosity to increase and the pigment concussion of much less than directly adding PRP-4440.What obtain under the lower PRP-4440 addition (10%) is to form coarse-grained relatively poor pre-composition in coating.
Based on these results, the Ludox HS pre-composition that contains 15%-90%PRP-4440 (the Ludox HS of 85%-10%) is for preferred.
Ludox FM silica/PRP-4440 pre-composition
Obtained the result of expectation with the Ludox FM pre-composition (referring to table 14, the Ludox HS of 80%-10%) of the PRP-4440 addition of 20%-90% preparation.The pre-composition that makes with the addition of this scope has big dope viscosity to increase and the pigment concussion of much less than directly adding PRP-4440.What obtain under the lower PRP-4440 addition (10%-15%) is to form coarse-grained relatively poor pre-composition in coating.
Based on these results, the Ludox FM pre-composition that contains 20%-90%PRP-4440 (the Ludox FM of 80%-10%) is for preferred.
Should be noted that Ludox HS and Ludox FM have better result than Ludox TM, especially under high PRP-4440 addition.Can believe that difference on the performance is that difference by negatively charged ion granularity and surface-area causes.Based on these results, granularity is preferred less than the silica of 50nm.Granularity less than the silica of 20nm for more preferably.
Silica/PRP-4440 the pre-composition of Ludox TMA aluminium modification
Obtained the result of expectation with the Ludox TMA pre-composition (referring to table 15, the Ludox TMA of 90%-10%) of the PRP-4440 addition of 10%-90% preparation.The pre-composition that makes with the addition of this scope has big dope viscosity to increase and less pigment concussion than directly adding PRP-4440.Under the PRP-4440 of 15%-60% addition (the Ludox TMA of 85%-40%), obtained optimum.These pre-compositions have increased coating concentration effectively and seldom have been with or without the pigment concussion as direct adding PRP-4440.Higher PRP-4440 addition has obtained high slightly pigment concussion in described Ludox TMA pre-composition.What obtain under the lower PRP-4440 addition (10%) is the relatively poor pre-composition that forms high slightly pigment concussion.
Based on these results, the Ludox TMA pre-composition that contains 10%-90%PRP-4440 (the Ludox TMA of 90%-10%) is for preferred.The Ludox TMA pre-composition that contains 15%-60%PRP-4440 (85%-40%Ludox TMA) is for more preferably.
Silica/PRP-4440 the pre-composition of Ludox AM aluminium modification
Obtained the result of expectation with the Ludox AM pre-composition (referring to table 16, the Ludox AM of 90%-10%) of the PRP-4440 addition of 10%-90% preparation.The pre-composition that makes with the addition of this scope has big dope viscosity to increase and less pigment concussion than directly adding PRP-4440.Under the PRP-4440 of 15%-60% addition (the Ludox AM of 80%-40%), obtained optimum.These pre-compositions have increased coating concentration effectively and seldom have been with or without the pigment concussion as direct adding PRP-4440.Higher PRP-4440 addition in described Ludox AM pre-composition has obtained medium pigment concussion.What obtain under the lower PRP-4440 addition (10%) is to form the coarse-grained relatively poor pre-composition of moderate in coating.
Based on these results, the Ludox AM pre-composition that contains 10%-90%PRP-4440 (the Ludox AM of 90%-10%) is for preferred.The Ludox AM pre-composition that contains 15%-60%PRP-4440 (the Ludox AM of 85%-40%) is for more preferably.
Embodiment 17-polymine/silica pre-composition
Method described in the use embodiment 2 prepares PEI/Ludox HS silica pre-composition with the PEI addition of 10%-50%.Test of the influence of various pre-compositions then to kaolin/water-ground limestone base coating brookfield viscosity described in the embodiment 3 and pigment concussion.
Directly in paper coating, add PEI and obtained heavy pigment concussion (referring to table 17).Obtained the performance of expectation with the PEI/Ludox HS pre-composition of the PEI addition of 10%-20% (the Ludox HS of 90%-80%) preparation.The pre-composition that makes with the addition of this scope has big dope viscosity to increase and the pigment concussion of much less than directly adding PEI.Higher PEI addition causes heavy pigment concussion.Yet when comparing with identical dope viscosity, described pigment concussion still is less than the caused pigment concussion by direct adding PEI.
Based on these results, the LudoxHS pre-composition that contains 10%-50%PEI (90%-50%Ludox HS) is for preferred.The LudoxHS pre-composition that contains 10%-20%PEI (90%-80%Ludox HS) is for more preferably.
Embodiment 18-acrylamide/DADMAC multipolymer/silica pre-composition
Method described in the use embodiment 2 prepares acrylamide/DADMAC multipolymer/Ludox HS silica pre-composition with acrylamide/DADMAC addition of 10%-90%.Test of the influence of every kind of pre-composition then to kaolin/water-ground limestone base coating brookfield viscosity described in the embodiment 3 and pigment concussion.
Directly in paper coating, add acrylamide/DADMAC multipolymer and obtained very heavy pigment concussion (referring to table 18).Only obtained the performance of expectation with the acrylamide/DADMAC multipolymer/Ludox HS pre-composition of 70% addition preparation.Lower acrylamide/DADMAC addition has produced the pre-composition of the flocculation of poor performance.Higher acrylamide/DADMAC multipolymer addition has produced heavy pigment concussion.Based on these results, the LudoxHS pre-composition that contains about 70% acrylamide/DADMAC multipolymer (30% Ludox HS) is for preferred.May can provide better properties with the mol ratio of different acrylamides and poly-DADMAC or other acrylamide/DADMAC multipolymer for preparing with different molecular weight.
The CLC of embodiment 19-wilkinite and silica pre-composition estimates
Based on the result of embodiment 15 and 16, select a series of pre-compositions on cylinder shape test coating machine, to estimate.With PRP-4440, Reten 203,75,000M wDMA-epi cationic polymers, Kymene 557 and Kymene 736 test as the cationic polymers component of pre-composition.The silica of wilkinite, silica and aluminium modification is tested as the anion particle component of pre-composition.Selected pre-composition compound is shown in the table 19.85: 15 wilkinites: the poly-DADMAC pre-composition is to prepare with the method for describing among 25% the solid use embodiment 5.Remaining pre-composition is to use the method described in embodiment 1 and 2 to prepare.The cylinder shape laboratory coating machine of describing among clay/carbonate coating compound described in the use embodiment 3 and the embodiment 10 is estimated.In all cases, selecting to provide with coating pigment to the addition of pre-composition is the cationic polymers addition of 0.075 part of benchmark, and 0.75% cationic polymers adds concentration.Before in joining coating, various pre-compositions were stirred 25 minutes under the interpolation concentration of selecting at least.Also use directly joins to be coated with less than dilution and tests described 85: 15 wilkinites in the slurry body: the poly-DADMAC pre-composition.Undressed coating is estimated in contrast.The TAPPI of use standard (Technical Association of the Pulp and Paper Industry) method is measured the opaqueness and the brightness of White Board.
Pre-composition by the poly-DADMAC PRP-4440 of lower molecular weight, high charge density preparation has provided optimum (referring to table 19).To in the same old way, the pre-composition of this 85: 15 wilkinites: PRP-4440 has obtained not going up the increase that transparency and brightness 0.4-0.8 are ordered in each coating one side with respect to undressed.When being diluted to 5% solid as the part of the coating preparation procedure of standard and with this pre-composition and joining in the final coating compound and join when being coated with in the slurry body when undiluted pre-composition, obtained excellent results.The pre-composition of 70: 30 wilkinites: PRP-4440 has provided similar opaqueness and brightness increases.The silica that is made by PRP-4440poly-DADMAC and the pre-composition of aluminium modified silica also improve optical property, the especially opacity of coating paper significantly.
With Reten 203,75,000M wDMA-epi cationic polymers, Kymene 557 and the pre-composition of Kymene 736 preparations has obtained less coating opaqueness and brightness increases.Usually, the pre-composition by the preparation of the cationic polymers of high charge density has bigger increase than the pre-composition that the cationic polymers with low charge density prepares in opaqueness and brightness.For example, compare with undressed reference sample, by Reten 203 or 75,000M wThe pre-composition that makes of DMA-epi cationic polymers in coating opacity and brightness, obtained the increase of 0.2-0.5 point (each coating one side).By the Kymene 557 of relative low charge density and the wilkinite pre-composition of Kymene 736 cationic polymerss preparation little increase (each coating 1 side 0-0.3 point) is only arranged in coating opacity and brightness.May be in being higher than the research under the addition of employed 0.075 part of cationic polymers, Kymene 557 and Kymene 736 basic pre-compositions can obtain bigger increase in opaqueness and brightness.
Based on these results, cationic charge density is that the cationic polymers of at least 2 milligramequivalent/grams is preferred.Cationic charge density for for the cationic polymers of at least 4 milligramequivalent/grams for more preferably.The poly-DADMAC cationic polymers is for most preferably.This pre-composition can make as anion particle with the silica of wilkinite, silica or aluminium modification.
Table 4
The % solid of (wilkinite/cationic polymers) Hydroxypropyl melon glue Initial viscosity Settling stability
1 day 1 week 2 weeks 4 weeks 8 weeks
21％ 0.4％ 732cps By The layer of Bao Erqing, failure - - -
21％ 0.6％ 1760cps By By The layer of Bao Erqing, failure - -
21％ 0.7％ 2170cps By By The layer of Bao Erqing, failure - -
21％ 0.8％ 2770cps By By By By The layer of Bao Erqing, failure
24％ 0.4％ 1020cps By The layer of Bao Erqing, failure - - -
24％ 0.6％ 2060cps By By By The layer of Bao Erqing, failure -
24％ 0.7％ 2590cps By By By By The layer of Bao Erqing, failure
24％ 0.8％ 3390cps By By By By By
Table 4 (continuous table)
The % solid of (wilkinite/cationic polymers) Hydroxypropyl melon glue Initial viscosity Settling stability
1 day 1 week 2 weeks 4 weeks 8 weeks
27％ 0.4％ 1200cps By The layer of Bao Erqing, failure - - -
27％ 0.5％ 1750cps By By By The layer of Bao Erqing, failure -
27％ 0.6％ 2510cps By By By By The layer of Bao Erqing, failure
27％ 0.7％ 3080cps By By By By By
30％ 0.3％ 988cps By The layer of Bao Erqing, failure - - -
30％ 0.4％ 1610cps By By The layer of Bao Erqing, failure - -
30％ 0.5％ 2220cps By By By By The layer of Bao Erqing, failure
30％ 0.6％ 3140cps By By By By By
Table 5-wilkinite/Reten 203-dope viscosity and pigment concussion
Polymkeric substance The ratio of wilkinite/polymkeric substance The % solid of pre-composition The % solid of polymkeric substance The polymkeric substance addition Dope viscosity Pigment concussion (mg/200g)
Contrast Blank - - - 470cps 0.3mg
Reten 203 Directly add - 0.75％ 0.060％ 965cps 3.5mg
Reten 203 Directly add - 0.75％ 0.075％ 1690cps 3.2mg
Reten 203 Directly add - 0.75％ 0.085％ 2300cps 5.1mg
Reten 203 95/5 15％ 0.75％ 0.10％ 1475cps 5.9mg
Reten 203 92.5/7.5 10％ 0.75％ 0.10％ 2000cps 4.1mg
Reten 203 90/10 7.5％ 0.75％ 0.10％ 2180cps 4.5mg
Reten 203 85/15 5.0％ 0.75％ 0.10％ 2450cps 1.8mg
Reten 203 80/20 3.75％ 0.75％ 0.10％ 2820cps 0.7mg
Reten 203 75/25 3.0％ 0.75％ 0.085％ 3000cps 1.3mg
Reten 203 70/30 2.5％ 0.75％ 0.085％ 3120cps 1.7mg
Reten 203 60/40 1.88％ 0.75％ 0.085％ 2450cps 1.8mg
Reten 203 50/50 1.5％ 0.75％ 0.085％ 2520cps 6.5mg
Table 6-wilkinite/PRP-4440-dope viscosity and pigment concussion
Polymkeric substance The ratio of wilkinite/polymkeric substance The % solid of pre-composition The % solid of polymkeric substance The polymkeric substance addition Dope viscosity Pigment concussion (mg/200g)
Contrast Blank - - - 480cps 0.1mg
PRP-4440 Directly add - 0.75％ 0.075％ 1980cps 11.1mg
PRP-4440 Directly add - 0.75％ 0.075％ 2180cps 7.9mg
PRP-4440 95/5 15％ 0.75％ 0.10％ 1250cps 6.7mg
PRP-4440 92.5/7.5 10％ 0.75％ 0.10％ 1730cps 2.3mg
PRP-4440 90/10 7.5％ 0.75％ 0.10％ 1995cps 1.6mg
PRP-4440 85/15 5.0％ 0.75％ 0.10％ 2530cps 0.7mg
PRP-4440 80/20 3.75％ 0.75％ 0.10％ 2220cps 1.9mg
PRP-4440 75/25 3.0％ 0.75％ 0.085％ 2190cps 0.1mg
PRP-4440 70/30 2.5％ 0.75％ 0.085％ 2160cps 1.0mg
PRP-4440 60/40 1.88％ 0.75％ 0.085％ 2420cps 4.9mg
PRP-4440 50/50 1.5％ 0.75％ 0.075％ 1850cps 7.4mg
Table 8-wilkinite/Perform 1279 DMA-Epi, M w-500,000-dope viscosity and pigment concussion
Polymkeric substance The ratio of wilkinite/polymkeric substance The % solid of pre-composition The % solid of polymkeric substance The polymkeric substance addition Dope viscosity Pigment concussion (mg/200g)
Contrast Blank - - - 470cps 0.0mg
Perform 1279 Directly add - 0.75％ 0.075％ 1060cps 23.3mg
Perform 1279 90/10 7.5％ 0.75％ 0.10％ 925cps 3.7mg
Perform 1279 80/20 3.75％ 0.75％ 0.10％ 1080cps 4.2mg
Perform 1279 70/30 2.5％ 0.75％ 0.10％ 1340cps 8.4mg
Perform 1279 60/40 1.88％ 0.75％ 0.10％ 1710cps 10.7mg
Perform 1279 50/50 1.5％ 0.75％ 0.085％ 1250cps 14.4mg
Perform 1279 40/60 1.25％ 0.75％ 0.085％ 1360cps 15.2mg
Perform 1279 30/70 1.07％ 0.75％ 0.085％ 1810cps 16.5mg
Table 9-wilkinite/DMA-Epi, M w-750,000-dope viscosity and pigment concussion
Polymkeric substance The ratio of wilkinite/polymkeric substance The % solid of pre-composition The % solid of polymkeric substance The polymkeric substance addition Dope viscosity Pigment concussion (mg/200g)
Contrast Blank - - - 450cps 0.0mg
DMA-Epi M w- 75,000 Directly add - 0.75％ 0.075％ 1140cps 29.7mg
DMA-Epi M w- 75,000 90/10 7.5％ 0.75％ 0.10％ 900cps 4.0mg
DMA-Epi M w- 75,000 80/20 3.75％ 0.75％ 0.10％ 1150cps 0.6mg
DMA-Epi M w- 75,000 70/30 2.5％ 0.75％ 0.10％ 1560cps 0.6mg
DMA-Epi M w- 75,000 60/40 1.88％ 0.75％ 0.10％ 1920cps 0.9mg
DMA-Epi M w- 75,000 50/50 1.5％ 0.75％ 0.085％ 1900cps 1.5mg
DMA-Epi M w- 75,000 40/60 1.25％ 0.75％ 0.075％ 1300cps 1.7mg
Table 9-wilkinite/DMA-Epi, M w-750,000-dope viscosity and pigment concussion
Polymkeric substance The ratio of wilkinite/polymkeric substance The % solid of pre-composition The % solid of polymkeric substance The polymkeric substance addition Dope viscosity Pigment concussion (mg/200g)
DMA-Epi M w- 75,000 30/70 1.07％ 0.75％ 0.075％ 1380cps 5.7mg
DMA-Epi M w- 75,000 20/80 0.94 0.75％ 0.075％ 1490cps 5.2mg
DMA-Epi M w- 75,000 10/90 0.84％ 0.75％ 0.075％ 1700cps 4.4mg
Table 10-wilkinite/Kymene 557-dope viscosity and pigment need swing
Polymkeric substance The ratio of wilkinite/polymkeric substance The % solid of pre-composition The % solid of polymkeric substance The polymkeric substance addition Dope viscosity Pigment concussion (mg/200g)
Contrast Blank - - - 470cps 0.3mg
Kymene 557 Directly add - 0.75％ 0.065％ 685cps 2.9mg
Kymene 557 Directly add - 0.75％ 0.075％ 800cps 5.2mg
Kymene 557 Directly add - 0.75％ 0.10％ 960cps 15.4mg
Kymene 557 90/10 7.5％ 0.75％ 0.10％ 576cps 2.3mg
Kymene 557 80/20 3.75％ 0.75％ 0.10％ 752cps 2.3mg
Kymene 557 70/30 2.5％ 0.75％ 0.10％ 670cps 2.0mg
Kymene 557 60/40 1.88％ 0.75％ 0.10％ 650cps 2.4mg
Kymene 557 50/50 1.5％ 0.75％ 0.10％ 710cps 0.2mg
Kymene 557 40/60 1.25％ 0.75％ 0.10％ 720cps 0.1mg
Kymene 557 30/70 1.07％ 0.75％ 0.10％ 772cps 0.8mg
Kymene 557 20/80 0.94％ 0.75％ 0.10％ 920cps 5.5mg
Kymene 557 10/90 0.84％ 0.75％ 0.10％ 910cps 3.2mg
Table 11-Kymene 736-dope viscosity and pigment concussion
Polymkeric substance The ratio of wilkinite/polymkeric substance The % solid of pre-composition The % solid of polymkeric substance The polymkeric substance addition Dope viscosity Pigment concussion (mg/200g)
Contrast Blank - - - 448cps 0.7mg
Kymene 736 Directly add - 0.75％ 0.075％ 1580cps 9.6mg
Kymene 736 90/10 7.5％ 0.75％ 0.10％ 688cps 1.9mg
Kymene 736 80/20 3.75％ 0.75％ 0.10％ 1060cps 0.8mg
Kymene 736 70/30 2.5％ 0.75％ 0.10％ 1920cps 0.0mg
Kymene 736 60/40 1.88％ 0.75％ 0.085％ 1710cps 1.8mg
Kymene 736 50/50 1.5％ 0.75％ 0.085％ 2000cps 0.8mg
Kymene 736 40/60 1.25％ 0.75％ 0.085％ 2590cps 2.0mg
Kymene 736 30/70 1.07％ 0.75％ 0.075％ 1740cps 0.6mg
Kymene 736 20/80 0.94％ 0.75％ 0.075％ 2080cps 2.8mg
Kymene 736 10/90 0.84％ 0.75％ 0.075％ 2210cps 3.2mg
Table 12-Ludox TM-50/PRP-4440-dope viscosity and pigment concussion
Polymkeric substance The ratio of anion particle/polymkeric substance The % solid of pre-composition The % solid of polymkeric substance The polymkeric substance addition Dope viscosity Pigment concussion (mg/200g)
Contrast Blank - - - 470cps 0.2mg
PRP-4440 Directly add - - - 478cps 0.1mg
PRP-4440 Directly add - 0.75％ 0.075％ 2050cps 5.0mg
PRP-4440 Directly add - 0.75％ 0.075％ 1760cps 8.0mg
PRP-4440 90/10 7.5％ 0.75％ 0.085％ 1330cps 0.8mg
PRP-4440 90/10 7.5％ 0.75％ 0.090％ 1610cps 1.1mg
PRP-4440 85/15 5.0％ 0.75％ 0.090％ 2980cps 0.4mg
PRP-4440 80/20 3.75％ 0.75％ 0.085％ 2580cps 1.1mg
PRP-4440 70/30 2.5％ 0.75％ 0.075％ 2270cps 1.2mg
PRP-4440 60/40 1.88％ 0.75％ 0.075％ 1890cps 0.3mg
PRP-4440 50/50 1.5％ 0.75％ 0.075％ 2540cps 0.7mg
PRP-4440 40/60 1.25％ 0.75％ 0.075％ 2170cps 11.4mg
PRP-4440 40/60 1.25％ 0.75％ 0.075％ 2225cps 18.5mg
PRP-4440 30/70 1.07％ 0.75％ 0.065％ 1640cps 10.8mg
PRP-4440 20/80 0.94％ 0.75％ 0.065％ 1735cps 10.3mg
PRP-4440 10/90 0.84％ 0.75％ 0.065％ 1820cps 11.1mg
Table 13-Ludox HS/PRP-4440-dope viscosity and pigment concussion
Polymkeric substance The ratio of anion particle/polymkeric substance The % solid of pre-composition The % solid of polymkeric substance The polymkeric substance addition Dope viscosity Pigment concussion (mg/200g)
Contrast Blank - - - 492cps 0.1mg
PRP-4440 Directly add - 0.75％ 0.075％ 1490cps 3.9mg
PRP-4440 90/10 7.5％ 0.75％ 0.10％ 820cps 2.6mg
PRP-4440 85/15 5.0％ 0.75％ 0.10％ 2330cps 0.3mg
PRP-4440 80/20 3.75％ 0.75％ 0.10％ 1970cps 0.1mg
PRP-4440 70/30 2.5％ 0.75％ 0.085％ 1620cps 0.7mg
PRP-4440 60/40 1.88％ 0.75％ 0.085％ 1800cps 1.0mg
PRP-4440 50/50 1.5％ 0.75％ 0.085％ 2410cps 0.8mg
PRP-4440 40/60 1.25％ 0.75％ 0.075％ 1850cps 0.8mg
PRP-4440 30/70 1.07％ 0.75％ 0.075％ 1620cps 0.6mg
PRP-4440 20/80 0.94％ 0.75％ 0.075％ 1750cps 0.6mg
PRP-4440 10/90 0.84％ 0.75％ 0.075％ 1970cps 0.7mg
Table 14-Ludox FM/PRP-4440-dope viscosity and pigment concussion
Polymkeric substance The ratio of anion particle/polymkeric substance The % solid of pre-composition The % solid of polymkeric substance The polymkeric substance addition Dope viscosity Pigment concussion (mg/200g)
Contrast Blank - - - 455cps 0.3mg
PRP-4440 Directly add - 0.75％ 0.075％ 2015cps 14.4mg
PRP-4440 90/10 7.5％ 0.75％ 0.10％ 905cps 59.1mg
PRP-4440 85/15 5.0％ 0.75％ 0.10％ 664cps 4.7mg
PRP-4440 80/20 3.75％ 0.75％ 0.10％ 1280cps 1.1mg
PRP-4440 70/30 2.5％ 0.75％ 0.085％ 1890cps 1.1mg
PRP-4440 60/40 1.88％ 0.75％ 0.085％ 2390cps 1.6mg
PRP-4440 50/50 1.5％ 0.75％ 0.075％ 2010cps 1.9mg
PRP-4440 40/60 1.25％ 0.75％ 0.075％ 2450cps 2.4mg
PRP-4440 30/70 1.07％ 0.75％ 0.065％ 2410cps 1.7mg
PRP-4440 20/80 0.94％ 0.75％ 0.060％ 1690cps 1.3mg
PRP-4440 10/90 0.84％ 0.75％ 0.060％ 1910cps 1.2mg
Table 15-Ludox TMA/PRP-4440-dope viscosity and pigment concussion
Polymkeric substance The ratio of anion particle/polymkeric substance The % solid of pre-composition The % solid of polymkeric substance The polymkeric substance addition Dope viscosity Pigment concussion (mg/200g)
Contrast Blank - - - 470cps 0.3mg
PRP-4440 Directly add - 0.75％ 0.065％ 1920cps 4.9mg
PRP-4440 Directly add - 0.75％ 0.075％ 2390cps 8.6mg
PRP-4440 90/10 7.5％ 0.75％ 0.075％ 1870cps 2.0mg
PRP-4440 85/15 5.0％ 0.75％ 0.070％ 1520cps 0.6mg
PRP-4440 80/20 3.75％ 0.75％ 0.065％ 2250cps 0.8mg
PRP-4440 70/30 2.5％ 0.75％ 0.060％ 1920cps 0.7mg
PRP-4440 60/40 1.88％ 0.75％ 0.060％ 1760cps 0.7mg
PRP-4440 50/50 1.5％ 0.75％ 0.060％ 1680cps 1.0mg
PRP-4440 40/60 1.25％ 0.75％ 0.060％ 1790cps 0.8mg
PRP-4440 30/70 1.07％ 0.75％ 0.065％ 2360cps 1.5mg
PRP-4440 20/80 0.94％ 0.75％ 0.065％ 2230cps 1.6mg
PRP-4440 10/90 0.84％ 0.75％ 0.065％ 2320cps 1.5mg
Table 16-Ludox AM/PRP-4440-dope viscosity and pigment concussion
Polymkeric substance The ratio of anion particle/polymkeric substance The % solid of pre-composition The % solid of polymkeric substance The polymkeric substance addition Dope viscosity Pigment concussion (mg/200g)
Contrast Blank - - - 452cps 0.0mg
PRP-4440 Directly add - 0.75％ 0.075％ 1800cps 32.7mg
PRP-4440 90/10 7.5％ 0.75％ 0.085％ 1685cps 6.5mg
PRP-4440 85/15 5.0％ 0.75％ 0.085％ 1410cps 0.3mg
PRP-4440 80/20 3.75％ 0.75％ 0.085％ 2280cps 0.1mg
PRP-4440 70/30 2.5％ 0.75％ 0.075％ 2210cps 0.9mg
PRP-4440 60/40 1.88％ 0.75％ 0.070％ 2040cps 0.4mg
PRP-4440 50/50 1.5％ 0.75％ 0.065％ 1675cps 0.4mg
PRP-4440 40/60 1.25％ 0.75％ 0.065％ 1890cps 0.4mg
PRP-4440 30/70 1.07％ 0.75％ 0.065％ 2020cps 2.5mg
PRP-4440 20/80 0.94％ 0.75％ 0.060％ 1710cps 2.8mg
PRP-4440 10/90 0.84％ 0.75％ 0.060％ 2240cps 2.1mg
Table 17-polymine (PEI)/HS-40 silica-dope viscosity and pigment concussion
Polymkeric substance The ratio of anion particle/polymkeric substance The % solid of pre-composition The % solid of polymkeric substance The polymkeric substance addition Dope viscosity Pigment concussion (mg/200g)
Contrast Blank - - - 480cps 1.4mg
PEI Directly add - 0.75％ 0.065％ 1260cps 5.7mg
PEI Directly add - 0.75％ 0.075％ 1780cps 115.6mg
PEI
90/10 7.5％ 0.75％ 0.085％ 1100cps 0.5mg
PEI
90/10 5.0％ 0.75％ 0.10％ 1260cps 1.5mg
PEI 80/20 3.75％ 0.75％ 0.085％ 1620cps 7.3mg
PEI
70/30 2.5％ 0.75％ 0.085％ 2310cps 20.7mg
PEI 60/40 1.88％ 0.75％ 0.085％ 2400cps 33.5mg
PEI
50/50 1.5％ 0.75％ 0.085％ 2980cps 31.5mg
Table 18-acrylamide/DADMAC multipolymer (ACM/DADMAC)/HS-40 silica-dope viscosity and pigment concussion
Polymkeric substance The ratio of anion particle/polymkeric substance The % solid of pre-composition The % solid of polymkeric substance The polymkeric substance addition Dope viscosity Pigment concussion (mg/200g)
Contrast Blank - - - 480cps 1.4mg
PEI Directly add - 0.75％ 0.075％ 944cps 79.8mg
PEI
90/10 7.5％ 0.75％ 0.085％ 608cps 547mg
PEI 70/30 2.5％ 0.75％ 0.10％ - Serious pigment concussion can't be filtered
PEI 50/50 1.5％ 0.75％ 0.10％ - Serious pigment concussion can't be filtered
PEI 40/60 1.25％ 0.75％ 0.10％ - Serious pigment concussion can't be filtered
PEI 30/70 1.07％ 0.75％ 0.10％ 1210cps 12.8mg
PEI
20/80 0.94％ 0.75％ 0.10％ 1240cps 51.2mg
PEI
10/90 0.84％ 0.75％ 0.10％ - Serious pigment concussion can't be filtered
The brightness of table 19-coating paper and the increase of opaqueness
Pre-composition The average increase of each side coating paper brightness The average increase of each side coating paper opaqueness
Untreated in the same old way - -
85: 15: wilkinite: the PRP-4440 dilution, add at last 0.42 the point 0.84 the point
85: 15: wilkinite: PRP-4440 was undiluted, joined in the starch 0.39 the point 0.65 the point
70: 30: wilkinite: PRP-4440 0.62 the point 0.54 the point
85: 15: wilkinite: Reten 203 0.49 the point 0.23 the point
70: 30 wilkinites: 75,000M w DMA-epi 0.39 the point 0.42 the point
50: 50 wilkinites: Kymene 736 0.10 the point 0.31 the point
40: 60 wilkinites: Kymene 557 0.27 the point 0.0 the point
70: 30Ludox FM silica: PRP-4440 0.13 the point 0.65 the point
70: 30Ludox TM silica: PRP-4440 0.23 the point 0.76 the point
70: 30Ludox AM aluminium modified silica: PRP-4440 0.28 the point 0.67 the point

Claims (111)

1. painted water-based system, it comprises:
(i) contain the additive pre-composition of cationic polymers and anion particle.
2. the system of claim 1, wherein said system packet content is the pre-composition of per 100 parts of about 2.0 dry parts of the about 0.01-of pigment in the described water-based system.
3. the system of claim 2, wherein said system amount is the pre-composition of per 100 parts of about 1.0 dry parts of the about 0.05-of pigment in the described water-based system.
4. the system of claim 3, wherein said system amount is the pre-composition of per 100 parts of about 0.5 dry parts of the about 0.1-of pigment in the described water-based system.
5. the system of claim 1, the solid content of wherein said pre-composition is about 5%-about 40%.
6. the system of claim 5, the solid content of wherein said pre-composition is about 15%-about 30%.
7. the system of claim 1, the weight-average molecular weight of wherein said cationic polymers are about 5, about 3,000,000 dalton of 000-.
8. the system of claim 7, the weight-average molecular weight of wherein said cationic polymers are about 10, about 1,000,000 dalton of 000-.
9. the system of claim 8, the weight-average molecular weight of wherein said cationic polymers are about 20, about 500,000 dalton of 000-.
10. the system of claim 1, the electric density of wherein said cationic polymers is the about 8 milligramequivalent/grams of about 0.1-.
11. the system of claim 10, the electric density of wherein said cationic polymers is the about 8 milligramequivalent/grams of about 1-.
12. the system of claim 11, the electric density of wherein said cationic polymers is the about 6.5 milligramequivalent/grams of about 2-.
13. the system of claim 1, wherein said cationic polymers comprises: the quaternary ammonium salt of (methyl) acrylic acid aminoalkyl ester (being total to) polymkeric substance that the N-alkyl replaces; The quaternary ammonium salt of polyamine and acrylic ester compound reaction product; (being total to) polymkeric substance of (methacryloyl oxygen ethyl) trimethyl ammonium chloride; (being total to) polymkeric substance of acrylamide and quaternary ammonium compound; Quaternised vinyl lactam-acrylamide (being total to) polymkeric substance; The quaternary ammonium salt of the unsaturated carboxylic acid polyester of hydroxyl; The quaternary ammonium salt of polyimide-amine; Quaternised polyamine; The quaternised reaction product of amine and polyester; The quaternary ammonium salt of the condensation of polyvinylamine and ethylene dichloride (being total to) polymkeric substance; The halid quaternized condensation product of polyalkylene-polyamines and epoxy; The quaternized condensation product of alkylidene group-polyamines and multifunctional halohydrin; The quaternized condensation product of alkylidene group-polyamines and halohydrin; Quaternised condensation (being total to) polymkeric substance of ammonia and halohydrin; The quaternary ammonium salt of polyvinyl benzyl trialkylamine; The quaternary ammonium salt of (being total to) polymkeric substance with vinyl-heterocyclic monomer of nitrogen in the ring; The poly dialkyl diallyl ammonium salt that comprises diallyl dimethyl ammoniumchloride; (being total to) polymkeric substance of vinyl unsaturated acid, its ester and acid amides and diallyldialkylammonihalide salt; PMAm base oxypropyl trimethyl ammonium chloride; The quaternary ammonium salt of ammonia-Ethylene Dichloride condensation (being total to) polymkeric substance; The quaternary ammonium salt of epoxy halogenide (being total to) polymkeric substance, and their mixture.
14. the system of claim 13, wherein said cationic polymers comprises: (being total to) polymkeric substance of diallyldialkylammonihalide salt; (being total to) polymkeric substance of diallyl amine; (being total to) polymkeric substance of diallyl alkylamine; Polymine; (being total to) polymkeric substance of dialkylamine/Epicholorohydrin; (being total to) polymkeric substance of polyamines/Epicholorohydrin; (being total to) polymkeric substance of multiamide/Epicholorohydrin; (being total to) polymkeric substance of multiamide amine; (being total to) polymkeric substance of multiamide amine/Epicholorohydrin; (being total to) polymkeric substance of dialkyl aminoalkyl acrylamide and Methacrylamide and quaternised (being total to) polymkeric substance; (being total to) polymkeric substance and quaternised (being total to) polymkeric substance with dialkyl aminoalkyl acrylate, methacrylic ester; And their mixture.
15. the system of claim 14, wherein said cationic polymers comprises: (being total to) polymkeric substance of diallyl dimethyl ammonium salt; (being total to) polymkeric substance of polyamines/Epicholorohydrin; Polymine; (being total to) polymkeric substance of dimethylamine/Epicholorohydrin; The polymkeric substance of multiamide amine/Epicholorohydrin; And their mixture.
16. the system of claim 15, wherein said cationic polymers comprises: (being total to) polymkeric substance of diallyl dimethyl ammonium salt, (being total to) polymkeric substance of dimethylamine/Epicholorohydrin and their mixture.
17. the system of claim 1, the concentration of wherein said cationic polymers in pre-composition is for being less than about 2.5%.
18. the system of claim 17, the concentration of wherein said cationic polymers in pre-composition is for being less than about 1.5%.
19. the system of claim 18, the concentration of wherein said cationic polymers in pre-composition is for being less than about 1.0%.
20. the system of claim 1, wherein said anion particle are the synthetic inorganic particle of band anionic charge of inorganic mineral, high surface area of the band anionic charge of high surface area and their mixture.
21. the system of claim 20, wherein said anion particle comprise swelling clay, silica base particle and their mixture.
22. the system of claim 21, wherein said silica base particle comprise colloided silica, colloidal aluminium modified silica, pure aluminium silicate and their mixture.
23. the system of claim 21, wherein said swelling clay comprises wilkinite, montmorillonite, polynite, beidellite, nontronite, hectorite, saponite, sepiolite or attapulgite.
24. the system of claim 23, wherein said anion particle is a wilkinite.
25. the system of claim 21, the granularity of wherein said swelling clay are about 1 nanometer-Yue 1 micron.
26. the system of claim 21, the surface-area of wherein said swelling clay is 50m at least 2/ g.
27. the system of claim 26, the surface-area of wherein said swelling clay is 100m at least 2/ g.
28. the system of claim 27, the surface-area of wherein said swelling clay is 200m at least 2/ g.
29. the system of claim 21, the granularity of wherein said silica base particle is for being lower than about 50 nanometers.
30. the system of claim 29, the granularity of wherein said silica base particle is for being lower than about 20 nanometers.
31. the system of claim 30, the granularity of wherein said silica base particle is about 10 nanometers of about 1-.
32. the system of claim 21, the surface-area of wherein said silica base particle is 50m at least 2/ g.
33. the system of claim 32, the surface-area of wherein said silica base particle is 100m at least 2/ g.
34. the system of claim 33, the surface-area of wherein said silica base particle is at least about 200m 2/ g.
35. the system of claim 1, wherein said additive pre-composition comprise the anion particle of the about 10 weight % of about 95 weight %-and the cationic polymers of the about 80 weight % of about 5 weight %-.
36. the system of claim 35, wherein said additive pre-composition comprise the anion particle of the about 20 weight % of about 90 weight %-and the cationic polymers of the about 80 weight % of about 10 weight %-.
37. the system of claim 36, wherein said additive pre-composition comprise the anionic polymer of the about 40 weight % of about 90 weight %-and the cationic polymers of the about 60 weight % of about 10 weight %-.
38. the system of claim 37, wherein said additive pre-composition comprise the anion particle of the about 60 weight % of about 85 weight %-and the cationic polymers of the about 40 weight % of about 15 weight %-.
39. the system of claim 1, wherein said anion particle is a wilkinite, and described cationic polymers is poly-DADMAC.
40. the system of claim 39, the ratio of wherein said wilkinite and poly-DADMAC are respectively about 92.5: about 60: 40 of 7.5-.
41. the system of claim 40, the ratio of wherein said wilkinite and poly-DADMAC are respectively about 70: about 85: 15 of 30-.
42. paper that has been coated with the coating of the painted water-based system that comprises claim 1.
43. a method that forms water-based system, it comprises:
(1) mixed anion particle and cationic polymers; Wherein formed the additive pre-composition,
(2) randomly filter described additive pre-composition;
(3) randomly in described additive pre-composition, add stablizer;
(4) randomly described additive pre-composition adding is coated with slurry body;
(5) randomly in described additive pre-composition, add biocide; With
(6) described additive pre-composition is added water-based system.
44. the method for claim 43, it further comprises:
(7) coating cellulose matrix; With
(8) dry described cellulosic matrix.
45. the method for claim 43, wherein said cationic polymers comprises: (being total to) polymkeric substance of diallyldialkylammonihalide salt; (being total to) polymkeric substance of diallyl amine; (being total to) polymkeric substance of diallyl alkylamine; Polymine; (being total to) polymkeric substance of dialkylamine/Epicholorohydrin; (being total to) polymkeric substance of polyamines/Epicholorohydrin; (being total to) polymkeric substance of multiamide/Epicholorohydrin; (being total to) polymkeric substance of multiamide amine; (being total to) polymkeric substance of multiamide amine/Epicholorohydrin; (being total to) polymkeric substance of dialkyl aminoalkyl acrylamide and Methacrylamide and quaternised (being total to) polymkeric substance; (being total to) polymkeric substance and quaternised (being total to) polymkeric substance with dialkyl aminoalkyl acrylate, methacrylic ester; And their mixture.
46. the method for claim 45, wherein said cationic polymers comprises: (being total to) polymkeric substance of diallyl dimethyl ammonium salt; (being total to) polymkeric substance of polyamines/Epicholorohydrin; Polymine; (being total to) polymkeric substance of dimethylamine/Epicholorohydrin; The polymkeric substance of multiamide amine/Epicholorohydrin; And their mixture.
47. the method for claim 46, wherein said cationic polymers comprises: (being total to) polymkeric substance of diallyl dimethyl ammonium salt, (being total to) polymkeric substance of dimethylamine/Epicholorohydrin and their mixture.
48. the method for claim 43, the concentration of wherein said cationic polymers in pre-composition is for being less than about 2.5%.
49. the method for claim 48, the concentration of wherein said cationic polymers in pre-composition is for being less than about 1.5%.
50. the method for claim 49, the concentration of wherein said cationic polymers in pre-composition is for being less than about 1.0%.
51. the method for claim 43, wherein said anion particle are the synthetic inorganic particle of band anionic charge of inorganic mineral, high surface area of the band anionic charge of high surface area and their mixture.
52. the method for claim 51, wherein said anion particle comprise swelling clay, silica base particle and their mixture.
53. the method for claim 52, wherein said silica base particle comprise colloided silica, colloidal aluminium modified silica, pure aluminium silicate and their mixture.
54. the method for claim 52, wherein said swelling clay comprises wilkinite, montmorillonite, polynite, beidellite, nontronite, hectorite, saponite, sepiolite or attapulgite.
55. the method for claim 54, wherein said anion particle is a wilkinite.
56. the method for claim 52, the granularity of wherein said swelling clay are about 1 nanometer-Yue 1 micron.
57. the method for claim 52, the surface-area of wherein said swelling clay is 50m at least 2/ g.
58. the method for claim 57, the surface-area of wherein said swelling clay is 100m at least 2/ g.
59. the method for claim 58, the surface-area of wherein said swelling clay is 200m at least 2/ g.
60. the method for claim 43, the granularity of wherein said silica base particle is for being lower than about 50 nanometers.
61. the method for claim 60, the granularity of wherein said silica base particle is for being lower than about 20 nanometers.
62. the method for claim 61, the granularity of wherein said silica base particle is about 10 nanometers of about 1-.
63. the method for claim 43, the surface-area of wherein said silica base particle is 50m at least 2/ g.
64. the method for claim 63, the surface-area of wherein said silica base particle is 100m at least 2/ g.
65. the method for claim 64, the surface-area of wherein said silica base particle is at least about 200m 2/ g.
66. the method for claim 43, wherein said stablizer are non-ionic or cationic.
67. the method for claim 43, wherein said stablizer comprises: the methylol Natvosol, the Natvosol of butylglycidyl ether modification, hydroxypropylcellulose, methyl hydroxyethylcellulose, methylhydroxypropylcellulose, methylcellulose gum, ethyl cellulose, the poly-N-vinyl pyrrolidone, polyvinyl alcohol, polyethylene oxide, poly(propylene oxide), polyacrylamide, starch ethers, starch ester, Sumstar 190, guar gum, pectin, carrageenan, Viscogum BE, xanthan gum, water soluble protein, lyophobic association type thickener for paints, cationic starch, Natvosol, hydroxypropylguar gum and cation guar gum.
68. the method for claim 67, wherein said stablizer comprises hydroxypropylguar gum or Natvosol.
69. the method for claim 68, wherein said stablizer is a hydroxypropylguar gum.
70. the method for claim 43, the addition of wherein said stablizer are the about 0.1%-about 5% based on described pre-composition gross weight.
71. the method for claim 70, the addition of wherein said stablizer are the about 0.2%-about 1.0% based on described pre-composition gross weight.
72. the method for claim 71, the addition of wherein said stablizer are the about 0.3%-about 0.7% based on described pre-composition gross weight.
73. the method for claim 43, the viscosity of wherein said water-based system is 1000cps at least.
74. the method for claim 73, the viscosity of wherein said water-based system is 2000cps at least.
75. the method for claim 74, the viscosity of wherein said water-based system is 3000cps at least.
76. the method for claim 43, the viscosity of wherein said water-based system is the about 3500cps of about 2000-.
77. plain matrix of the method coated fibres with claim 44.
78. a method for preparing stable pre-composition, it comprises:
(a) form the pre-composition that comprises anion particle and cationic polymers;
(b) in described pre-composition, add stablizer, wherein formed stable pre-composition; With
(c) randomly in described pre-composition, add biocide.
79. the method for claim 78, wherein said cationic polymers comprises: (being total to) polymkeric substance of diallyldialkylammonihalide salt; (being total to) polymkeric substance of diallyl amine; (being total to) polymkeric substance of diallyl alkylamine; Polymine; (being total to) polymkeric substance of dialkylamine/Epicholorohydrin; (being total to) polymkeric substance of polyamines/Epicholorohydrin; (being total to) polymkeric substance of multiamide/Epicholorohydrin; (being total to) polymkeric substance of multiamide amine; (being total to) polymkeric substance of multiamide amine/Epicholorohydrin; (being total to) polymkeric substance of dialkyl aminoalkyl acrylamide and Methacrylamide and quaternised (being total to) polymkeric substance; (being total to) polymkeric substance and quaternised (being total to) polymkeric substance with dialkyl aminoalkyl acrylate and methacrylic ester; And their mixture.
80. the method for claim 79, wherein said cationic polymers comprises: (being total to) polymkeric substance of diallyl dimethyl ammonium salt; (being total to) polymkeric substance of polyamines/Epicholorohydrin; Polymine; (being total to) polymkeric substance of dimethylamine/Epicholorohydrin; The polymkeric substance of multiamide amine/Epicholorohydrin; And their mixture.
81. the method for claim 80, wherein said cationic polymers comprise (being total to) polymkeric substance of diallyl dimethyl ammonium salt, (being total to) polymkeric substance of dimethylamine/Epicholorohydrin and their mixture.
82. the method for claim 78, the concentration of wherein said cationic polymers in pre-composition is for being less than about 2.5%.
83. the method for claim 82, the concentration of wherein said cationic polymers in pre-composition is for being less than about 1.5%.
84. the method for claim 83, the concentration of wherein said cationic polymers in pre-composition is for being less than about 1.0%.
85. the method for claim 78, wherein said anion particle are the synthetic inorganic particle of band anionic charge of inorganic mineral, high surface area of the band anionic charge of high surface area and their mixture.
86. the method for claim 85, wherein said anion particle comprise swelling clay, silica base particle and their mixture.
87. the method for claim 86, wherein said silica base particle comprise colloided silica, colloidal aluminium modified silica, pure aluminium silicate and their mixture.
88. the method for claim 86, wherein said swelling clay comprises wilkinite, montmorillonite, polynite, beidellite, hectorite, nontronite, saponite, sepiolite or attapulgite.
89. the method for claim 88, wherein said anion particle is a wilkinite.
90. the method for claim 86, the granularity of wherein said swelling clay are about 1 nanometer-Yue 1 micron.
91. the method for claim 86, the surface-area of wherein said swelling clay is 50m at least 2/ g.
92. the method for claim 91, the surface-area of wherein said swelling clay is 100m at least 2/ g.
93. the method for claim 92, the surface-area of wherein said swelling clay is 200m at least 2/ g.
94. the method for claim 86, the granularity of wherein said silica base particle is for being lower than about 50 nanometers.
95. the method for claim 86, the granularity of wherein said silica base particle is for being lower than about 20 nanometers.
96. the method for claim 95, the granularity of wherein said silica base particle is about 10 nanometers of about 1-.
97. the method for claim 86, the surface-area of wherein said silica base particle is 50m at least 2/ g.
98. the method for claim 97, the surface-area of wherein said silica base particle is 100m at least 2/ g.
99. the method for claim 98, the surface-area of wherein said silica base particle is at least about 200m 2/ g.
100. the method for claim 78, wherein said stablizer are non-ionic or cationic.
101. the method for claim 78, wherein said stablizer comprises: the methylol Natvosol, the Natvosol of butylglycidyl ether modification, hydroxypropylcellulose, methyl hydroxyethylcellulose, methylhydroxypropylcellulose, methylcellulose gum, ethyl cellulose, the poly-N-vinyl pyrrolidone, polyvinyl alcohol, polyethylene oxide, poly(propylene oxide), polyacrylamide, starch ethers, starch ester, Sumstar 190, guar gum, pectin, carrageenan, Viscogum BE, xanthan gum, water soluble protein and lyophobic association type thickener for paints, cationic starch, Natvosol, hydroxypropylguar gum and cation guar gum.
102. the method for claim 101, wherein said stablizer comprises hydroxypropylguar gum or Natvosol.
103. the method for claim 102, wherein said stablizer is a hydroxypropylguar gum.
104. the method for claim 78, the addition of wherein said stablizer are the about 0.1%-about 5% based on described pre-composition gross weight.
105. the method for claim 104, the addition of wherein said stablizer are the about 0.2%-about 1.0% based on described pre-composition gross weight.
106. the method for claim 105, the addition of wherein said stablizer are the about 0.3%-about 0.7% based on described pre-composition gross weight.
107. the method for claim 78, wherein said stable pre-composition viscosity is 1000cps at least.
108. the method for claim 107, wherein said stable pre-composition viscosity is 2000cps at least.
109. the method for claim 108, wherein said stable pre-composition viscosity is 3000cps at least.
110. the method for claim 78, wherein said stable pre-composition viscosity is the about 3500cps of about 2000-.
111. pre-composition according to the stable anion particle/cationic polymers of the method for claim 78 preparation.
CN 200480011927 2003-05-02 2004-04-30 Aqueous systems containing additive pre-mixes and processes forming the same Pending CN1784458A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
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CN103635630A (en) * 2011-06-30 2014-03-12 凯米罗总公司 Fixative composition, thick stock composition and process for fixating hydrophobic and/or anionic substances on fibres
CN103917608A (en) * 2011-11-10 2014-07-09 巴斯夫欧洲公司 Paper coating slip additive comprising acid monomer, associative monomer and nonionic monomer
CN104389239A (en) * 2014-09-28 2015-03-04 金东纸业（江苏）股份有限公司 Paint and coated paper
CN111670224A (en) * 2018-02-08 2020-09-15 株式会社资生堂 Powder-containing composition, powder for aqueous solvent, and method for producing powder for aqueous solvent
WO2020207372A1 (en) * 2019-04-08 2020-10-15 Main Choice Paper Products Limited Germ-repellent book and food paper packaging, and method of manufacture

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103635630A (en) * 2011-06-30 2014-03-12 凯米罗总公司 Fixative composition, thick stock composition and process for fixating hydrophobic and/or anionic substances on fibres
CN103635630B (en) * 2011-06-30 2016-05-18 凯米罗总公司 For lyophobic dust and/or anionic species are fixed on to the fixative composition on fiber, thick paste compound and method
CN103917608A (en) * 2011-11-10 2014-07-09 巴斯夫欧洲公司 Paper coating slip additive comprising acid monomer, associative monomer and nonionic monomer
CN104389239A (en) * 2014-09-28 2015-03-04 金东纸业（江苏）股份有限公司 Paint and coated paper
CN111670224A (en) * 2018-02-08 2020-09-15 株式会社资生堂 Powder-containing composition, powder for aqueous solvent, and method for producing powder for aqueous solvent
WO2020207372A1 (en) * 2019-04-08 2020-10-15 Main Choice Paper Products Limited Germ-repellent book and food paper packaging, and method of manufacture

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