CN101906734A - Additive for papermaking - Google Patents
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- CN101906734A CN101906734A CN200910164105XA CN200910164105A CN101906734A CN 101906734 A CN101906734 A CN 101906734A CN 200910164105X A CN200910164105X A CN 200910164105XA CN 200910164105 A CN200910164105 A CN 200910164105A CN 101906734 A CN101906734 A CN 101906734A
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Abstract
An object of the invention is to provide an additive for papermaking containing amphiprotic acrylamide polymer, which has excellent paper force improvement effect, excellent water filtration character and stuffing preserving rate. The additive for papermaking containing amphiprotic acrylamide polymer is characterized in that it has a specific relationship, the weight average molecular weight/average number molecular weight, intrinsic viscosity, gyroradius, solid content, viscosity coefficient, PH and light transmittance ratio are specific scope, and is obtained by performing polymerization using specific amount of specific monomer.
Description
Technical field
The present invention relates to additive for papermaking.Relate more specifically to contain the additive for papermaking of both sexes acrylamide polymer.
Background technology
Consider from the deterioration of raw material supplying situation and the angle of cost, the use of magma is restricted, and then for energy-conservation, efficent use of resources, utilize the necessity of old paper further to strengthen, and cause the closed circulation rate of plain boiled water to improve according to draining regulation etc., cause the amount of copying paper system inner salt and field trash to increase day by day.
Therefore, the paper power compared with the past additive for papermaking that improves the effect excellence and have excellent drainability and a filler retention becomes the target that people pursue always.
As the example of such additive for papermaking, the someone proposed in the presence of ethylene glycol etc., to make polymerization such as acrylamide monomer and the acrylamide polymer that obtains as additive for papermaking (for example with reference to patent documentation 1).In addition, the somebody has proposed to contain the paper grade (stock) chemicals (for example with reference to patent documentation 2) of the acrylamide polymer that has used particular monomers.
But, can't satisfy the requirement of additive for papermaking that paper power improves the effect excellence and has the retention rate of excellent drainability and filler.
[prior art document]
[patent documentation 1] Japanese kokai publication hei 08-269890 communique
[patent documentation 2] WO2003/070796 number
Summary of the invention
Problem of the present invention is to provide paper power to improve the effect excellence and has the excellent drainability and the additive for papermaking that contains the both sexes acrylamide polymer of filler retention.
The inventor furthers investigate in order to solve above-mentioned problem, found that the additive for papermaking that contains specific both sexes acrylamide polymer by use just can solve above-mentioned problem, thereby has finished the present invention.
That is the invention provides, as the means that solve above-mentioned problem:
＜1〉a kind of additive for papermaking that contains the both sexes acrylamide polymer is characterized in that, satisfies the full terms of following (1)～(9):
(1) weight average molecular weight is 500,000～10,000,000,
(2) weight average molecular weight is less than 1,000, and the quality of 000 composition is divided by weight average molecular weight 1,000, and the value of the quality of the composition more than 000 is below 5.0,
(3) weight average molecular weight is 1.3～10.0 divided by the value of number-average molecular weight,
(4) intrinsic viscosity is 0.3～3.0 (dl/g),
(5) radius of gyration (weight average root mean square radius) is 20～100 (nm),
(6) solid content is 10～35 (quality %),
(7) be 10 quality % at solid content, Brooker Fil moral (Brookfield) viscosity 25 ℃ the time is 30～30,000 (mPas),
(8) pH is 2～6,
(9) light transmittance at 0.1 quality % dilution of isoelectric point is 5～90 (%);
Described both sexes acrylamide polymer by adopt following composition (i)～(v) carrying out polymerization obtains:
(i) (methyl) acrylamide (a) 70～99 (mol%)
(ii) can with the vinyl monomer that contains carboxyl of (a) composition copolymerization and salt (b-1) thereof and use as required can with the vinyl monomer and the salt (b-2) 0.1～15 (mol%) thereof that contain the anionic property group beyond the carboxyl of (a) composition copolymerization
(iii) can with the vinyl monomer that contains the cationic group and the salt (c) 0.1～15 (mol%) thereof of (a) composition copolymerization
(iv) can with the cross-linkable monomer (d) 0.05～1.5 (mol%) of (a) composition copolymerization
(v) can with the chain transfer monomer (e) 0.05～3.0 (mol%) of (a) composition copolymerization.
＜2〉above-mentioned＜1〉additive for papermaking, cross-linkable monomer (d) is that N replaces the mix monomer that (methyl) acrylamide or N replace (methyl) acrylamide and have the multi-functional vinyl monomer of a plurality of vinyl.
＜3〉above-mentioned＜1〉or＜2 additive for papermaking, chain transfer monomer (e) is for having (methyl) allylic monomer.
The invention effect
The additive for papermaking that contains the both sexes acrylamide polymer of the present invention is compared with the known additive for papermaking that contains acrylamide polymer, even in the pH of the pulp owing to copying paper change, follow that the increase of the electrical conductivity of sneaking into, copying paper plain boiled water of the field trash that the deterioration of paper making raw material causes and the increase of microfibre etc. cause be difficult to improve under the situation of paper power, also can obtain excellent paper power and improve effect, and have excellent drainability and filler retention.
The specific embodiment
The additive for papermaking that contains the both sexes acrylamide polymer that uses among the present invention satisfies the full terms of following (1)～(9):
(1) weight average molecular weight is 500,000～10,000,000,
(2) weight average molecular weight is less than 1,000, and the quality of 000 composition is divided by weight average molecular weight 1,000, and the value of the quality of the composition more than 000 is below 5.0,
(3) weight average molecular weight is 1.3～10.0 divided by the value of number-average molecular weight,
(4) intrinsic viscosity is 0.3～3.0 (dl/g),
(5) radius of gyration is 20～100 (nm),
(6) solid content is 10～35 (quality %),
(7) be 10 quality % at solid content, the Brooker Fil moral viscosity 25 ℃ the time is 30～30,000 (mPas),
(8) pH is 2～6,
(9) light transmittance at 0.1 quality % dilution of isoelectric point is 5～90 (%);
And be necessary for contain by adopt following composition (i)～(v) carry out the additive for papermaking of the both sexes acrylamide polymer that polymerization obtains:
(i) (methyl) acrylamide (a) 70～99 (mol%)
(ii) can with the vinyl monomer that contains carboxyl of (a) composition copolymerization and salt (b-1) thereof and use as required can with the vinyl monomer and the salt (b-2) 0.1～15 (mol%) thereof that contain the anionic property group beyond the carboxyl of (a) composition copolymerization
(iii) can with the vinyl monomer that contains the cationic group and the salt (c) 0.1～15 (mol%) thereof of (a) composition copolymerization
(iv) can with the cross-linkable monomer (d) 0.05～1.5 (mol%) of (a) composition copolymerization
(v) can with the chain transfer monomer (e) 0.05～3.0 (mol%) of (a) composition copolymerization.
In addition, the value of (1) of the present invention～(5) is the value of measuring, obtaining with the GPC-MALS-VIS method, and the condition determination of GPC-MALS-VIS method is as described below.
The GPC main frame: Agilent Technologies makes LC1100
Splitter: TSKgel G6000PWXL, TSKgel G3000PWXL
Leacheate: N/5 phosphate buffer (pH6.8)
Flow velocity: 1.0ml/min
Detector 1: U.S. Wyatt Technology makes multi-angle light scattering detector DAWN
Detector 2: U.S. Wyatt Technology makes viscosity detector ViscoStar
These conditions are interrelated, can not play effect of the present invention when all not satisfying, and each composition is as described below.
The weight average molecular weight that contains the additive for papermaking of both sexes acrylamide polymer need be 500,000～10,000,000.Weight average molecular weight was less than 500,000 o'clock, and it is insufficient that paper power improves effect and drainability, retention rate improves effect; Greater than 10,000,000 o'clock, viscosity significantly increased, and operation is poor, the excessive aggegation of paper pulp fiber, and the paper quality that obtains is poor, and it is insufficient that paper power improves effect.
The weight average molecular weight of additive for papermaking that contains the both sexes acrylamide polymer is less than 1,000, and the quality of 000 composition is divided by weight average molecular weight 1,000, and the value of the quality of the composition more than 000 need be for below 5.0.Weight average molecular weight is less than 1,000, and the quality of 000 composition is divided by weight average molecular weight 1,000, and the value of the quality of the composition more than 000 was greater than 5 o'clock, and it is insufficient that paper power improves effect and drainability, retention rate improves effect.
The weight average molecular weight that contains the additive for papermaking of both sexes acrylamide polymer need be 1.3～10.0 divided by the value of number-average molecular weight.Greater than 10 o'clock, it is insufficient that paper power improves effect and drainability, retention rate improves effect divided by the value of number-average molecular weight for weight average molecular weight.
The intrinsic viscosity that contains the additive for papermaking of both sexes acrylamide polymer need be 0.3～3.0dl/g.This value was less than 0.3 o'clock, and it is insufficient that paper power improves effect, drainability, retention rate improves effect; This value was greater than 3.0 o'clock, and it is insufficient that paper power improves effect.
The radius of gyration (weight average root mean square radius) that contains the additive for papermaking of both sexes acrylamide polymer need be 20～100nm.Above-mentioned weight average root mean square radius (Root Mean Square Radius) is normally used＜S
2 1/2Represent.The radius of gyration is during less than 20nm, and it is insufficient that paper power improves effect and drainability, retention rate improves effect; During greater than 100nm, the excessive aggegation of paper pulp fiber, the paper quality that obtains is poor, and it is insufficient that paper power improves effect.
The solid content that contains the additive for papermaking of both sexes acrylamide polymer need be 10～35 quality %.Solid content is during less than 10 quality %, and shipment and delivery cost increases, and is uneconomical.
The additive for papermaking that contains the both sexes acrylamide polymer is that the Brooker Fil moral viscosity under the condition of 10 quality % and 25 ℃ need be 30～30,000mPas at solid content.At solid content is Brooker Fil moral viscosity under the condition of 10 quality % and 25 ℃ during less than 30mPas, and it is insufficient that paper power improves effect and drainability, retention rate improves effect; At solid content be Brooker Fil moral viscosity under the condition of 10 quality % and 25 ℃ greater than 30, during 000mPas, operation is poor, it is insufficient that paper power improves effect.
The pH that contains the additive for papermaking of both sexes acrylamide polymer need be 2～6.PH less than 2 or pH greater than 6 o'clock, storage stability reduces, it is insufficient that paper power improves effect and drainability after the long preservation, retention rate improves effect.
The light transmittance at 0.1 quality % dilution of isoelectric point that contains the additive for papermaking of both sexes acrylamide polymer need be 5～90%.At the light transmittance of 0.1 quality % dilution of isoelectric point less than 5% o'clock, the excessive aggegation of paper pulp fiber, the paper quality that obtains is poor, it is insufficient that paper power improves effect; , reduced to the set of paper pulp fiber greater than 90% o'clock at the light transmittance of 0.1 quality % dilution of isoelectric point, it is insufficient that paper power improves effect and drainability, retention rate improves effect.
In addition, must be to contain to adopt following composition (i)～(v) carry out polymerization and the both sexes acrylamide polymer that obtains is the additive for papermaking of feature.
(i) (methyl) acrylamide is acrylamide and/or Methacrylamide, needs to use 70～99mol%.When being less than 70mol%, it is insufficient that paper power improves effect; During greater than 99mol%, it is insufficient that drainability, retention rate improve effect.Be preferably 80～97mol%.
(ii) can with the vinyl monomer that contains carboxyl of (a) composition copolymerization and salt (b-1) thereof and use as required can be with the vinyl monomer that contains the anionic property group beyond the carboxyl of (a) composition copolymerization and salt (b-2) thereof, promptly have vinyl monomer ((b-1) and total (b-2)) needs use a 0.1～15mol% of anionic property group.When being less than 0.1mol%, do not satisfy the condition (9) in above-mentioned (1)～(9), drainability, that retention rate improves effect is insufficient; During greater than 15mol%, it is insufficient that paper power improves effect and drainability, retention rate improves effect.Be preferably 0.5～10mol%.
Can enumerate acrylic acid as above-mentioned monomer (its meaning is meant the polymerism vinyl monomer that contains carboxyl) and salt (b-1) thereof with carboxyl, methacrylic acid, cinnamic acid, crotonic acid, unsaturated monocarboxylic acids such as 2-acrylamide glycollic acid and 2-Methacrylamide glycollic acid, fumaric acid, maleic acid, itaconic acid, unsaturated dicarboxylic acid such as citraconic acid and muconic acid, aconitic acid, the 3-butene-1,2,3-tricarboxylic acids and 4-amylene-1,2, unsaturated tricarboxylic acids such as 4-tricarboxylic acids, 1-amylene-1,1,4, the 4-tetrabasic carboxylic acid, 4-amylene-1,2,3,4-tetrabasic carboxylic acid and 3-hexene-1,1,6, unsaturated tetrabasic carboxylic acid and salt (b-1) thereof such as 6-tetrabasic carboxylic acid.Has preferred unsaturated dicarboxylic acid in the monomer of carboxyl at these.
For having the monomer of carboxyl and an anionic property monomer the salt (b-1) thereof, can enumerate the monomer (its meaning is meant the polymerism vinyl monomer that contains phosphate) that contains sulfonic monomer (its meaning is meant and contains sulfonic polymerism vinyl monomer), contains phosphate as the vinyl monomer that uses as required and salt (b-2) thereof except above-mentioned with the anionic property group beyond the carboxyl.
Contain sulfonic monomer and can enumerate for example vinyl sulfonic acid, styrene sulfonic acid, allyl sulphonic acid, methallylsulfonic acid and 2-acrylamide-2-methyl propane sulfonic acid etc. as above-mentioned.
Can enumerate vinyl phosphonate and 1-phenyl vinyl phosphonic acids etc. as the above-mentioned monomer that contains phosphate.
In addition, can also use the monomer that contains carboxyl, contain sulfonic monomer and contain the salt of the monomer of phosphate.As the above-mentioned monomer that contains carboxyl, above-mentionedly contain sulfonic monomer or the above-mentioned salt that contains the monomer of phosphate can be enumerated alkali metal salt, alkali salt and ammonium salt etc.
These materials can be used alone, also can be also with more than two kinds.
(iii) can need be 0.1～15mol% with the vinyl monomer that contains the cationic group and the salt (c) thereof of (a) composition copolymerization.When being less than 0.1mol%, do not satisfy the condition (9) in above-mentioned (1)～(9), drainability, that retention rate improves effect is insufficient; During greater than 15mol%, it is insufficient that paper power improves effect.Be preferably 0.5～10mol%.
Can enumerate vinyl monomer, vinyl monomer, have the vinyl monomer of uncle's amino and have vinyl monomer of quaternary ammonium salt etc. as (c) cationic vinyl monomer with secondary amino group with primary amino radical.
Can enumerate allyl amine, methacrylic amine and their salt etc. as above-mentioned vinyl monomer with primary amino radical.Can enumerate inorganic acid salt and organic acid salts such as formates and acetate such as hydrochloride and sulfate as these salts.
Can enumerate diallylamine, DMAA and their salt etc. as above-mentioned vinyl monomer with secondary amino group.Can enumerate inorganic acid salt and organic acid salts such as formates and acetate such as hydrochloride and sulfate as these salts.
In addition, can enumerate the monomer that forms the hydrochlorate of secondary amine by any one reaction of above-mentioned vinyl monomer with primary amino radical such as allyl amine and methacrylic amine and dialkyl group sulfuric acid, chloropropylene oxides etc. such as halo aralkyls such as halogenated alkanes such as chloromethane and bromomethane, benzyl chloride and cylite, dimethyl sulfate and diethyl sulfuric acid as above-mentioned vinyl monomer with secondary amino group.
Can enumerate for example acrylic acid dimethylamino ethyl ester as the vinyl monomer of the above-mentioned uncle's of having amino, dimethylaminoethyl methacrylate, acrylic acid diethylamino ethyl ester, diethyl aminoethyl methacrylate, acrylic acid dimethylamino propyl ester, the amino propyl ester of dimethylaminoethyl acrylate methyl base, the amino alkane ester of (methyl) propenoic acid dialkyls such as acrylic acid diethylamino propyl ester and methacrylic acid diethylamino propyl ester class, the dimethylaminopropyl acrylamide, the dimethylaminopropyl Methacrylamide, dialkyl aminoalkyl (methyl) acrylic amides such as diethylamino propyl group acrylamide and diethylamino propyl methyl acid amides and their salt etc.Can enumerate inorganic acid salt and organic acid salts such as formates and acetate such as hydrochloride and sulfate as these salts.
In addition, can enumerate by diallylamine and DMAA etc. are above-mentioned as the vinyl monomer of the above-mentioned uncle's of having amino and have the vinyl monomer of secondary amino group and a monomer that any one reactions such as alkylsurfuric acid, chloropropylene oxide such as halo aralkyls such as halogenated alkanes such as chloromethane and bromomethane, benzyl chloride and cylite, dimethyl sulfate and diethyl sulfuric acid form the hydrochlorate of tertiary amine.
Can enumerate diallyldimethylammonium chloride, dimethyl-allyl alkyl dimethyl ammonium chloride, diallyl diethyl ammonium chloride and dimethyl-allyl diethyl ammonium chloride etc. as above-mentioned vinyl monomer with quaternary ammonium salt.
In addition, vinyl monomer and the quaternizing agent (4 Gradeization drug) that can enumerate by the above-mentioned uncle's of having amino as above-mentioned vinyl monomer with quaternary ammonium salt reacts the vinyl monomer that obtains.Can enumerate alkylsurfuric acids such as halo aralkyls such as halogenated alkanes such as chloromethane and bromomethane, benzyl chloride and cylite, dimethyl sulfate and diethyl sulfuric acid, chloropropylene oxide, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and glycidyl tri alkyl ammomium chloride etc. as above-mentioned quaternizing agent.Can enumerate for example 2-hydroxy-n as the vinyl monomer that contains the quaternary ammonium salt that obtains by the quaternizing agent reaction, N, N, N ', N '-pentamethyl-N '-[3-{ (1-oxygen-2-propenyl) amino } propyl group]-1,3-propane dichloride two ammoniums etc.
These vinyl monomers with primary amino radical, secondary amino group, uncle's amino or quaternary ammonium salt can be used alone, also can be also with more than two kinds.
(iv) can need to use 0.05～1.5mol% with the cross-linkable monomer (d) of (a) composition copolymerization.When being less than 0.05mol%, it is insufficient that paper power improves effect, drainability, retention rate improves effect; During greater than 1.5mol%, viscosity significantly increases, and operation is poor.Be preferably 0.1～1.0mol%.
Can enumerate multi-functional vinyl monomer with a plurality of vinyl, N as cross-linkable monomer (d) and replace (methyl) acrylamide, be monomer, water-soluble aziridine based compound, water-soluble multi-functional epoxy compound etc., wherein preferably use N replacement (methyl) acrylamide by having monomer, the silicon that vinyl and chain transfer point have a crosslinked action.These monomers can be used alone, also can be also with more than two kinds.
As above-mentioned multi-functional vinyl monomer with a plurality of vinyl, difunctionality vinyl monomers such as two (methyl) esters of acrylic acid, two (methyl) acrylic amide and divinyl ester class be can enumerate, trifunctional sex ethylene base monomer, four functionality vinyl monomers etc. also can be enumerated.
Can enumerate for example glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethylacrylate, triethylene glycol diacrylate, triethylene glycol dimethylacrylate, propylene glycol diacrylate, propylene glycol dimethylacrylate, glycerine diacrylate and glycerine dimethylacrylate etc. as above-mentioned two (methyl) esters of acrylic acid, these monomers can be used alone, also can be also with more than two kinds.
Can enumerate for example N as above-mentioned two (methyl) acrylic amides, N-methylene-bisacrylamide, N, N-di-2-ethylhexylphosphine oxide Methacrylamide, ethylenebis acrylamide, ethylenebis Methacrylamide, hexa-methylene bisacrylamide, the two Methacrylamides of hexa-methylene, N, N-bisacrylamide acetic acid, N, N-bisacrylamide methyl acetate, N, N-benzal bisacrylamide and N, two (acrylamide methylene) ureas of N-etc., these monomers can be used alone, also can be also with more than two kinds.
Can enumerate for example adipic acid divinyl ester, decanedioic acid divinyl ester, diallyl phthalate ester, diallyl maleate ester and diallyl succinate etc. as above-mentioned divinyl ester class, these monomers can be used alone, also can be also with more than two kinds.
Can enumerate for example allyl acrylate, allyl methacrylate, divinylbenzene and di isopropenylbenzene etc. as the difunctionality monomer beyond above-mentioned, these monomers can be used alone, also can be also with more than two kinds.
For example can enumerate 1 as above-mentioned trifunctional sex ethylene base monomer; 3; 5-triacryl six hydrogen-1; 3; 5-triazine (Triacrylformal), triallyl isocyanurate, N, N-diallyl acrylamide, N, N-diallyl Methacrylamide, triallylamine and triallyl pyromellitic acid ester etc.; these monomers can be used alone, also can be also with more than two kinds.
Can enumerate for example tetramethylol methane tetraacrylate, tetraallyl pyromellitic acid ester, N as above-mentioned four functionality vinyl monomers, N, N ', N '-tetraallyl-1,4-diaminobutane, tetraallyl amine (salt) and tetraallyl oxidative ethane etc., these monomers can be used alone, also can be also with more than two kinds.
Replace (methyl) acrylamide as above-mentioned N and can enumerate N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N-isopropyl (methyl) acrylamide, N-(2-hydroxyethyl) acrylamide and uncle's N-octyl group (methyl) acrylamide etc.
Can enumerate for example N hydroxymethyl acrylamide, glycidyl acrylate and glycidyl methacrylate etc. as above-mentioned by having the monomer that vinyl and chain transfer point have a crosslinked action, these monomers can be used alone, also can be also with more than two kinds.
As above-mentioned silicon is that monomer can be enumerated for example 3-acryloxy MTMS, 3-methacryloxy MTMS, 3-acryloxy propyl group dimethoxy-methyl silane, 3-methacryloxypropyl dimethoxy-methyl silane, 3-acryloxy propyl trimethoxy silicane, the 3-methacryloxypropyl trimethoxy silane, 3-acryloxy propyl group dimethyl dichlorosilane (DMCS), 3-methacryloxypropyl dimethyl dichlorosilane (DMCS), 3-acryloxy octadecyl triacetoxysilane, 3-methacryloxy octadecyl triacetoxysilane, 3-acryloxy-2,5-dimethyl hexyl diacetoxy methyl-monosilane, 3-methacryloxy-2,5-dimethyl hexyl diacetoxy methyl-monosilane and vinyl-dimethyl base acetoxylsilane etc., these monomers can be used alone, also can be also with more than two kinds.
Can enumerate for example tetramethylol methane-three-β-'-aziridino propionic ester, trimethylolpropane-three-β-'-aziridino propionic ester and 4 as above-mentioned water-soluble aziridine based compound, 4 '-two (ethylenimine carbonylamino) diphenyl methane etc., these monomers can be used alone, also can be also with more than two kinds.
For example can enumerate (gathering) ethylene glycol diglycidylether, (gathering) propylene glycol diglycidylether, (gathering) glycerin diglycidyl ether and (gathering) T 55 etc. as above-mentioned water-soluble multi-functional epoxy compound, these monomers can be used alone, also can be also with more than two kinds.
(v) can need to use 0.05～3.0mol% with the chain transfer monomer (e) of (a) composition copolymerization.When being less than 0.05mol%, viscosity significantly increases, and operation is poor, and it is insufficient that paper power improves effect; During greater than 3.0mol%, viscosity significantly reduces, and it is insufficient that paper power improves effect and drainability, retention rate improves effect.Be preferably 0.1～2.8mol%.
(e) can enumerate the monomer that has one or more carbon-to-carbon unsaturated bonds in molecule as the chain transfer monomer, for example (methyl) allyl alcohol and ester derivant thereof, (methyl) allyl amine, diallylamine, DMAA and amide derivatives, triallylamine, trimethyl allyl amine, (methyl) allyl sulphonic acid and salt thereof, allyl sulfide ethers, allyl sulfide alcohols.These monomers can be used alone, also can be also with more than two kinds.In addition, as known chain-transferring agent, can also and be used as the compound that has 1～a plurality of hydroxyls in the molecule alcohols such as isopropyl alcohol, butanols, ethylene glycol, glycerine are for example arranged, oligomer such as poly(ethylene oxide), polyglycereol and polymer class, carbohydrate and vitaminss such as glucose, ascorbic acid, sucrose; As the compound that in molecule, comprises one or more sulfydryls butanethiol, mercaptoethanol, thioglycolic acid and ester thereof are for example arranged, mercaptopropionic acid and ester thereof, thioglycerol, cysteamine and salt thereof etc.; Also has ortho phosphorous acid.
The preferred radical polymerization of polymerization about the additive for papermaking that contains the both sexes acrylamide polymer.Water, ethanol, acetone, dimethyl formamide, N-Methyl pyrrolidone, oxolane, 1,4-diox isopolarity solvent still it is desirable to make water as solvent in the same manner with the condition of manufacturing paper with pulp of paper as additive for papermaking applicable to polymer solvent.
Of the present inventionly to contain the additive for papermaking of both sexes acrylamide polymer and when carrying out polymerization, can use known in the past polymerization initiator in order to obtain.Can use persulfates such as sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate particularly, peroxide such as benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, bromate such as sodium bromate, potassium bromate, perborate such as sodium perborate, ammonium pertorate, percarbonate such as SODIUM PERCARBONATE, potassium percarbonate, percarbonic acid ammonium, superphosphates such as peroxophosphoric acid sodium, potassium superphosphate, ammonium superphosphate.At this moment, can be used singly or in combination of two or more, and can with reductant and with and as the redox system polymerization initiator.Can enumerate bisulfites such as sulphite, sodium hydrogensulfite such as sodium sulfite as reductant, N, N, N ', reducing sugar such as organic amine such as N '-tetramethylethylenediamine and aldose etc.And these reductants can be used alone or two or more kinds may be used.In addition, can also use azodiisobutyronitrile, 2,2 '-azo, two-2-amidine propane hydrochloride, 2,2 '-azo two-2,4 '-methyl pentane nitrile, 4, azos such as 4 '-azo, two-4-cyanopentanoic acid and salt thereof are polymerization initiator.
The synthetic of additive for papermaking that contains the both sexes acrylamide polymer of the present invention carries out according to the step of following [1], [2] or [3] record usually.
[1] as one-step polymerization, under atmosphere of inert gases such as nitrogen, add the monomer of mentioned component (a)～(e) and as the water (can and use organic solvent) of solvent to the reaction vessel of regulation, under agitation, under set point of temperature, add above-mentioned polymerization initiator and begin polymerization, thereby obtain the additive for papermaking that contains the both sexes acrylamide polymer of the present invention.
[2], suitably cut apart any one above monomer of the monomer of mentioned component (a)～(e) in advance as cutting apart the interpolation polymerization.Under the atmosphere of inert gases such as nitrogen, add any one above monomer of the described monomer of cutting apart good mentioned component (a)～(e) and as the water (can also use organic solvent) of solvent to the reaction vessel of regulation, under agitation, under set point of temperature, add above-mentioned polymerization initiator and begin polymerization, add monomer more than any one of the described monomer of cutting apart good remaining mentioned component (a)～(e) to reaction vessel in the polymerization way, thereby obtain the additive for papermaking that contains the both sexes acrylamide polymer of the present invention.
[3] as dripping polymerization, under atmosphere of inert gases such as nitrogen, to the water (can and use organic solvent) of the reaction vessel adding of stipulating as solvent, under agitation drip the monomer class of (a)～(e) and as the water (can and use organic solvent) of solvent, drip above-mentioned polymerization initiator simultaneously and begin polymerization, thereby obtain the additive for papermaking that contains the both sexes acrylamide polymer of the present invention.
The additive for papermaking that contains the both sexes acrylamide polymer of the present invention can be brought into play the retention rate that paper power improves effect and drainability, filler etc. and improves effect by adding to when making paper or paperboard in the pulp.Can use bleaching such as kraft pulp and sulfite pulp or bleached chemical paper pulps not as paper pulp raw material, bleaching such as ground wood pulp, mechanical pulp and thermo-mechanical pulp or any one of old paper paper pulp such as high yield paper pulp bleaching and old newspaper, outdated magazine, the old paper of corrugated paper and the old paper of deinking not.
When the additive for papermaking that contains the both sexes acrylamide polymer of the present invention is manufactured paper with pulp paper or paperboard in acidity to neutral and even alkaline zone, can use in any pH condition of manufacturing paper with pulp.
In addition, in order to represent the rerum natura of various paper type requirements, also can be to the additive for papermaking that contains the both sexes acrylamide polymer of the present invention and with other additive for papermaking.As and other additive for papermaking of usefulness for example can enumerate filler, dyestuff, aluminum sulfate, polyaluminium chloride, aluctyl, acidity and copy paper and copy paper with rosin series cementing agent, neutrality and fasten jelly, alkylene succinyl oxide with rosin series cementing agent, alkyl ketene dimer and fasten jelly, special modified rosin and fasten faintly acid, neutrality and alkalescence such as jelly and copy paper usefulness cementing agent, starch, wet strength agent, retention agent, filter aid, coagulating agent, leavening agent, the thick improving agent of paper and defoamer etc.These additives can be used alone or two or more kinds may be used.Can enumerate clay, talcum, titanium oxide, heavy or precipitated calcium carbonate, white carbon black etc. as filler.
In addition, in the additive for papermaking that contains the both sexes acrylamide polymer of the present invention, the two or more above-mentioned both sexes acrylamide polymer that with good grounds the present invention synthesizes be can contain, anionic property acrylamide polymer, Mannich modified propylene acid amides based polymer, Huffman modified propylene acid amides based polymer, starch and aluminum sulfate etc. also can be contained.In addition, additive for papermaking of the present invention can use separately, also can and use with anionic property acrylamide polymer, Mannich modified propylene acid amides based polymer, Huffman modified propylene acid amides based polymer, starch and aluminum sulfate etc.
The kind that contains the paper that additive for papermaking was suitable for of both sexes acrylamide polymer of the present invention is not particularly limited, and can enumerate various paper, paperboard.Kind about paper can be enumerated PPC paper, ink jet printing paper, laser stamping paper, tabulating paper, heat-transferring printing paper, the thermal photography body paper, record-paper and body paper thereof such as pressure sensitive recording body paper, art paper, cast-coated paper, bodystock papers such as last matter coated paper, brown paper, package papers such as pure white coil paper, matter paper on other, middle matter paper, Notepaper, book printing paper, various printing paper, newspaper paper, various paper such as high bulking paper (Western paper), sanitary papers such as toilet paper, milk box body paper, liquid containers such as cupstock body paper, take a picture with print paper body paper, Manila board, white board, paper container boards such as cardboard, boxboard, corrugating medium, paper tube base paper, paperboards such as plasterboard body paper.
[embodiment]
Enumerate Production Example and embodiment below and specifically describe effect of the present invention, but the present invention is not limited in these examples.In addition, when not having specified otherwise, following " part " and " % " are meant parts by mass and quality %.
Embodiment 1
In the 1 liter of four-hole boiling flask that has mixer, thermometer, reflux condensing tube and nitrogen ingress pipe, add 483 parts of entry, 267.06 parts of 50% acrylamide aqueous solutions, 1.57 parts of dimethylaminoethyl methacrylate, 18.67 parts of the quaternized thing aqueous solution of 76% dimethylaminoethyl methacrylate benzyl chloride, 5.2 parts of itaconic acids, N, 1.19 parts of N-DMAAs, 1.49 parts in methallylsulfonic acid sodium, then add 1.8 parts of 30% aqueous sulfuric acids, making pH is 3.0, is warming up to 60 ℃ under nitrogen atmosphere.Then, add 4.56 parts of 5% ammonium persulfate aqueous solutions as polymerization initiator, the beginning polymerization is warming up to 90 ℃, and is incubated under nitrogen atmosphere.Polymerization begins to append after 1 hour 9.12 parts of 5% ammonium persulfate aqueous solutions, and polymerization begins to be cooled to room temperature after 2 hours, stops polymerization.The solid content of the additive for papermaking that contains the both sexes acrylamide polymer that obtains is that 20.2%, 10% dilution viscosity (25 ℃, use Brooker Fil moral rotation viscometer) is that 350mPas, pH are 4.1.The proterties of the additive for papermaking that obtains is illustrated in the table 2.
Embodiment 2,3
As shown in table 1, in changing embodiment 1, the kind of the composition of (a)～(e), the amount, carry out operation similarly to Example 1, obtain additive for papermaking.The proterties of the additive for papermaking that obtains is illustrated in the table 2.
Embodiment 4
To having mixer, thermometer, add 835.94 parts of entry in 1 liter of four-hole boiling flask of reflux condensing tube and nitrogen ingress pipe, 77.72 parts of Methacrylamides, 7.86 parts of dimethylaminoethyl methacrylate, 64.7% 2-hydroxy-n, N, N, N ', N '-pentamethyl-N '-[3-{ (1-oxygen-2-propenyl) amino } propyl group]-1,5.32 parts of 3-propane dichloride two aqueous ammoniums, 2.6 parts of itaconic acids, 0.49 part of maleic anhydride, N, 0.07 part of N-DMAA, 0.02 part of methylene-bisacrylamide, 0.16 part in methallylsulfonic acid sodium, then add 8.0 parts of 30% aqueous sulfuric acids, making pH is 3.0, is warming up to 60 ℃ under nitrogen atmosphere.Then, add 2.28 parts of 5% ammonium persulfate aqueous solutions as polymerization initiator, the beginning polymerization is warming up to 90 ℃, and is incubated under nitrogen atmosphere.Polymerization begins to append after 1 hour 4.56 parts of 5% ammonium persulfate aqueous solutions, and polymerization begins to be cooled to room temperature after 2 hours, stops polymerization.The solid content of the additive for papermaking that contains the both sexes acrylamide polymer that obtains is that 10.1%, 10% dilution viscosity (25 ℃, use Brooker Fil moral rotation viscometer) is that 10000mPas, pH are 3.6.The proterties of the additive for papermaking that obtains is illustrated in the table 2.
Embodiment 5
In the 1 liter of four-hole boiling flask that has mixer, thermometer, reflux condensing tube and nitrogen ingress pipe, add 380.1 parts of entry, 377.01 parts of 50% acrylamide aqueous solutions, 21.3 parts of the quaternized thing aqueous solution of 76% acrylic acid dimethylamino ethyl ester benzyl chloride, 33.61 parts of the quaternized thing aqueous solution of 76% dimethylaminoethyl methacrylate benzyl chloride, 7.81 parts of itaconic acids, 2.7 parts of 80% acrylic acid aqueous solutions, N, 3.82 parts of N-diethyl acrylamides, 12.34 parts in methallylsulfonic acid sodium, making pH is 3.0, is warming up to 60 ℃ under nitrogen atmosphere.Then, add 6.84 parts of 5% ammonium persulfate aqueous solutions as polymerization initiator, the beginning polymerization is warming up to 90 ℃, and is incubated under nitrogen atmosphere.Polymerization begins to append after 1 hour 13.7 parts of 5% ammonium persulfate aqueous solutions, and polymerization begins to be cooled to room temperature after 2 hours, stops polymerization.The solid content of the additive for papermaking that contains the both sexes acrylamide polymer that obtains is that 30.3%, 10% dilution viscosity (25 ℃, use Brooker Fil moral rotation viscometer) is that 60mPas, pH are 4.1.The proterties of the additive for papermaking that obtains is illustrated in the table 2.
Embodiment 6
To having mixer; thermometer; add 495.3 parts of entry in 1 liter of four-hole boiling flask of reflux condensing tube and nitrogen ingress pipe; 264.16 parts of 50% acrylamide aqueous solutions; 3.14 parts of dimethylaminoethyl methacrylate; 22.41 parts of the quaternized thing aqueous solution of 76% dimethylaminoethyl methacrylate benzyl chloride; 2.6 parts of itaconic acids; N; 0.4 part of N-DMAA; 1; 3; 5-triacryl six hydrogen-1; 3; 0.05 part of 5-triazine; 1.82 parts of 75% dimethyl hydroxyl ethyl-methyl allyl ammonium chlorides; then add 3.0 parts of 30% aqueous sulfuric acids; making pH is 3.0, is warming up to 60 ℃ under nitrogen atmosphere.Then, add 4.56 parts of 5% ammonium persulfate aqueous solutions as polymerization initiator, the beginning polymerization is warming up to 90 ℃ under nitrogen atmosphere, adds 3.9 parts of itaconic acids in the moment that reaches 75 ℃ in the way of heating up.Polymerization begins to append after 1 hour 9.12 parts of 5% ammonium persulfate aqueous solutions, and polymerization begins to be cooled to room temperature after 2 hours, stops polymerization.The solid content of the additive for papermaking that contains the both sexes acrylamide polymer that obtains is that 20.1%, 10% dilution viscosity (25 ℃, use Brooker Fil moral rotation viscometer) is that 340mPas, pH are 3.5.The proterties of the additive for papermaking that obtains is illustrated in the table 2.
Embodiment 7
In the 1 liter of four-hole boiling flask that has mixer, thermometer, reflux condensing tube and nitrogen ingress pipe, add 433.62 parts of entry, 263.96 parts of 50% acrylamide aqueous solutions, 6.29 parts of dimethylaminoethyl methacrylate, 5.98 parts of itaconic acids, 0.46 part of fumaric acid, N, 0.51 part of N-diethyl acrylamide, 0.05 part of triallyl isocyanurate, 1.11 parts in methallylsulfonic acid sodium, 0.51 part of 75% triethyl group methacrylic chlorination ammonium, then add 6.0 parts of 30% aqueous sulfuric acids, making pH is 3.0, is warming up to 60 ℃ under nitrogen atmosphere.Then, add 4.56 parts of 5% ammonium persulfate aqueous solutions as polymerization initiator, the beginning polymerization is warming up to 90 ℃ under nitrogen atmosphere, add 14.2 parts of the quaternized things of 76% acrylic acid dimethylamino ethyl ester benzyl chloride in the moment that reaches 90 ℃.Polymerization begins to append after 1 hour 9.12 parts of 5% ammonium persulfate aqueous solutions, and the reaction beginning was cooled to room temperature after 2 hours, stopped polymerization.The solid content of the additive for papermaking that contains the both sexes acrylamide polymer that obtains is that 20.5%, 10% dilution viscosity (25 ℃, use Brooker Fil moral rotation viscometer) is that 360mPas, pH are 3.8.The proterties of the additive for papermaking that obtains is illustrated in the table 2.
Comparative example 1～4
As shown in table 1, in changing embodiment 1, the kind of the composition of (a)～(e), the amount, carry out operation similarly to Example 1, obtain the aqueous solution of copolymer.The proterties of the aqueous solution of the copolymer that obtains is illustrated in the table 2.
Table 1
The corresponding following material of abbreviation in the table 1.
AAm: acrylamide
MAAm: Methacrylamide
AA: acrylic acid
IA: itaconic acid
MA: maleic anhydride
FA: fumaric acid
VPA: vinyl phosphonate
DMAA:N, the N-DMAA
DEAA:N, N-diethyl acrylamide
HEAA:N-(2-hydroxyethyl) acrylamide
MBAAm: methylene-bisacrylamide
TAF:1,3,5-triacryl six hydrogen-1,3,5-triazines
TAIC: triallyl isocyanurate
SMAS: methallylsulfonic acid sodium
HEMAC: dimethyl hydroxyl ethyl-methyl allyl ammonium chloride
TEMAC: triethyl group methacrylic chlorination ammonium
DM: dimethylaminoethyl methacrylate
DMBz: the quaternized thing of dimethylaminoethyl methacrylate benzyl chloride
DABz: the quaternized thing of acrylic acid dimethylamino ethyl ester benzyl chloride
DPA: dimethylaminopropyl acrylamide
The BQA:2-hydroxy-n, N, N, N ', N '-pentamethyl-N '-[3-{ (1-oxygen-2-propenyl) amino } propyl group]-1,3-propane dichloride two ammoniums
Do not have: the monomer on this hurdle is not used in expression.
/: the time of representing to stagger is added monomer in reaction vessel.
Table 2
| (1) | (2) | (3) | (4) | (5) | (6) | (7) | (8) | (9) | |
| Embodiment 1 | 300 | 1.36 | 6.25 | 1.22 | 64 | 20.2 | 350 | 4.1 | 70 |
| Embodiment 2 | 430 | 0.96 | 8.94 | 1.43 | 69 | 20.1 | 380 | 3.1 | 80 |
| Embodiment 3 | 120 | 1.54 | 2.87 | 1.21 | 44 | 20.6 | 330 | 4.2 | 13 |
| Embodiment 4 | 240 | 1.12 | 3.53 | 2.10 | 63 | 10.1 | 10000 | 3.6 | 60 |
| Embodiment 5 | 200 | 1.02 | 3.01 | 0.70 | 46 | 30.3 | 60 | 4.1 | 85 |
| Embodiment 6 | 190 | 1.51 | 4.88 | 1.13 | 54 | 20.1 | 340 | 3.5 | 9 |
| Embodiment 7 | 350 | 1.13 | 4.65 | 1.41 | 63 | 20.5 | 360 | 3.8 | 10 |
| Comparative example 1 | 60 | 4.62 | 2.35 | 1.10 | 34 | 20.4 | 280 | 3.5 | 100 |
| Comparative example 2 | 230 | 1.10 | 7.01 | 1.25 | 69 | 20.2 | 300 | 4.9 | 100 |
| Comparative example 3 | 40 | 16.8 | 2.50 | 0.80 | 31 | 20.0 | 75 | 3.9 | 80 |
| Comparative example 4 | 210 | 1.37 | 4.51 | 1.22 | 60 | 20.2 | 320 | 4.0 | 65 |
The meaning of (1) in the table 2～(9) is as follows:
(1): weight average molecular weight (ten thousand)
(2): weight average molecular weight is less than 1,000, and the quality of 000 composition is divided by weight average molecular weight 1,000, the value of the quality of the composition more than 000
(3): weight average molecular weight is divided by the value of number-average molecular weight
(4): intrinsic viscosity (dl/g)
(5): the radius of gyration (nm)
(6) solid content (quality %)
(7) be 10 quality % at solid content, the Brooker Fil moral viscosity (mPas) 25 ℃ the time
(8)pH
(9) at the light transmittance (%) of 0.1 quality % dilution of isoelectric point
Estimate by (paperboard)
To the beating degree that obtains by old corrugated paper (Canadian Standard Freeness) be adjusted into 350, pulp density is to add 1.5% aluminum sulfate in 2.4% the pulp, then adds the additive for papermaking that obtains in 0.2% embodiment 1～7, the comparative example 1～4.And, the situation that does not have to add the additive for papermaking that contains the both sexes acrylamide polymer is set at comparative example 5.After stirring this pulp, by the water of pH6.0 pulp density is diluted to 0.8% after, with The Noble ﹠amp; Wood company makes handshcet former and copies paper, and the extruding back 100 ℃ of 120 seconds of drying, obtains grammes per square metre 120g/m with cylindrical drier
2Paper.The evaluation result of the paper that obtains is illustrated in the table 3.
Evaluation method
Than pop strength: carry out according to JIS P 8112.
Than compressing intensity: carry out according to JIS P 8126.
DDT: " dynamic drainage instrument (Dynamic Drainage Jar) " same device of the 46th page of record of employing and Tappi, the 56th volume No. 10 (1973), pulp (concentration 0.8%) 500mL after the dilution is injected the jar of diameter 7.5cm, when stirring, opens the rotating speed with 600rpm the bottom valve, filter with 100 purpose wire nettings, mensuration reaches the time of certain amount of filtrate, and this value can be used for the evaluation of drainability.Measure the time that amount of filtrate reaches 150g.The more little expression drainability of numerical value is good more.
Estimate by (Western paper)
To the beating degree (Canadian Standard Freeness) with the mixed pulp of bleached hardwood kraft pulp (LBKP)/coniferous tree bleached kraft pulp (NBKP)=8/2 be adjusted into 400, pulp density is to add calcium carbonate (Tama Pearl 121: Ao Duomo industry (strain) is made) 12%, cationization tapioca CATO308 (national starch chemical company make) 0.5%, aluminum sulfate 0.5% in 2.4% the pulp successively, then adds the additive for papermaking that obtains in 0.2% the foregoing description 1～7, the comparative example 1～4.And, the situation that does not have to add the additive for papermaking that contains the both sexes acrylamide polymer is set at comparative example 5.After stirring this pulp, with pulp concentration dilution to 0.8%, and then under agitation add 0.01% retention agent RD7153 (starlight PMC (strain) manufacturing), use The Noble﹠amp by the water of pH8.0; Wood company makes handshcet former and copies paper, and the extruding back 110 ℃ of 90 seconds of drying, obtains grammes per square metre 80g/m with cylindrical drier
2Paper.The evaluation result of the paper that obtains is illustrated in the table 3.
Evaluation method
Internal bond strength: carry out according to JAPAN TAPPI 18-2.
Ash content rate: carry out according to JIS P 8128.
DDT: measure by said method.
Table 3
Claims (3)
1. an additive for papermaking that contains the both sexes acrylamide polymer is characterized in that, satisfies the full terms of following (1)～(9):
(1) weight average molecular weight is 500,000～10,000,000,
(2) weight average molecular weight is less than 1,000, and the quality of 000 composition is divided by weight average molecular weight 1,000, and the value of the quality of the composition more than 000 is below 5.0,
(3) weight average molecular weight is 1.3～10.0 divided by the value of number-average molecular weight,
(4) intrinsic viscosity is 0.3～3.0dl/g,
(5) radius of gyration is 20～100nm,
(6) solid content is 10～35 quality %,
(7) be 10 quality % at solid content, the Brooker Fil moral viscosity 25 ℃ the time is 30～30,000mPas,
(8) pH is 2～6,
(9) light transmittance at 0.1 quality % dilution of isoelectric point is 5～90%;
Described both sexes acrylamide polymer by with following composition (i)～(v) polymerization obtains:
(i) (methyl) acrylamide (a) 70～99mol%,
(ii) can with the vinyl monomer that contains carboxyl of (a) composition copolymerization and salt (b-1) thereof and use as required can with the vinyl monomer and salt (b-2) 0.1～15mol% thereof that contain the anionic property group beyond the carboxyl of (a) composition copolymerization,
(iii) can with the vinyl monomer that contains the cationic group and salt (c) 0.1～15mol% thereof of (a) composition copolymerization,
(iv) can with cross-linkable monomer (d) 0.05～1.5mol% of (a) composition copolymerization,
(v) can with chain transfer monomer (e) 0.05～3.0mol% of (a) composition copolymerization.
2. additive for papermaking according to claim 1 is characterized in that, cross-linkable monomer (d) replaces (methyl) acrylamide for N or N replaces (methyl) acrylamide and the mix monomer with multi-functional vinyl monomer of a plurality of vinyl.
3. additive for papermaking according to claim 1 and 2 is characterized in that, chain transfer monomer (e) is for having (methyl) allylic monomer.
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| CN103911902A (en) * | 2013-01-09 | 2014-07-09 | 荒川化学工业株式会社 | Toilet paper additive, toilet paper making method using toilet paper additive and toilet paper |
| CN104032621A (en) * | 2013-03-06 | 2014-09-10 | 荒川化学工业株式会社 | Paper Strengthening Agent, Manufacturing Method For The Same, And Paper |
| CN105463935A (en) * | 2014-09-30 | 2016-04-06 | 荒川化学工业株式会社 | Papermaking additive and paper obtained by using same |
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