CN104746388B - A kind of method of the sizing efficiency for the ASA lotions for improving macromolecule emulsifier emulsification - Google Patents
A kind of method of the sizing efficiency for the ASA lotions for improving macromolecule emulsifier emulsification Download PDFInfo
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- CN104746388B CN104746388B CN201310728543.0A CN201310728543A CN104746388B CN 104746388 B CN104746388 B CN 104746388B CN 201310728543 A CN201310728543 A CN 201310728543A CN 104746388 B CN104746388 B CN 104746388B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
- D21H17/15—Polycarboxylic acids, e.g. maleic acid
- D21H17/16—Addition products thereof with hydrocarbons
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
- D21H17/29—Starch cationic
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/31—Gums
- D21H17/32—Guar or other polygalactomannan gum
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
Abstract
The present invention relates to the method for the sizing efficiency that ASA sizing agents are improved in paper-making process.Specifically, this method include the use of macromolecule emulsifier emulsification ASA lotions paper pulp is glued as sizing agent, wherein, in the paper pulp be added with hydroxyl naturally the compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide as papermaking filler.
Description
Technical field
The present invention relates to the method for the sizing efficiency that ASA sizing agents are improved in paper-making process.In particular it relates to
In paper-making sizing, using hydroxyl, naturally hydrocarbon macromolecule polysaccharide compound handles papermaking filler particle, to improve macromolecule
The method of the sizing efficiency of the ASA lotions of emulsifier.
Background technology
Paper be have typical polarity, strongly hydrophilic feature containing cellulose fibrous composite, that is to say, that it can
Easily to be soaked and be swollen by water-based system.When writing and printing, and when paper conversion, this causes water and other liquid
(such as ink, printing ink) excessively and uncontrollably infiltrated fiber network.Resulting problem especially includes interior fiber
The slackening of bonding force, the deterioration of mechanical performance, dimensional stability reduces and the excessively poor property write and impressionability.
In order to control moistening and permeability behavior, using alleged sizing agent, it resists above-mentioned behavior by part hydrophobization.
These auxiliary agents can be added in aqueous fiber element paper pulp (internal sizing), can also by using suitable coating system (such as
Sizing press, molding machine, coating machine etc.) (top sizing) is surface-treated to the paper web formed and is applied.It is right
In the paper of certain type, both approaches can be used in combination.
In neutral or slightly alkaline copy paper, using neutral sizing agent, typical neutral sizing agent includes such as alkyl ketene
Dimer (AKD) and alkenyl succinic anhydride (ASA).In recent years, paper and cardboard are glued complete using neutral sizing agent
Ball has become universal.In general, neutral sizing agent is insoluble in the grease of water in itself, therefore, it is added to dispensing
For that must be emulsion state before being finally glued.In order to obtain stable neutral sizing agent emulsion, suitable emulsifying agent is phase
When important.Cationic starch and synthetic polymer based on acrylamide are typically used as emulsifying agent.Reach applying for target
Glue effect, it usually needs substantial amounts of cationic starch emulsifying agent, and the synthetic polymer of opposite much less can realize it is similar
Effect, therefore, compared with cationic starch, polymer emulsifier has attracted more concerns.Moreover, use substantial amounts of sun
Ionic starch is significantly increased from chemical oxygen demand (COD) level in the water of paper mill discharge, this will cause serious ring
Pollute in border.From the angle of environmental protection, it is expected to replace cationic starch using cation property copolymer.
On the other hand, for the needs for reducing cost, more and more fillers such as CaCO is added into paper now3、
TiO2, to reduce fiber consumption.
However, these fillers generally used can bring adverse effect to the sizing of alkaline paper, with ash content ratio
Increase, i.e. increased filler is more, and neutral sizing is more unfavorable be subject to being influenced.Particularly, make using polymer emulsifier
In the case of for emulsifying agent, with using cationic starch, compared with the situation of emulsifying agent, the effect of neutral sizing is often not
It is preferable.
Once there is document report to carry out surface modification to filler excessively to improve the report of sizing efficiency in the past, but mainly filled out
The hydrophobic modification and treatment technology of material.United States Patent (USP) 5411639, which reports, is gelatinized starch, by the aqueous solution of starch with
Fatty acid soaps (sodium salt or sylvite of aliphatic acid) mix, and starch/fatty acid soaps compound are can obtain under certain condition, by this
Compound is used to modify filler, can effectively improve the sizability of AKD.United States Patent (USP) 5527430 also reports a kind of use
The surface modification of filler is carried out by using macromolecule, makes filler surface hydrophobicity so as to the method for improving ASA sizing efficiencies.At this
In two methods, aliphatic acid or soap are all employ, and the dosage of starch/fatty acid soaps compound is larger, causes whole
Process complexity is cumbersome, and the calcium carbonate surface modification chemicals dosage used is very much, for economic value, is unfavorable for actual
Using.
The content of the invention
In view of the defects of above-mentioned prior art, the technical problems to be solved by the invention are to provide a kind of raising macromolecule latex
The method of the sizing efficiency of the ASA lotions of agent emulsification, it can significantly improve the situation using macromolecule emulsifier as emulsifying agent
Under neutral sizing efficiency.
The present inventor has made intensive studies to solve the above problems, it turns out that natural by using hydroxyl
The compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide can effectively improve macromolecule emulsifier as papermaking filler
The sizing efficiency of the ASA lotions of emulsification.Moreover, it was also surprisingly found that using only the natural hydrocarbon high score of a small amount of hydroxyl
Sub- compound of polysaccharide, which is modified papermaking filler particle, can be achieved the effect above.
That is, the present invention includes a kind of sizing efficiency for the ASA lotions that macromolecule emulsifier emulsification is improved in paper-making process
Method, this method include the use of macromolecule emulsifier emulsification ASA lotions the paper pulp is glued as sizing agent, institute
State in paper pulp added with hydroxyl naturally the compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide as papermaking filler.
In addition, the present invention also provides a kind of method of papermaking, it comprises the following steps：By the natural hydrocarbon macromolecule of hydroxyl
Compound of polysaccharide is modified papermaking filler particle and is added in paper pulp, while or before this or thereafter, by macromolecule emulsifier breast
The ASA lotions of change are added in paper pulp.
According to the present invention it is possible to the sizing efficiency of ASA sizings when significantly improving using macromolecule emulsifier as emulsifying agent.
According to the present invention, the sizing efficiency of the ASA lotions of macromolecule emulsion is synthesized, not less than boiling cationic starch emulsifying agent (at present
Most effective ASA is glued emulsifying agent) sizing efficiencies of the ASA lotions of emulsification.
The embodiment of invention
Unless otherwise specified, the implication that the implication of the scientific and technical terminology in this specification is commonly understood by with those skilled in the art
It is identical, but if any conflict, then the definition in this specification shall prevail.
The present invention provides a kind of side of the sizing efficiency for the ASA lotions that macromolecule emulsifier emulsification is improved in paper-making process
Method, this method include：The ASA lotions emulsified using macromolecule emulsifier are glued the paper pulp as sizing agent, described
In paper pulp added with hydroxyl naturally the compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide as papermaking filler.
ASA
In the present specification, ASA refers to alkenyl succinic anhydride, it is known neutral sizing agent (United States Patent (USP)
US3102064).ASA sizing agents can use commercial product, such as nail (unit of length) section product N7540, N7542, N7543, the production of Kai meter companies
Product AS2300 etc..ASA is insoluble in the grease of water, and the mixture of itself and water exists in the form of an emulsion, in order to obtain stabilization
ASA lotions, it is necessary to use emulsifying agent.
Macromolecule emulsifier
As the emulsifying agent for emulsifying ASA lotions, such as cationic starch can be included and based on acrylamide
Synthetic polymer.In the present specification, macromolecule emulsifier can be water-soluble polyacrylamide class compound, it is selected from third
The crosslinked acrylamide of copolymer and glyoxal of acrylamide and cationic monomer and the copolymer of cationic monomer.
Here, the cationic monomer can be selected from dimethylallylammonium chloride, methylacryoyloxyethyl front three
Ammonium chloride, N, N, N- trimethyls -3- (2- methallyls acylamino-) third ammonium of -1- chlorinations, methacrylic acid N, N'- diformazan ammonia second
Ester, methacrylic acid N, N'- diformazan ammonia ethyl ester quaternary ammonium salt cationic, dimethylamino ethyl acrylate, acrylic acid dimethylamino second
One or both of ester quat, acrylic acid diethylaminoethyl and acrylic acid diethylaminoethyl quaternary ammonium salt are a variety of.
For example, the macromolecule emulsifier can be the copolymer of acrylamide and cationic monomer, its weight average molecular weight
For 10000~1000000 dalton, in the copolymer ratio of cationic monomer unit and acrylamide unit for 1/99 to
20/80, such as 2/98 to 18/82, in another example 5/95 to 15/85.
In the present specification, " cationic monomer unit " refers to the part that cationic monomer is derived from polymer；" propylene
Amide units " refer to the part that acrylamide is derived from polymer, and " glyoxal unit " refers to derive from second two in polymer
The part of aldehyde.
For another example the macromolecule emulsifier can be the copolymerization of the crosslinked acrylamide of glyoxal and cationic monomer
Thing, its weight average molecular weight are 100000~3000000 dalton, in the copolymer, acrylamide unit and cationic monomer list
The ratio of member is 5/95 to 95/5, the ratio of glyoxal unit and acrylamide unit be 60/40 to 5/95, such as 50/50 to
10/90, in another example 45/55 to 10/90.
More specifically, the macromolecule emulsifier can be selected from MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and acryloyl
The copolymer and dimethyl diallyl ammonium chloride acrylamide glyoxal cross-linking agent of amine.
As commercially available macromolecule emulsifier, can include such as Ondeo Nalco Co. N7541, N63007 and
Bubond650 of Buckman companies etc..
The ASA lotions of macromolecule emulsifier emulsification
The ASA lotions of macromolecule emulsifier emulsification are known in the art, may refer to such as United States Patent (USP)
4657946 and United States Patent (USP) 6491790.The ASA lotions of macromolecule emulsifier emulsification can for example be prepared as follows：To such as 0.01
The macromolecule emulsifier of~10 parts by weight is mixed with the water of 50~99.9 parts by weight, then adds the ASA of 0.01~40 parts by weight,
Stir 1~2 minute under high shear conditions.Here, shear conditions refer to allow ASA to be distributed in water by the method for mechanical force
Lotion is formed, the method for realizing shear conditions is known in the art, such as can be come using homogenizer or turbine pump
Realize.In the ASA lotions of macromolecule emulsifier emulsification, the content of ASA can be such as 0.01-10 weight %.Gained emulsifies ASA
The particle diameter of particle can be such as 0.1-5 microns, in another example for 0.2-2 microns, then for example, 0.5-1.5 microns.
The natural compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide of hydroxyl
In this specification, naturally the compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide includes hydroxyl：Core, its
Formed by the aggregation of single papermaking filler particle or papermaking filler particle；And clad, it is by the natural hydrocarbon height of hydroxyl
Molecular polysaccharide is formed, and coats the surface of the core.In this specification, naturally hydrocarbon macromolecule polysaccharide compound changes hydroxyl
Property papermaking filler particle can be only made of above-mentioned core and clad.In this specification, " clad is naturally hydrocarbon by hydroxyl
Macromolecule polysaccharide is formed " refer to only include hydroxyl naturally hydrocarbon macromolecule polysaccharide changing as papermaking filler particle in clad
Property agent.
In this specification, naturally hydrocarbon macromolecule polysaccharide refers to by monosaccharide monomers (C hydroxyl6H10O6) by glycosidic bond and
The polymerization sugar polymeric carbohydrate of formation.Can be specifically selected from cellulose, cationic cellulose, chitosan, cation
It is more than one or both of chitosan, guar gum, cation guar gum, boiling ative starch and boiling cationic starch.Such as
Can be cooking starch with more than one or both of cellulose, chitosan, guar gum or their cation compound
Combination, then for example can be cooking starch (referring to boiling ative starch and/or boiling cationic starch in this specification), and example
It such as can be boiling ative starch.
In the present specification, " papermaking filler " is a kind of important paper making raw material, and alternative a large amount of paper pulp fibers are used to make
Paper process, its application can significantly reduce papermaking cost, improve into the whiteness of paper, opacity, smoothness, glossiness, prints suitable
Ying Xing, writes adaptability and/or dimensional stability etc., can also improve drainage of the paper stock in paper making wet part under certain condition,
Reduce papermaking cost.The papermaking filler can be inorganic filler or organic filler.The inorganic filler can be example
One kind such as in kaolin, calcium carbonate, talcum powder, titanium dioxide, aluminium hydroxide, calcium sulfate and amorphous silicate or
Two or more, e.g. calcium carbonate is with being selected from kaolin, talcum powder, titanium dioxide, aluminium hydroxide, calcium sulfate and amorphous silicon
Combination more than one or both of hydrochlorate, in another example being calcium carbonate.The calcium carbonate can be anion calcium carbonate, such as
Anion grinding calcium carbonate or anion winnofil；Can also be cation calcium carbonate, such as precipitated cationic calcium carbonate
Or cation grinding calcium carbonate.The organic filler can be selected from synthesis high score subclass filler, starch based filler, wood powder
It is more than one or both of filler.The synthesis high score subclass filler can be such as vinylidene chloride/acrylonitrile compolymer
Thing, Lauxite agglomerate filler and starch based filler.The papermaking filler for example can be such as calcium carbonate with being selected from kaolinite
Soil, talcum powder, titanium dioxide, aluminium hydroxide, calcium sulfate, amorphous silicate, high score subclass filler, starch based filler, wood powder
Combination more than one or both of filler.The papermaking filler can be long time without surface modification or pass through table
What face was modified.The surface modification can use the surface modifier of the art routine, such as ative starch, cationic starch
Etc. carrying out.
In the present specification, " papermaking filler particle " refers to the particle of the papermaking filler, and its long time without surface modification.Make
Paper wadding particle can be primary particle (single papermaking filler particle) or secondary (papermaking filler particle it is poly-
Collective).The particle diameter of the papermaking filler particle is not particularly limited, is used as long as not influencing it as papermaking filler.
The particle diameter of the papermaking filler particle can be such as 0.1~200 micron, in another example 2~100 microns, then such as 10~50 micro-
Rice.
In the present specification, " clad " refers to the layer for being coated on the surface of the core.The clad and the core
The weight ratio of the heart can be such as 0.1：100~5：100, in another example 0.2：100~2：100, then such as 0.3：100~1.5：
100。
Naturally the compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide can for example use following systems to the hydroxyl
Method is made to prepare.The manufacture method includes：
1. prepare the solution or dispersion liquid of the natural hydrocarbon macromolecule polysaccharide of hydroxyl.The solution or dispersion liquid can be examples
Such as aqueous solution or dispersion liquid.It is not special for the content of the natural hydrocarbon macromolecule polysaccharide of hydroxyl in the solution or dispersion liquid
Limitation, can suitably select as needed, such as can be 0.1~20 weight %, in another example can be 0.2~10 weight %,
For example can be 0.5~5 weight % again.
2. prepare the suspension of papermaking filler particle.The suspension can be such as aqueous suspension.For described suspended
The content of papermaking filler particle is not particularly limited in liquid, can suitably be selected as needed, such as can be 1-60 weights
% is measured, in another example can be 5-30 weight %, then for example can be 10-20 weight %.
3. by the outstanding of the hydroxyl naturally solution of hydrocarbon macromolecule polysaccharide or dispersion liquid and the papermaking filler particle
Turbid mixes so that naturally hydrocarbon macromolecule polysaccharide coats the surface of the papermaking filler particle to hydroxyl.Contain hydroxyl for described
Naturally the mixed proportion of the solution of hydrocarbon macromolecule polysaccharide or dispersion liquid and the suspension of the papermaking filler particle is no special for base
Different limitation, can suitably select as needed, such as relative to the papermaking in the suspension of the papermaking filler particle
100 parts by weight of filler grain, the hydroxyl of the hydroxyl of addition naturally in the solution or dispersion liquid of hydrocarbon macromolecule polysaccharide are natural
Hydrocarbon macromolecule polysaccharide is such as 0.1~20 parts by weight, in another example 0.2~10 parts by weight, then such as 0.5~5 parts by weight.Mixing
In and/or mixing after can promote to mix for example, by stirring.Gained mixed liquor can be used directly as papermaking filler,
Can be by the means such as filtering, centrifuging by the natural compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide of the hydroxyl of preparation
Separate.Can be by adjusting the hydroxyl naturally solution of hydrocarbon macromolecule polysaccharide or dispersion liquid and the papermaking filler
The mixed proportion of the suspension of particle, incorporation time, stirring condition, filtering/centrifugal condition etc. adjust the hydroxyl day of preparation
Hydroxyl naturally hydrocarbon macromolecule polysaccharide and papermaking filler grain in the right hydrocarbon compound modified papermaking filler particle of macromolecule polysaccharide
The weight ratio of son, this is that those skilled in the art can suitably select.
The natural natural hydrocarbon high score of the hydroxyl in the compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide of hydroxyl
The part by weight of sub- polysaccharide and papermaking filler particle can such as measure with the following method：By the natural hydrocarbon high score of gained hydroxyl
Sub- compound of polysaccharide is modified papermaking filler particle such as heat drying and removes medium (such as water, organic solvent) therein, weighs,
It is counted as M1；By the hydroxyl after heat drying, naturally the compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide uses medium again
(such as water, organic solvent) immersion makes hydroxyl, and naturally hydrocarbon macromolecule polysaccharide layer is swollen, then using physical method (example
Such as polished with sand paper) hydroxyl naturally hydrocarbon macromolecule polysaccharide layer is removed, gained papermaking filler particle is for example heated again
The dry medium for removing attachment removal, weighs, is counted as M2 again；The weight ratio is M1-M2/M2..For another example filled out in the papermaking
Material particle be calcium carbonate when non-flammable inorganic filler, the weight ratio can be measured for example with following methods：By gained
The hydroxyl naturally compound modified papermaking filler particulate filter separation of hydrocarbon macromolecule polysaccharide, it is dry at such as 120 DEG C, remove
Medium (such as water, organic solvent), takes a certain amount of hydroxyl being completely dried naturally hydrocarbon macromolecule polysaccharide is compound modified and make
Paper wadding particle, weighs, and is counted as M1；When heating 2 is small in air at such as 550 DEG C, weighs again, be counted as M2；The weight
Than for M1-M2/M2.
Paper-making process
In the present specification, " paper-making process " refers to the process from pulp manufacture paper products, main aqueous including being formed
Cellulosic papermaking ingredients, dispensing drainage is formed into paper and dries paper.
In the present specification, " paper pulp " refers to the product that pulping process obtains.Slurrying refers to utilize chemical method or machinery
The method that method or both combines dissociates plant fiber material, forms true qualities paper pulp (brown stock) or further forms bleached paper
The production process of slurry.Paper pulp can be paper pulp known to any type, include but not limited to, mechanical pulp, chemical pulp, chemistry
Mechanical pulp, reclaimed waste paper slurry etc., the paper pulp e.g. comprising mechanical pulp and/or regenerated fiber.
In the present specification, paper pulp can be known as by being beaten and being made after condiment for the fibrous suspension that copy paper uses
" paper stock ", to be different from the slurry for not being beaten and being not added with filler.
In the present specification, " l Water Paper page (wet paper sheet) " refers to：Paper stock is successively by head box, forming section
And press section is formed and product that is partially dehydrated, and obtaining, the mass dryness fraction of l Water Paper page can be 35%~50%.In order to carry out area
Not, the product by being come out from forming section but not yet through press section press dehydration is known as " wet web (wet paper web) ", wet
The mass dryness fraction of paper web can be 15%~25%.
In the present specification, " page (paper sheet) " refers to：L Water Paper page is dried by drying section, and is obtained
Product, the mass dryness fraction of page can be 92%~97%.
The present invention in terms of one in a kind of method of papermaking is also provided, it comprises the following steps：
(a) paper pulp is provided；
(b) by hydroxyl, naturally the compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide is added in paper pulp, at the same time
Or before this or thereafter, the ASA lotions of macromolecule emulsifier emulsification are added in paper pulp, obtain paper stock；
(c) the paper stock shaping made, obtains wet web (wet paper web)；
(d) press dewatering is carried out to the wet web obtained in step (c), obtains l Water Paper page (wet paper sheet)；With
And
(e) the wet paper page drying position that will be obtained in step (d), obtains page (paper sheet).
1. the processing before paper stock online, including
(1) paper stock is prepared：Paper stock can be made in paper pulp, and the preparation of paper stock includes mashing and condiment (sizing material, filler, colorant
And the addition of the additive such as auxiliary agent).Paper pulp is first had to by mashing, the fiber of paper pulp is carried out it is necessary prescind, swollen and thin
The processing such as fibrosis, so that physical property and mechanical strength properties required by paper acquirement paper kind, and can meet paper machine
It is required that.In order to enable page to be used to write the dipping with resistant to liquids, improve the color, whiteness and tone of paper, increase the impermeable of paper
Lightness, improves printing performance of paper etc., and slurry can be glued, filled and dyeing, can also add various chemical assistants,
To assign paper some special performances (such as improve dry strength, wet strength, gas and eliminate bubble).In this stage, can be by institute
Part or all for stating the natural compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide of hydroxyl is added to as filler
In paper pulp.Independently, while or before this or thereafter, can be by one of the ASA lotions that the macromolecule emulsifier emulsifies
Divide or be all added to as sizing agent in paper pulp.The hydroxyl naturally hydrocarbon height can be only added as filler, in paper pulp
The compound modified papermaking filler particle of molecular polysaccharide；And/or as sizing agent, the macromolecule latex can be only added in paper pulp
The ASA lotions of agent emulsification.Certainly, optionally, other fillers and/or other sizing agents can also be added in paper pulp.
(2) paper stock is supplied to pulp feeding system：Paper stock stored into pulp feeding system, screened, purified, removed the gred, removed sand,
The processing such as degassing, discharges mixed metal in paper stock, nonmetallic inclusion, fibre bundle, slurry group and air etc., to avoid finished product is influenced
The quality of paper and bring difficulty to paper making process.Slurry through it is with slurry, dilute, thicken, measure, eliminate pressure pulse after enter
Head box online copy paper.
2. paper is manufactured paper with pulp, including
(1) slurry streaming：Paper stock is sent to forming section (wet end) by head box.Head box can make fiber dispersed, again
Slurry can be made steadily to surf the Internet.Paper can be added during slurry streams and does the additive for paper making such as the wet strong auxiliary agent of strong auxiliary agent, paper.
In this stage, can by the hydroxyl naturally a part for the compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide or
All it is added to as filler in paper pulp.Independently, while or before this or thereafter, can by the macromolecule emulsifier breast
Part or all of the ASA lotions of change is added in paper pulp as sizing agent.Can only it be added as filler, in paper pulp described
The natural compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide of hydroxyl；And/or as sizing agent, can be only in paper pulp
Add the ASA lotions of the macromolecule emulsifier emulsification.Certainly, optionally, can also be added in paper pulp other fillers and/or
Other sizing agents.
(2) shape：In forming section, the paper stock of head box conveying in online drainage by forming wet web, forming section
Also known as wet end.The mass dryness fraction of wet web can be 15%~25%.
The step (c) can carry out for example, by the step (1) and (2), but not limited to this.
(3) press dewatering：In press section, the wet web from forming section passes through mechanical expression, forms l Water Paper page.L Water Paper
The mass dryness fraction of page can be 35%~50%.
The step (d) can carry out for example, by the step (3), but not limited to this.
(4) it is dry：In drying section, the l Water Paper page from press section forms page using drying cylinder evaporation moisture.Page
Mass dryness fraction can be 92%~97%.
The step (e) can carry out for example, by the step (4), but not limited to this.
The additive amount of the natural compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide of the hydroxyl in paper pulp（When
Refer to total addition level when dividing multiple stages additions）It can suitably be selected as needed by those skilled in the art, such as can be
Finally into the 20-30 weight % of paper.For example, relative to 100 parts by weight of absolute dried paper pulp, the natural hydrocarbon macromolecule of the hydroxyl of addition
The total amount that compound of polysaccharide is modified papermaking filler particle can be such as 1~50 parts by weight, in another example 10~30 parts by weight, and example
Such as 15-30 parts by weight, in another example 20-30 parts by weight.Sizing in the above-mentioned two stage is known as paper internal sizing, is making for the present invention
Resin application methods in paper method.The additive amount of the ASA lotions of the macromolecule emulsifier emulsification（It is when adding in a point multiple stages
Refer to total addition level）Can suitably it be selected as needed by those skilled in the art, this selection is the normal of those skilled in the art
Advise technical ability.The additive amount of the ASA lotions of the macromolecule emulsifier emulsification for example can be in terms of ASA, relative to absolute dried paper pulp
100 parts by weight, can be 0.05~0.5 parts by weight, be, for example, 0.05~0.1 parts by weight.
In addition, press polish can also be carried out to page as needed, batches and cut paper, selects the finisher such as paper or rewinding, packing
Sequence, makes tablet or scroll-like finished paper.In addition, in order to improve the quality of page, table can also be carried out in drying section
Face sizing, coating and online soft calendaring or the outer supercalendering of machine.
In paper-making process, the paper stock provided by paper stock preparation system will generally pass through pulp feeding system (progress paper stock online
Preceding processing), head box and forming section, press section, drying section etc..
Embodiment
Hereinafter, embodiment and comparative example are included more specific description is carried out to the present invention, but the present invention is from these realities
Apply the restriction of example.
1. the preparation of the natural hydrocarbon macromolecule polysaccharide of cooking starch or other hydroxyls
As the natural hydrocarbon macromolecule polysaccharide compound of hydroxyl, for starch, (ative starch or cationic starch are equal
Can), used after needing boiling, a certain amount of starch is added to the water, boiling lower gelatinization, the concentration of starch is 2 weight %.For
The natural hydrocarbon macromolecule polysaccharide compound of other hydroxyls, is configured to the solution or dispersion liquid of 1 weight % concentration at room temperature,
In case use.
2. by using cooking starch or other hydroxyls, naturally prepared by hydrocarbon macromolecule polysaccharide cladding papermaking filler particle
The natural compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide of hydroxyl
Certain density calcium carbonate suspension is placed in beaker, under stirring, is added in calcium carbonate particle a certain amount of
The natural hydrocarbon macromolecule polysaccharide of hydroxyl, continues stir about 10 minutes, and naturally hydrocarbon macromolecule polysaccharide compound adds hydroxyl
Afterwards, calcium carbonate particle particle diameter significantly increases.
3. the preparation of the ASA lotions of macromolecule emulsifier emulsification
0.01~10 gram of N7541 or N63007 (nail (unit of length) section product) are mixed with 50-99.9 grams of water, then added
0.01~40 gram of ASA, stirs 1-2 minutes, obtains the ASA lotions for sizing under high shear conditions.
4. the test of laboratory handsheet process and paper water repelling property
The composition of fibre stuff is：20% long fibre (NBKP), 20% staple fiber (LBKP), 20% mechanical defibrator process
Learn slurry (BCTMP).
A certain amount of fibre stuff is taken, adds the pretreated filler of respective amount, after mixing 5 seconds, adds starch in slurry,
After mixing 15 seconds, the ASA lotions of macromolecule emulsifier emulsification are added, after mixing 25 seconds, adds and retains auxiliary agent nail (unit of length) section product N-
61067, mixing stops stirring after 40 seconds, and the slurry is transferred to Rapid Kothen Sheet Former handsheets, and handsheet is used
Filled wet end furnish being filled with for every 100 parts by weight in slurry, 20-30 parts by weight are filled out for the calcium carbonate of polysaccharide processing
Material.As control, also serve as filler without the hydroxyl calcium carbonate that naturally hydrocarbon macromolecule polysaccharide compound pre-processes and be added to
Handsheet in fibre stuff.The paper of a diameter of 20cm is formed by 100 mesh form wire drainages, then by the scraps of paper in 96 DEG C of vacuum bars
It is 8 minutes dry under part, it is placed under 24 DEG C of constant temperatures and is dried overnight.
The water-resistance of pattern tests (Hercules Sizing Test, HST) by Hercules water resistant test method.
HST test methods are that the resistance of infiltration of the paper to aqueous infiltrating thing is measured by optical method, are that one kind is used for degree of sizing
Useful universal testing method.Time of penetration of the tested inks in paper assesses paper water repelling property, is made in experiment
Contain 1% formic acid in ink (referring to Tappi Official Method530)..
5. experimental result and the analysis to experimental result
Embodiment 1：Take a certain amount of anion calcium carbonate suspension, under conditions of stirring add concentration be 1% sun from
Seed chitosan solution, stir about 20 minutes.Before untreated, the average grain diameter of calcium carbonate is 1.9 μm, through cationic chitosan solution
After processing, increase to about 7-10 μm.It has been confirmed that cationic chitosan and the weight ratio of calcium carbonate are about 0.3 in particle：100
~1.5：100.The calcium carbonate suspension handled well is added in paper pulp, according to 4 handsheet of above-mentioned steps, ASA breasts used in handsheet
Agent is nail (unit of length) section product N7541, its structure is the methylacryoyloxyethyl trimethyl ammonia chloride of the cationic charge containing 10%mol
The copolymer of ammonium and acrylamide (DMAEM*MCQ (Dimethylammoniumethylmethyacrylated
methylchloride quat)/AcAm(acrylamide)).The content of calcium carbonate is accounted for finally into the about 27-30% of paper weight,
In the i.e. last filled absolute dried paper pulp of 100 parts by weight, about 27-30 parts by weight are calcium carbonate.The dosage of ASA in the paper-making process,
Cationic chitosan handles CaCO3Dosage and particle diameter, HST test results and handsheet ash content be shown in table 1 in the lump.
Table 1
As can be seen from the above data, cationic chitosan processing calcium carbonate, it is possible to increase the ASA lotions of macromolecule emulsion
Sizing efficiency.For example, it is in the addition that calcium carbonate is unprocessed, additive amount of filler is about 28-29 weight %, ASA
Under conditions of 0.5kg/ tons, the HST values of pattern obtained by handsheet are 2.8 seconds；And filler passes through the cation shell that dosage is 15kg/ tons
After glycan processing, the increase of HST values is 26.5 seconds.Calcium carbonate is unprocessed, additive amount of filler is about 28-29 weight %, ASA
Addition be 0.9kg/ ton under conditions of, the HST values of pattern obtained by handsheet are 36.1 seconds, and filler is 15kg/ by dosage
After the cationic chitosan processing of ton, the increase of HST values is 177.0 seconds.
Embodiment 2：A certain amount of anion calcium carbonate suspension is taken, adds the guar gum solution that concentration is 1%, guar gum
Degree ofacationic substitution be 0.04, stir about 20 minutes.Before untreated, the average grain diameter of calcium carbonate is 1.9 μm, guar gum solution
After processing, according to the difference of guar gum amount used, particle increases to about 9-30 μm.It has been confirmed that guar gum and carbonic acid in particle
The weight ratio of calcium is about 0.3：100~1.5：100.The calcium carbonate suspension handled well is added to handsheet in paper pulp, handsheet institute
It is nail (unit of length) section product N7541 with ASA emulsifying agents.The content of calcium carbonate is accounted for finally into about 30 weight % of paper weight, i.e., and last 100
In the filled paper pulp of parts by weight, about 30 parts by weight are calcium carbonate.The dosage of ASA, guar gum processing CaCO in the paper-making process3's
Dosage and particle diameter, HST test results and handsheet ash content are shown in table 2 in the lump.
Table 2
As can be seen from the above data, cation guar gum processing calcium carbonate, it is possible to increase the ASA lotions of macromolecule emulsion
Sizing efficiency.For example, it is in the addition that calcium carbonate is unprocessed, additive amount of filler is about 28-29 weight %, ASA
Under conditions of 0.6kg/ tons, the HST values of pattern obtained by handsheet are 4.5 seconds；And filler passes through the cation melon that dosage is 15kg/ tons
After your glue processing, the increase of HST values is 32.7 seconds.Calcium carbonate is unprocessed, additive amount of filler is about 28-29 weight %, ASA
Addition be 1.0kg/ ton under conditions of, the HST values of pattern obtained by handsheet are 15.5 seconds；And filler is 15kg/ by dosage
After the cation guar gum processing of ton, the value increase of HST is 143.1 seconds.
Embodiment 3：A certain amount of anion winnofil suspension is taken, it is 2% that concentration is added under conditions of stirring
Boiling cationic starch solution, stir about 20 minutes.Before untreated, 1.9 μm of the average grain diameter of calcium carbonate, starch solution processing
Afterwards, about 100 μm are increased to.It has been confirmed that the weight ratio of boiling cationic starch and calcium carbonate is about 0.3 in particle：100~
1.5：100.The calcium carbonate suspension handled well is added to handsheet in paper pulp, the content of calcium carbonate is accounted for finally into the pact of paper weight
30%, i.e., in the last filled paper pulp of 100 parts by weight, about 30 parts by weight are calcium carbonate.The composition of fibre pulp used is：20%
NBKP+60%LBKP+20%BCTMP, the grammes per square metre of paper is 100g/m2.Macromolecule emulsifier used is nail (unit of length) section product in experiment
N63007.Table 3 is the water-resistance test data of handsheet.
Table 3
As can be seen from the above data, boiling cationic starch processing calcium carbonate, it is possible to increase the ASA breasts of macromolecule emulsion
The sizing efficiency of liquid.For example, calcium carbonate is unprocessed, additive amount of filler is about 28-29%, the addition of ASA is 0.5kg/
Under conditions of ton, the HST values of pattern obtained by handsheet are 6.2 seconds；And filler passes through the boiling cationic starch that dosage is 15kg/ tons
After processing, the increase of HST values is 110.2 seconds.In the addition that calcium carbonate is unprocessed, filler additive amount is about 28-29%, ASA
Under conditions of 0.9kg/ tons, the HST values of pattern obtained by handsheet are 68.3 seconds；And filler passes through the boiling that dosage is 15kg/ tons
After cationic starch processing, the value increase of HST is 395.6 seconds.
Embodiment 4：A certain amount of anion calcium carbonate suspension is taken, the boiling that concentration is 2% is added under conditions of stirring
Ative starch solution, stir about 20 minutes.Before untreated, 2 μm of the average grain diameter of calcium carbonate, after starch solution processing, according to starch
The difference of dosage, increases to about 17-50 μm.It has been confirmed that the weight ratio of boiling ative starch and calcium carbonate is about 0.3 in particle：
100~1.5：100.The calcium carbonate suspension handled well is added to handsheet in paper pulp, the content of calcium carbonate is accounted for finally into paper weight
The 28-30% of amount, i.e., in the last filled paper pulp of 100 parts by weight, about 28-30 parts by weight are calcium carbonate.The group of fibre pulp used
Become：20%NBKP+60%LBKP+20%BCTMP, the grammes per square metre of paper is 100g/m2.Macromolecule emulsifier used is to receive in experiment
You are section product N63007.Table 4 is the water-resistance test data of handsheet.
Table 4
As can be seen from the above data, boiling ative starch processing calcium carbonate, it is possible to increase the ASA lotions of macromolecule emulsion
It is glued efficiency.For example, it is 0.5kg/ in the addition that calcium carbonate is unprocessed, additive amount of filler is about 28-30 weight %, ASA
Under conditions of ton, the HST values of pattern obtained by handsheet are 2.6 seconds；And filler by dosage be 15kg/ ton ative starch handle after,
The increase of HST values is 122.1 seconds.It is in the addition that calcium carbonate is unprocessed, additive amount of filler is about 28-30 weight %, ASA
Under conditions of 0.9kg/ tons, the HST values of pattern obtained by handsheet are 16.3 seconds；And filler is former by the boiling that dosage is 15kg/ tons
After starch processing, the increase of HST values is 240.5 seconds.
Embodiment 5：Compared with starch is as the situation of emulsifying agent
Cationic starch is emulsifying agent the most frequently used and best sizing efficiency in ASA sizings, and the purpose of the present embodiment is
Compare using 7541 and be used as emulsifying agent, CaCO3Sizing efficiency of the filler after starch is handled is with cationic starch directly as emulsification
The sizing efficiency of agent.In experiment, during using 7541 as emulsifying agent, the calcium carbonate being added in slurry is handled through starch, to locate
Manage CaCO3Boiling ative starch dosage be 10kg starch calcium carbonate per ton.United States Patent (USP) 5411639 utilizes starch and octadecyl
Carboxylic acid sodium handles pearl filler to improve sizing efficiency, compared for adding octadecyl carboxylic in cooking starch at the same time in this experiment
Influence of the compound processing calcium carbonate that sour sodium is formed to ASA sizing efficiencies.Experiment discovery, the sizing for macromolecule emulsifier
The raising of effect, single starch processing filler are more more effective than the compound processing of starch octadecyl carboxylic acid sodium.While I
It has also been found that, calcium carbonate after treatment, using N7541 as emulsifying agent, compares CaCO3When unprocessed, made with cationic starch
It is more effective for emulsifying agent.
Table 5N7541 is glued after pretreatment of starch as emulsifying agent, filler with cationic starch as the ASA of emulsifying agent
The contrast of effect
a:In cooking starch for pre-processing pearl filler, the octadecyl carboxylic acid sodium containing 5 weight %, dosage is
10kg/ tons of calcium carbonate.The addition of calcium carbonate is finally into about the 30% of paper weight.
Embodiment 6：Different CaCO3The influence of content
In the present embodiment, in the case of comparing different filling adding amounts, starch handle filler for macromolecule emulsion
The influence of agent sizing efficiency, starch used are the ative starch without cationization of boiling.The composition of fibre pulp used is：
20%NBKP+60%LBKP+20%BCTMP, the grammes per square metre of paper is 100g/m2, macromolecule emulsifier used produces for nail (unit of length) section in experiment
Product N7541.
The ASA lotions sizing effect that different filler additive amounts emulsifies macromolecule emulsifier when table 6N7541 is as emulsifying agent
The influence of fruit
As can be seen from Table 6, as the increase of filler additive amount, the sizing efficiency of ASA decline, with processing calcium carbonate
Starch dosage increase, the sizing efficiency of ASA is improved.
Claims (9)
1. a kind of sizing efficiency of alkenyl succinic anhydride " ASA " lotion that macromolecule emulsifier emulsification is improved in paper-making process
Method, this method include：
The ASA lotions emulsified using macromolecule emulsifier are glued paper pulp as sizing agent, and,
In the paper pulp added with hydroxyl naturally the compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide as papermaking
Filler,
Naturally the compound modified papermaking filler particle of hydrocarbon macromolecule polysaccharide includes wherein described hydroxyl：
Core, it is formed by the aggregation of single papermaking filler particle or papermaking filler particle；And
Clad, it coats the surface of the core, and its by hydroxyl, naturally hydrocarbon macromolecule polysaccharide is formed, the hydroxyl
Natural hydrocarbon macromolecule polysaccharide be selected from boiling cationic starch, boiling ative starch, chitosan, cationic chitosan, guar gum and
Cation guar gum or its any combinations；
Wherein, the macromolecule emulsifier is selected from the crosslinked propylene of copolymer and glyoxal of acrylamide and cationic monomer
The copolymer of acid amides and cationic monomer, and
Wherein, the macromolecule emulsifier is the copolymer of the crosslinked acrylamide of glyoxal and cationic monomer, its is heavy respectively
Son amount be 100,000~3,000,000 dalton, and the ratio between acrylamide unit and cationic monomer unit are 5/ in the copolymer
95 to 95/5, and the ratio between glyoxal unit and acrylamide unit are 60/40 to 5/95.
2. according to the method described in claim 1, wherein the ratio between glyoxal unit and acrylamide unit are 50/50 to 10/90.
3. according to the method described in claim 2, wherein the ratio between glyoxal unit and acrylamide unit are 45/55 to 10/90.
4. method according to any one of claim 1-3, wherein, the papermaking filler particle is calcium carbonate particle.
5. method according to any one of claim 1-3, wherein, the cationic monomer is selected from dimethyl-allyl chlorine
Change ammonium, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, N, N, N- trimethyls -3- (2- methallyls acylamino-) -1- chlorinations third
Ammonium, methacrylic acid N, N'- diformazan ammonia ethyl ester, methacrylic acid N, N'- diformazan ammonia ethyl ester quaternary ammonium salt cationic, acrylic acid diformazan
Aminoethyl, dimethylamino ethyl acrylate quaternary ammonium salt, acrylic acid diethylaminoethyl, and acrylic acid diethylaminoethyl season
Ammonium salt.
6. method according to any one of claim 1-3, wherein, the macromolecule emulsifier is selected from methacryloxypropyl
The copolymer and dimethyl diallyl ammonium chloride acrylamide glyoxal of ethyl-trimethyl salmiac and acrylamide are crosslinked
Thing.
7. method according to any one of claim 1-3, wherein, the natural hydrocarbon macromolecule polysaccharide chemical combination of the hydroxyl
In the papermaking filler particle that thing is modified, naturally hydrocarbon macromolecule polysaccharide compound and the weight ratio of papermaking filler particle are hydroxyl
0.1:100~5:100.
8. according to the method described in claim 7, wherein hydroxyl naturally hydrocarbon macromolecule polysaccharide compound and papermaking filler grain
The weight ratio of son is 100.2:100~2:100.
9. according to the method described in claim 8, wherein hydroxyl naturally hydrocarbon macromolecule polysaccharide compound and papermaking filler grain
The weight ratio of son is 0.3:100~1.5:100.
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| CN201310728543.0A CN104746388B (en) | 2013-12-25 | 2013-12-25 | A kind of method of the sizing efficiency for the ASA lotions for improving macromolecule emulsifier emulsification |
| MX2016008434A MX2016008434A (en) | 2013-12-25 | 2014-12-18 | Method for improving sizing efficiency of asa emulsion emulsified by a polymer emulsifier. |
| CA2929377A CA2929377A1 (en) | 2013-12-25 | 2014-12-18 | Method for improving sizing efficiency of asa emulsion emulsified by a polymer emulsifier |
| US15/108,383 US20160326698A1 (en) | 2013-12-25 | 2014-12-18 | Methods, Processes, and Compositions for Treating Pulp |
| EP14873734.9A EP3087223A4 (en) | 2013-12-25 | 2014-12-18 | Method for improving sizing efficiency of asa emulsion emulsified by a polymer emulsifier |
| JP2016539963A JP2017500454A (en) | 2013-12-25 | 2014-12-18 | Method for improving size efficiency of ASA emulsion emulsified with polymeric emulsifier |
| PCT/US2014/071139 WO2015100125A1 (en) | 2013-12-25 | 2014-12-18 | Method for improving sizing efficiency of asa emulsion emulsified by a polymer emulsifier |
| KR1020167020200A KR20160103067A (en) | 2013-12-25 | 2014-12-18 | Method for improving sizing efficiency of asa emulsion emulsified by a polymer emulsifier |
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| CA3026422A1 (en) | 2016-06-10 | 2017-12-14 | Ecolab Usa Inc. | Low molecular weight dry powder polymer for use as paper-making dry strength agent |
| WO2019028001A1 (en) | 2017-07-31 | 2019-02-07 | Ecolab Usa Inc. | Process for fast dissolution of powder comprising low molecular weight acrylamide-based polymer |
| US11214926B2 (en) | 2017-07-31 | 2022-01-04 | Ecolab Usa Inc. | Dry polymer application method |
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| CN108329425B (en) * | 2018-01-02 | 2020-03-17 | 江苏富淼科技股份有限公司 | Emulsifier for alkenyl succinic anhydride |
| CN108329421B (en) * | 2018-01-02 | 2020-04-03 | 江苏富淼科技股份有限公司 | Emulsifier for emulsifying alkenyl succinic anhydride |
| CN108425270A (en) * | 2018-03-30 | 2018-08-21 | 王建东 | A kind of preparation method of copy paper |
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| US20200354892A1 (en) * | 2019-05-06 | 2020-11-12 | Gpcp Ip Holdings Llc | Paper sheet mulches and methods of making the same |
| CN115075050B (en) * | 2021-03-10 | 2023-08-22 | 上海昶法新材料有限公司 | Cationic rosin size and preparation method thereof |
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| CN101611196B (en) * | 2007-01-26 | 2011-08-31 | 播磨化成株式会社 | Additive for papermaking and paper containing filler |
| JP2008248398A (en) * | 2007-03-29 | 2008-10-16 | Nippon Paper Industries Co Ltd | Method for producing paper, and paper |
| EP2145049A1 (en) * | 2007-05-09 | 2010-01-20 | Buckman Laboratories International, Inc. | Asa sizing emulsions for paper and paperboard |
| CN101942780B (en) * | 2010-09-15 | 2011-09-07 | 山东轻工业学院 | Method for preparing AKD emulsion sizing agent |
| US8840759B2 (en) * | 2010-11-02 | 2014-09-23 | Ecolab Usa Inc. | Method of using aldehyde-functionalized polymers to increase papermachine performance and enhance sizing |
| US8709207B2 (en) * | 2010-11-02 | 2014-04-29 | Nalco Company | Method of using aldehyde-functionalized polymers to increase papermachine performance and enhance sizing |
| CN102677543B (en) * | 2012-06-11 | 2014-03-12 | 岳阳林纸股份有限公司 | Method for fill feeding in papermaking |
-
2013
- 2013-12-25 CN CN201310728543.0A patent/CN104746388B/en not_active Expired - Fee Related
-
2014
- 2014-12-18 JP JP2016539963A patent/JP2017500454A/en active Pending
- 2014-12-18 MX MX2016008434A patent/MX2016008434A/en unknown
- 2014-12-18 US US15/108,383 patent/US20160326698A1/en not_active Abandoned
- 2014-12-18 CA CA2929377A patent/CA2929377A1/en not_active Abandoned
- 2014-12-18 EP EP14873734.9A patent/EP3087223A4/en not_active Withdrawn
- 2014-12-18 WO PCT/US2014/071139 patent/WO2015100125A1/en active Application Filing
- 2014-12-18 KR KR1020167020200A patent/KR20160103067A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP3087223A4 (en) | 2017-08-02 |
| CN104746388A (en) | 2015-07-01 |
| US20160326698A1 (en) | 2016-11-10 |
| JP2017500454A (en) | 2017-01-05 |
| KR20160103067A (en) | 2016-08-31 |
| WO2015100125A1 (en) | 2015-07-02 |
| EP3087223A1 (en) | 2016-11-02 |
| MX2016008434A (en) | 2016-10-14 |
| CA2929377A1 (en) | 2015-07-02 |
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