CN1621614A - Adhesive for paper making - Google Patents
Adhesive for paper making Download PDFInfo
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- CN1621614A CN1621614A CNA2004100917214A CN200410091721A CN1621614A CN 1621614 A CN1621614 A CN 1621614A CN A2004100917214 A CNA2004100917214 A CN A2004100917214A CN 200410091721 A CN200410091721 A CN 200410091721A CN 1621614 A CN1621614 A CN 1621614A
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- based copolymer
- acrylamide
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- adhesive
- paper making
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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
- D21H21/06—Paper forming aids
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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
- 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
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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
- 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
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
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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
- 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
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A papermaking viscous agent contains an acrylamide-based copolymer obtained by copolymerizing acrylamide with at least a vinyl-based monomer having an anionic group, and the acrylamide-based copolymer satisfies the following viscosity conditions. The viscosity of a table salt aqueous solution containing the acrylamide-based copolymer and 4 mass% table salt is higher than that of a pure water solution of the acrylamide-based copolymer having the same concentration as that in the table salt aqueous solution.
Description
Technical field
The present invention relates to adhesive for paper making.The application is willing to require priority 2003-398922 number to the spy in application on November 28th, 2003, quotes its content herein.
Background technology
When making Japan paper, thin paper, toilet paper, tissue,, since ancient times, carry out and use the paper process of disperseing binding agent in order to improve the dispersiveness of paper stock in water.This dispersion binding agent is called adhesive for paper making, natural goodses such as the extraction mucus of for example known sunset abelmoschus root.But the natural goods Sunset Abelmoschus Root has because of corruption causes rotten or quality is unstable, make shortcomings such as extracting operating difficulties, price instability, does not now industrially almost use.
In addition, as disperseing binding agent also can use synthetic macromolecular compound, for example use the acrylamide polymer of polyethylene glycol oxide, anionic property.
When making thin paper or tissue, in paper stock, add the cationic macromolecular compound of moistening paper power reinforcing agent etc. mostly, in addition, also add the cationic medicament of softener, dyestuff, pigment etc. sometimes.Therefore, when the adhesive for paper making that will contain the anionic property acrylamide polymer is used in the paper stock that contains cationic macromolecular compound or cationic medicament, because of the effect of electric charge, so the aggegation of paper stock fiber is the problem of difficulties in dispersion when having papermaking.In addition, though use at above-mentioned additive under the situation of fewer toilet paper, can use the acrylamide polymer of anionic property, but, produce simultaneously under the situation of toilet paper and thin paper using a kind of adhesive for paper making, or contain in mixing under the situation of plain boiled water of moistening paper power reinforcing agent, existence can not be used the problem of anionic property acrylamide polymer.
So, the general nonionic adhesive for paper making that does not have charge effect that uses.As concrete nonionic adhesive for paper making, for example can enumerate polyethylene glycol oxide is adhesive for paper making.Now, as the nonionic adhesive for paper making, most of occasion is used polyethylene glycol oxide.
Following motion is arranged in addition: with the method that the high polymer polyacrylamide of polyethylene glycol oxide and nonionic is used in combination, compare, obtain the paper (for example, with reference to Patent Document 1) that texture evenness is significantly improved with the occasion of using polyacrylamide individually.
Following motion is arranged in addition: the adhesive for paper making (for example, with reference to Patent Document 2) that constitutes by the copolymer that contains acrylamide monomer units and N-vinyl carboxylic acid amide monomer unit.
Following motion is arranged in addition: the viscosity that contains the common salt aqueous solution of acrylamide nonionic (being total to) polymer and salt, than the viscosity height that in pure water, contains with the pure water solution of acrylamide nonionic (being total to) polymer of above-mentioned common salt aqueous solution same concentrations, when using such acrylamide nonionic (being total to) polymer, use suppresses to add acrylamide nonionic (being total to) polymer of water decomposition and constitute adhesive for paper making (with reference to Patent Document 3).
[Patent Document 1] special public clear 52-15681 communique
[Patent Document 2] spy opens the 2000-290892 communique
[Patent Document 3] spy opens the 2003-253587 communique
Summary of the invention
But, add polyethylene glycol oxide as adhesive for paper making, owing to reduce, therefore have stably problems such as papermaking is not easy, price height because of dissolution conditions causes polyethylene glycol oxide generation viscosity.In addition, because of polyethylene glycol oxide can foam in the papermaking operation, so the volume of having to is added the defoamer that suppresses foaming.
In Patent Document 1 described invention, though the foaming of polyethylene glycol oxide reduces, but in making the such manufacturing that contains cationic macromolecular compound and cationic medicament of thin paper and tissue, compare, can not obtain full and uniform texture evenness with independent use polyethylene glycol oxide.In addition, because the molecular weight of polyacrylamide is low, so have the many shortcomings of addition of adhesive for paper making.
In Patent Document 2 described inventions, there is N-vinyl carboxylic acid acid amides price height, perhaps obtain the problems such as N-vinyl carboxylic acid acid amides difficulty of stabilised quality.In addition, compare with polyethylene glycol oxide, the strong tendency of paper stock fiber aggegation is arranged, Papermaking Performance is insufficient.
The dissolution velocity of Patent Document 3 described adhesive for paper making is slow, dissolving needs for a long time, therefore, if use, has the problem that papermaking fault etc. takes place because of dissolved matter not when dissolving is insufficient.
In addition, be that adhesive for paper making is compared with polyethylene glycol oxide, the polyacrylamide of nonionic is that the dissolution velocity of adhesive for paper making is slow.Therefore, with polyethylene glycol oxide be adhesive for paper making and polyacrylamide be adhesive for paper making mix to use the time, during than independent use polyethylene glycol oxide, mixing time is necessary to prolong.The mixing power that contains the aqueous solution of polyethylene glycol oxide in reinforcement, when perhaps prolonging mixing time, because the shearing force that the polyethylene glycol oxide part is caused by stirring can increase to more than necessity, so there is the problem that causes viscosity to reduce, has to be difficult to set the such shortcoming of dissolution conditions.
The present invention In view of the foregoing even what will do is to add cationic macromolecule or cationic medicament in the papermaking of for example thin paper, tissue etc., also can gives the paper stock fiber with dispersiveness, thereby can improve the stability and the production efficiency of papermaking.The object of the present invention is to provide the adhesive for paper making of inexpensive performance height and processing ease.
The inventor carries out all found that of research with keen determination for solving above-mentioned problem, by making extremely a spot of anionic property monomer and acrylamide copolymerization, can obtain the acrylamide based copolymer that dissolution velocity is increased sharply, in addition, use this acrylamide based copolymer, even with cationic macromolecule or cationic medicament and usefulness, the aggegation of paper stock fiber does not also take place or takes place hardly, can make adhesive for paper making, the numerical value of the viscosity of its aggegation degree and common salt aqueous solution and the viscosity of pure water solution is relevant, thereby has finished the present invention.
That is, adhesive for paper making of the present invention is characterized in that, contains the acrylamide based copolymer that the ethene base system monomer that has the anionic property base at least and acrylamide copolymerization form, and aforesaid propylene acid amides based copolymer satisfies following viscosities.
(viscosities)
Contain the viscosity of the common salt aqueous solution of acrylamide based copolymer and 4 quality % salt, than the viscosity height that contains with the pure water solution of the acrylamide based copolymer of above-mentioned common salt aqueous solution same concentrations.
Here, the amount with ethene base system monomer of anionic property base can be selected arbitrarily, with respect to the aforesaid propylene acid amides based copolymer of 100 moles of %, preferably has the above-mentioned ethene base system monomer of 0.1～1.5 mole of %.
Above-mentioned ethene base system monomer can be selected arbitrarily, preferably acrylic acid (salt) and/or acrylamide-2-methyl propane sulfonic acid (salt).
The viscosity 2000mPas or more than it preferably of 1 quality % pure water solution that contains the aforesaid propylene acid amides based copolymer of 1 quality % in the pure water.
In addition, adhesive for paper making of the present invention preferably also contains polyethylene glycol oxide.And preferred aforesaid propylene acid amides based copolymer is 20～75 quality %, and polyethylene glycol oxide is 25～80 quality %.
Adhesive for paper making of the present invention, even in the papermaking of thin paper and tissue etc., add cationic macromolecule or cationic medicament, also can give the paper stock fiber to open equal or the dispersiveness more than it of the described nonionic adhesive for paper making of 2003-253587 communique with the spy, improve with stability that makes papermaking and production efficiency, and dissolution velocity also improves sharp.Because of the raising of dissolution velocity, reduced when using by not dissolving the problem that part causes, can shorten dissolution time simultaneously.
In addition, when containing polyethylene glycol oxide in the adhesive for paper making of the present invention, deterioration Min. can be limited to, and the performance that paper stock is disperseed can be improved.
The specific embodiment
Below, explain the present invention.
Adhesive for paper making of the present invention contains water soluble propene's acid amides based copolymer.
As the acrylamide based copolymer, use contains the viscosity of the common salt aqueous solution of this acrylamide based copolymer and 4 quality % salt, than the high acrylamide copolymer of viscosity that contains in pure water with the pure water solution of the acrylamide based copolymer of above-mentioned common salt aqueous solution same concentrations.
In addition, the salt that uses is in this application represented with sodium chloride.And, in this application, the acrylamide based copolymer that has the ethene base system monomer of anionic property base and acrylamide copolymerization at least only sketched be the acrylamide based copolymer.
In the present invention, for example can use the high 100mPas of viscosity or its above acrylamide based copolymer of 1 quality % pure water solution of the acrylamide based copolymer that contains 1 quality % in the ratio of viscosities pure water of 1 quality % common salt aqueous solution of the acrylamide based copolymer that contains 1 quality % and 4 quality % salt.In addition, more preferably use high 150mPas or its above acrylamide based copolymer, further preferred high 200mPas or its above acrylamide based copolymer of using.
In addition, the what is called among the present invention " viscosity " be meant use Brookfield viscometer (rotor: No.2, winding number 6rpm), under measuring 25 ℃ of temperature, measure the value of adding to the acrylamide based copolymer in 4 quality % saline solutions or the pure water, stirring the solution that obtained in 3 hours.
The common salt aqueous solution by measuring acrylamide based copolymer as described above and the viscosity of pure water solution, according to following reason, can know what of anionic property base amount of acrylamide based copolymer, can obtain acrylamide based copolymer and cation constituent aggegation and cause the supposition substantially of the tendency of paper stock aggegation.
Promptly, when the acrylamide based copolymer has anionic property bases such as carboxyl, sulfonic group, when making such acrylamide based copolymer be dissolved in the pure water, intramolecular electrostatic repulsion because of the anionic property base, the elongation of acrylamide copolymer molecule, molecule is unfolded and is become big in the aqueous solution, and the viscosity of liquid rises.On the other hand, when being dissolved in the such electrolyte solution of saline solution, because the intramolecular electrostatic repulsion of intramolecular anionic property base is suppressed, so the rising of the liquid viscosity that is caused by the elongation of molecule also just is suppressed.On the other hand, the acrylamide based copolymer does not contain ionic when base, and electrostatic repulsion does not take place in pure water, just can not cause the rising of the viscosity when being dissolved in the pure water yet.Therefore, compare in the time of in the electrolytical aqueous solution such with the acrylamide based copolymer being dissolved in the saline solution that contains 4 quality %, the viscosity of pure water solution is just low.
The anionic property base that contains in the acrylamide based copolymer is many more, and electrostatic repulsion is also just big more, and the viscosity in pure water rises also just big more.
Usually, be used for the acrylamide based copolymer of adhesive for paper making,, still,, the slack-off tendency of dissolution velocity arranged on the other hand in the occasion of pure nonionic from preventing and this point of cationic substance reaction preferably do not have the anionic property base.
The inventor finds when studying the condition that satisfies this opposite rule, the dissolubility of acrylamide based copolymer is improved hastily by containing extremely a spot of ionic base, on the other hand, so long as the anionic property base of the amount of certain qualification, in the papermaking of reality system, just can not cause aggegation rapidly, and the numerical value of the viscosity of the degree of its aggegation and above-mentioned common salt aqueous solution and the viscosity in the pure water is relevant.That is,, when the viscosity of more above-mentioned common salt aqueous solution and the viscosity of above-mentioned pure water solution, when the viscosity of above-mentioned common salt aqueous solution is high, just can not cause that paper stock swashs acute aggegation for the acrylamide based copolymer.
Can obtain the high acrylamide based copolymer of viscosity of the above-mentioned pure water solution of ratio of viscosities of above-mentioned common salt aqueous solution, specifically, can obtain acrylamide based copolymer, have the acrylamide based copolymer of the ethene base system monomer of 0.1～1.5 mole of % with anionic property base with respect to 100 moles of %.
When having 0.1 mole of % of quantity not sufficient of ethene base system monomer of anionic property base, the dissolution velocity of adhesive for paper making to improve effect little, when surpassing 1.5 moles of %, the viscosity of pure water solution uprises, and in the aggegation that causes paper stock in the use-case that makes of reality.In addition, the amount of above-mentioned ethene base system monomer is more preferably at 1.0 moles of % or below it, most preferably at 0.8 mole of % or below it.In addition, lower limit is more preferably at 0.4 mole of % or more than it.
In addition, the application's acrylamide based copolymer also can contain nonionic ethene base system monomer that does not have the anionic property base as other etc.
As ethene base system monomer, can exemplify out acrylic acid, acrylamide-2-methyl propane sulfonic acid, methacrylic acid, maleic acid, fumaric acid, itaconicacid, citraconic acid and their salt thereof etc. with anionic property base.Can use in them a kind or more than or equal to 2 kinds.Acrylic acid (salt) and/or acrylamide-2-methyl propane sulfonic acid (salt) wherein, because of can obtaining in industrial cheapness and high-quality, so preferred, most preferably acrylic acid (salt) so long as contain the monomer of anionic property base, does not just limit this.
In addition, in the present invention, so-called acrylic acid (salt), acrylamide-2-methyl propane sulfonic acid (salt) are represented acrylic acid and/or acrylates, acrylamide-2-methyl propane sulfonic acid and/or acrylamide-2-methyl propane sulfonic acid salt respectively.
In addition, preferably the anionic property base is taken as the form of salt, does not have no relations even part is not neutralized also.Ethene base system monomer with such anionic property base is directed in the acrylamide based copolymer by copolymerization.In addition, use the method that adds water decomposition also the anionic property base can be imported in the acrylamide based copolymer by the acrylamide residue, but because narrow range few as the import volume of target, that allow, so, preferably import the anionic property base by copolymerization from doing one's utmost to suppress to add the water decomposition aspect.
The acrylamide based copolymer can be the product that acrylamide only becomes with the ethene base system monomer copolymerization that contains the anionic property base, also can be and and the copolymer of other non-ionic monomer.As above-mentioned non-ionic monomer, can enumerate Methacrylamide, N-vinyl acetamide, N-vinyl formamide, N-vinyl-N-methylacetamide, N-vinyl-N-methylformamide, N-methyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, methyl (methyl) acrylate, vinyl acetate, allyl alcohol, N-vinyl pyrrolidone, N-isopropylacrylamide, diacetone acrylamide, acrylonitrile etc.Also can use separately or more than or equal to 2 kinds of non-ionic monomers that use beyond the acrylamides.
Acrylamide with respect to the whole monomers that constitute copolymer 50 quality % or more than it preferably, is more preferably 70 quality % or more than it, especially preferably 90 quality % or more than it.The ratio of general acrylamide is high more, and the molecular weight of the polymer that obtains has the tendency of increase, can obtain the high acrylamide based copolymer of viscosity.
In addition, because the acrylamide based copolymer is to use as adhesive for paper making, so in the scope that dissolubility does not worsen, viscosity is high more good more, specifically, the viscosity of above-mentioned 1 quality % pure water solution is preferably at 2000mPas or more than it, more preferably at 2500mPas or more than it, further preferably at 3000mPas or more than it.In addition, contain the viscosity of common salt aqueous solution of aforesaid propylene acid amides based copolymer and 4 quality % salt also preferably at 2000mPas or more than it.
Adhesive for paper making of the present invention also can also contain acrylamide based copolymer composition in addition, for example can contain the polyethylene glycol oxide, the Sunset Abelmoschus Root that are generally used for the papermaking purposes alone or in combination more than or equal to 2 kinds and extract mucus etc.But in order to manifest effect of the present invention, the composition beyond the preferred acrylamide based copolymer is non-ionic substance.
Adhesive for paper making of the present invention also contains polyethylene glycol oxide, and preferred aforesaid propylene acid amides based copolymer is 20～75 quality %, and polyethylene glycol oxide is 25～80 quality %.
Because it is fast to be used for aforesaid propylene acid amides based copolymer dissolution velocity of the present invention, so when using as adhesive for paper making in that this acrylamide based copolymer and polyethylene glycol oxide are mixed, the difference of the dissolution velocity of acrylamide based copolymer and polyethylene glycol oxide is little, needn't excessively prolong the time that is used to dissolve.Therefore, can be with the degradation inhibiting of the polyethylene glycol oxide in when dissolving to Min..And when containing aforesaid propylene acid amides based copolymer and polyethylene glycol oxide, with independent use acrylamide based copolymer or use polyethylene glycol oxide to compare separately, the performance that can obtain paper stock is disperseed improves such multiplication effect.In addition, do not produce the problem of polyethylene glycol oxide foaming yet.
The containing ratio of polyethylene glycol oxide when 80 quality % or its are following, the cost step-down of adhesive for paper making.In addition, the containing ratio of polyethylene glycol oxide is when 25 quality % or its are above, and expression is big as the value of the adhesive for paper making suction pipe viscosity of the performance of the adhesive for paper making value more independent than polyethylene glycol oxide.That is, the adhesive for paper making with less amount just can carry out stable papermaking.
The lower limit of the containing ratio of polyethylene glycol oxide is more preferably 33 quality %, especially preferably 40 quality %.The upper limit of the containing ratio of polyethylene glycol oxide is more preferably 75 quality %, especially preferably 67 quality %.
In addition, the containing ratio of polyethylene glycol oxide and acrylamide based copolymer is more near 1 to 1, compare with the suction pipe viscosity of the suction pipe viscosity of the independent aqueous solution of polyethylene glycol oxide, the independent aqueous solution of acrylamide based copolymer or with the corresponding addition mean value of containing ratio in the adhesive for paper making of polyethylene glycol oxide and acrylamide based copolymer, the multiplication effect that improves the suction pipe viscosity of adhesive for paper making increases more.
The manufacture method of the acrylamide based copolymer that the present invention is used, just do not do special qualification as long as can access the high acrylamide based copolymer of viscosity of the ratio of viscosities pure water solution of common salt aqueous solution, can adopt known polymerizations such as aqueous solution polymerization, suspension polymerization.The general polymerization of acrylamide based copolymer is to use the aqueous solution polymerization of radical polymerization initiator or Photoepolymerizationinitiater initiater, especially preferably uses the aqueous solution polymerization of Photoepolymerizationinitiater initiater.
In aqueous solution polymerization, the concentration of the acrylamide in the aqueous solution (being designated hereinafter simply as " monomer concentration ") is 10～75 quality % normally, but the lower limit of monomer concentration is preferably at 15 quality % or more than it, more preferably at 20 quality % or more than it.On the other hand, the upper limit of monomer concentration is preferably at 50 quality % or below it.
In a single day monomer concentration uprises, the tendency that just has productivity ratio to improve, in case the monomer concentration step-down, the tendency that just has the dissolubility of the polymer that obtains to improve.
As common polymerization initiator, can use Photoepolymerizationinitiater initiater, azo series initiators, redox series initiators etc.
As Photoepolymerizationinitiater initiater, can use Alpha-hydroxy ketone, acylphosphanes oxygen compound etc.Example as these compounds; can enumerate azodiisobutyronitrile; 2,2'-Azobis(2,4-dimethylvaleronitrile); 2; 2 '-azo two (2-amidine propane) dihydrochloride; 2; 2 '-azo two [2-methyl-N-(2-hydroxyethyl)-propionamide]; 1-hydroxy-cyclohexyl phenyl ketone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone; two (2; 4; the 6-trimethylbenzoyl)-the phenyl phosphine oxygen; 2; 4,6-trimethylbenzoyl diphenyl phosphine oxygen; benzoin; benzoin ethyl ether; benzophenone etc.
The azo series initiators can be used as Photoepolymerizationinitiater initiater or thermal decomposition polymerization initiator, for example can enumerate azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2 '-azo two (2-amidine propane) dihydrochloride, 2,2 '-azo two [2-(2-benzimidazoline-2-yl) propane] dihydrochloride, 2,2 '-azo two [2-methyl-N-(2-hydroxyethyl)-propionamide] etc.
As the redox series initiators, can enumerate the combination of reductants such as peroxide such as persulfate or tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide and sulphite, bisulfites, thiosulfate, sodium formaldehyde sulphoxylate, ferrous sulfate, glucose, amine.
Polymerization initiator can be separately or more than or equal to more than 2 kinds and use.The addition of polymerization initiator is decided by the molecular weight of the polymer that obtains and the balance of polymerization time or remaining amount of monomer, and for example, the occasion of Photoepolymerizationinitiater initiater is with respect to whole monomers normally about 1～1000ppm.
Usually, because with Powdered use adhesive for paper making, so can be with the acrylamide based copolymer drying that obtains and powdered.Dry method is not made special regulation, but in order to prevent to add the deliquescent deterioration of water decomposition and acrylamide based copolymer, it is satisfied adopting the little drying means of thermic load.
Acrylamide based copolymer continuous drying and be ground into powder.Its particle diameter is not made special regulation.The spended time when dissolving because if particle diameter is excessive, particle diameter is little, and problem that powder flies up etc. then takes place, so can at random select as required.
In addition, acrylamide based copolymer of the present invention as long as in use do not go wrong, also can be used with any state, and can be used with Any shape or size.
The acrylamide based copolymer preferred dissolution that obtains is good.Herein, estimate dissolubility and be, add the acrylamide based copolymer of 0.1 quality % in 3kg water, stirs after 3 hours, the metal mesh filter of usefulness aperture 180 μ m is estimated with the quality of the aqueous gel matrix held back on the wire netting.Its amount is few more good more, and the aqueous gel matrix quality is at 20g or below it, preferably at 10g or below it, more preferably at 6g or below it usually.
The powder of the acrylamide based copolymer that the present invention obtains can be separately or is mixed polyethylene glycol oxide again and use as adhesive for paper making.
In adhesive for paper making of the present invention, when also containing polyethylene glycol oxide as described above, the mixing of polyethylene glycol oxide and acrylamide based copolymer can be pre-mixed each other with powder, supplies with powder respectively in the time of also can dissolving and mixes in dissolving tank.In addition, also can distinguish dissolving polyoxyethylene and acrylamide based copolymer and mix each other the aqueous solution.When mixing,, must mix for more even with aqueous solution state.
In addition, also can only constitute adhesive for paper making of the present invention by aforesaid propylene acid amides based copolymer.In the time of also can be with the papermaking of this adhesive for paper making and circulation other commercially available adhesive for paper making for example polyethylene glycol oxide be that adhesive for paper making is mixed with each other with powder or mixes in dissolving tank and be used for papermaking.As above,, also can not cause the deterioration of other adhesive for paper making, can bring into play its good performance even adhesive for paper making of the present invention mixes with other adhesive for paper making.
As mentioned above, because the viscosity height of the ratio of viscosities pure water solution of the above-mentioned common salt aqueous solution of the acrylamide based copolymer that adhesive for paper making of the present invention contains, so the monomer unit with anionic property base in the acrylamide based copolymer is few.
Consequently, can prevent the aggegation with cationic medicament and time spent paper stock fiber, good dispersion in the papermaking, the stability of papermaking and productivity ratio improve.In addition, because of the effect of a small amount of monomer unit that exists with anionic property base, have dissolution velocity fast, use and have the few advantage of insoluble matter easily, simultaneously.In addition, inexpensive, Papermaking Performance is good.
In addition, even adhesive for paper making of the present invention when also containing polyethylene glycol oxide, does not produce the problem of such in the past polyethylene glycol oxide deterioration yet.Owing to can also contain polyethylene glycol oxide, further tackify effect is arranged, and then improved the performance of paper stock fiber dispersion, so improved stability, the manufacturing efficient of papermaking, reduced the use amount of adhesive for paper making.
[embodiment]
By the following examples and comparative example, the present invention is described in further detail, but the present invention does not do any qualification to this.
(embodiment 1)
[modulation of acrylamide based copolymer]
Modulate acrylamide based copolymer in the following manner by the copolymer acrylates that constitute, that contain 0.4 mole of % of acrylamide and sodium acrylate.
To contain 50 quality % acrylamide aqueous solution 329.05g, 50 quality % acrylic acid aqueous solution 1.35g, 33 quality % sodium hydrate aqueous solution 1.14g, phosphorous acid disodium 50ppm (below, ppm represents the mass ratio with respect to whole amount of liquid) aqueous solution 413g join in 1 liter the conical flask modulation monomer solution.
Under lucifuge, with 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone 10ppm and 2,2 '-azo two (2-amidine propane) dihydrochloride 150ppm joins in the monomer solution, conical flask is put into 10 ℃ Water Tank with Temp.-controlled, keep intact and under condition of nitrogen gas, replace 30 minutes dissolved oxygens in the aqueous solution.
Prepare container as follows: on the periphery of the corrosion resistant plate of thickness 1mm, make the inner bottom surface of this corrosion resistant plate become the square of 200 * 200mm, and paste the rubber bar of 24mm on one side of section.Apply the transparent thin-film (stack membrane that constitutes by the polyvinylidene chloride of the polyethylene terephthalate of thickness 12 μ m and thickness 4 μ m) of 16 μ m in the inboard of this container, on this film, supply with the above-mentioned aqueous solution of polymerizable monomer.Be connected with the aqueous solution with above-mentioned transparent thin-film of the same race cover the aqueous solution above.By monomer solution constitute the layer thickness be 10mm.In addition, from supplying with before the monomer solution, jet 10 ℃ water and the inboard of cooling off corrosion resistant plate are with the adjustment to 10 of corrosion resistant plate ℃.In addition, until polymerization 10 ℃ the water of jetting continuously of ending always.
Above the container of supplying with above-mentioned monomer solution, 20W type fluorescence chemical lamp is set.Make exposure intensity be adjusted into 5W/m
2The fluorescence chemical lamp in advance on the aqueous solution surface irradiation 10 minutes.Then, make exposure intensity be adjusted into 10W/m
2The fluorescence chemical lamp on aqueous solution surface, shone 20 minutes.Make exposure intensity be adjusted into 60W/m thereafter,
2The fluorescence chemical lamp on aqueous solution surface, shone 30 minutes, finish polymerization, obtain containing the aqueous gel shape sheet of polymer.Peak temperature during polymerization that the aqueous solution or aqueous gel shape sheet reach is 55 ℃.
With the carefully disconnected aqueous gel shape sheet that obtains of pliers, with 60 ℃ air drier drying.Then, pulverize dry thing, obtain pulverous acrylamide based copolymer with Weir Lay (ウ イ レ) formula pulverizer.
[evaluation of the aqueous solution rerum natura of acrylamide based copolymer]
(1) mensuration of the viscosity of pure water solution
The viscosity of the acrylamide based copolymer pure water solution of the 1 quality % that mensuration obtains.
The pure water of 495g is packed in the beaker of 500ml, under stirring condition, add the above-mentioned acrylamide based copolymer that obtains of 5g, continuous stirring was carried out viscosimetric analysis by Brookfield viscometer after 3 hours under 25 ℃.The rotor that use this moment is No.2, and winding number is taken as 6rpm.
(2) mensuration of the viscosity of common salt aqueous solution
The viscosity of the acrylamide based copolymer common salt aqueous solution of the 1 quality % that mensuration obtains.
The pure water of 475g is packed in the beaker of 500ml, under stirring condition, add 5g acrylamide based copolymer, stirred 3 hours.Add 20g salt then, stir after 30 minutes, under 25 ℃, carry out viscosimetric analysis by Brookfield viscometer.The rotor that use this moment is same as described above.
(3) water does not dissolve the mensuration of part
2997g pipeline water is joined in the beaker of 3000ml, under stirring condition, add 3g acrylamide based copolymer, dissolve after 3 hours,, measure the quality of placing after 10 minutes with the metal mesh filter of aperture 180 μ m.Then, the quality of the wire netting that deduction is measured in advance obtains the quality that water does not dissolve part.
(4) mensuration of dissolution time
2997g pipeline water is joined in the beaker of 3000ml, under stirring condition, add 3g acrylamide based copolymer, behind the dissolving official hour, with the metal mesh filter of aperture 180 μ m, place after 10 minutes, measure the quality of aqueous gel shape thing residual on the wire netting.Quality measurement after the wire netting quality that deduction is measured in advance.At dissolution time is to carry out said determination under 30 minutes, 60 minutes, 90 minutes, 120 minutes, 150 minutes, 180 minutes, and the time that does not change quality in fact is taken as dissolution time.
[modulation of paper stock slurry]
As paper stock, use the NBKP (coniferous tree paper pulp) of beating degree 650ml CFS (Canadian standard freeness), be modulated into the paper pulp of 0.2 quality %.At this moment,, add the polyamide polymeric amine epichlorohydrin (エ ピ Network ロ Le ヒ De リ Application) that the moistening paper power of the cationic reinforcing agent of medicament is added in the conduct of 0.2 quality %, fully stir, obtain the paper stock slurry with respect to paper pulp.
[performance evaluation of adhesive for paper making]
For the adhesive for paper making that the powder by the acrylamide based copolymer that obtains with said method constitutes, assess performance.
For above-mentioned paper stock slurry, add with the adhesive for paper making aqueous solution of the concentration dissolving of 0.1 quality % making it reach 2ppm as the pure composition of adhesive for paper making, to the slurry solution after mixing, measure the compendency and the drainability of paper stock.
(1) paper stock compendency
Be added with the paper stock slurry solution of adhesive for paper making with shearing analyzer stirring after, visual judgement paper stock state.Evaluation criterion is as follows.In addition, following standard is in top good more (for example following ◎ represents most preferably) more.
◎: there is not compendency, no problem fully during use.
Zero: aggegation a little, no problem during use.
△: a small amount of aggegation, the texture evenness of papermaking goods may be disorderly.
*: aggegation can not be used for papermaking.
(2) drainability
The Bu Shi suction funnel that will be covered with the aperture 62mm of filter cloth is arranged on the top of the graduated cylinder of 500ml, and the paper stock slurry behind the interpolation mixing adhesive for paper making is poured in the Bu Shi suction funnel, measures the drainage amount.
Herein, the drainage amount is few more, and the dispersiveness of expression paper stock is good more, and is also few with the final necessary binding agent use amount of certain dispersiveness with regard to meaning for giving paper stock.
(3) the texture evenness of paper
With the paper stock slurry solution that has not directly added adhesive for paper making by filter etc., visual judgement is 13.0g/m by the quality that cylinder yankee paper machine (Yankee machine) papermaking obtains
2Paper.Evaluation criterion is as follows.
◎: evenly good.
Zero: good.
△: inhomogeneous.
*: bad, can not papermaking or the hole be empty paper.
(4) foaminess
In with the aqueous solution behind the concentration dissolving adhesive for paper making of 0.1 quality %, be blown into air, have or not foaming with visual valuation.Evaluation criterion is as follows.
Zero: do not foam.
△: foaming slightly, for papermaking must be added defoamer.
*: foaming is many, and the defoamer of volume must be arranged for papermaking.
Table 2 gathers the evaluation result of having represented adhesive for paper making.
(embodiment 2)
Except the sodium hydrate aqueous solution 1.70g modulation monomer solution of acrylic acid aqueous solution 2.02g, the 33 quality % of the acrylamide aqueous solution 328.38g, the 50 quality % that get 50 quality %, carry out polymerization with method similarly to Example 1, obtain containing the acrylamide based copolymer of 0.6 mole of % acrylates.The evaluation result of the aqueous solution rerum natura of acrylamide based copolymer is shown in table 1, and the evaluation result of the adhesive for paper making that will be made of the acrylamide based copolymer that obtains is shown in table 2 respectively.
(embodiment 3)
Acrylic acid aqueous solution 2.68g, the sodium hydrate aqueous solution 2.25g of 33 quality % except the acrylamide aqueous solution 327.72g, the 50 quality % that get 50 quality %, beyond the modulation monomer solution, carry out polymerization with method similarly to Example 1, obtain containing the acrylamide based copolymer of 0.8 mole of % acrylates.The evaluation result of the aqueous solution rerum natura of acrylamide based copolymer is shown in table 1, and the evaluation result of the adhesive for paper making that will be made of the acrylamide based copolymer that obtains is shown in table 2 respectively.
(embodiment 4)
Except the sodium hydrate aqueous solution 2.81g of acrylic acid aqueous solution 3.34g, the 33 quality % of the acrylamide aqueous solution 327.06g, the 50 quality % that get 50 quality %, carry out polymerization with method similarly to Example 1, obtain containing the acrylamide based copolymer of 1.0 moles of % acrylates.The evaluation result of the aqueous solution rerum natura of acrylamide based copolymer is shown in table 1, and the evaluation result of the adhesive for paper making that will be made of the acrylamide based copolymer that obtains is shown in table 2 respectively.
(embodiment 5)
Except the sodium hydrate aqueous solution 4.32g of acrylic acid aqueous solution 5.02g, the 33 quality % of the acrylamide aqueous solution 325.38g, the 50 quality % that get 50 quality %, carry out polymerization with method similarly to Example 1, obtain containing the acrylamide based copolymer of 1.5 moles of % acrylates.The evaluation result of the aqueous solution rerum natura of acrylamide based copolymer is shown in table 1, and the evaluation result of the adhesive for paper making that will be made of the acrylamide based copolymer that obtains is shown in table 2 respectively.
(comparative example 1)
Except the sodium hydrate aqueous solution 0g of acrylic acid aqueous solution 0g, the 33 quality % of the acrylamide aqueous solution 330.40g, the 50 quality % that get 50 quality %, carry out polymerization with method similarly to Example 1, obtain containing the acrylamide based copolymer of 0 mole of % acrylates.The evaluation result of the aqueous solution rerum natura of acrylamide based copolymer is shown in table 1, and the evaluation result of the adhesive for paper making that will be made of the acrylamide based copolymer that obtains is shown in table 2 respectively.
(comparative example 2)
Except the sodium hydrate aqueous solution 5.65g of acrylic acid aqueous solution 6.71g, the 33 quality % of the acrylamide aqueous solution 323.69g, the 50 quality % that get 50 quality %, carry out polymerization with method similarly to Example 1, obtain containing the acrylamide based copolymer of 2.0 moles of % acrylates.The evaluation result of the aqueous solution rerum natura of acrylamide based copolymer is shown in table 1, the evaluation result of adhesive for paper making is shown in table 2 respectively.
(comparative example 3)
Except the sodium hydrate aqueous solution 14.10g of acrylic acid aqueous solution 16.75g, the 33 quality % of the acrylamide aqueous solution 313.65g, the 50 quality % that get 50 quality %, carry out polymerization with method similarly to Example 1, obtain containing the acrylamide based copolymer of 5.0 moles of % acrylates.The evaluation result of the aqueous solution rerum natura of acrylamide based copolymer is shown in table 1, and the evaluation result of the adhesive for paper making that will be made of the acrylamide based copolymer that obtains is shown in table 2 respectively.
Table 1
| Acrylates content (mol%) | The aqueous solution rerum natura of acrylamide based copolymer | ||||
| Saline solution medium viscosity (mPas) | Pure water medium viscosity (mPas) | Do not dissolve part (g) | Dissolution time (sec) | ||
| Comparative example 1 | ??0 | ??3805 | ??3440 | ??0.0 | ??180＜ |
| Embodiment 1 | ??0.4 | ??3730 | ??3275 | ??0.0 | ??120 |
| Embodiment 2 | ??0.6 | ??3865 | ??3475 | ??0.0 | ??90 |
| Embodiment 3 | ??0.8 | ??3785 | ??3500 | ??0.0 | ??90 |
| Embodiment 4 | ??1.0 | ??3815 | ??3570 | ??0.0 | ??90 |
| Embodiment 5 | ??1.5 | ??3910 | ??3775 | ??0.0 | ??60 |
| Comparative example 2 | ??2.0 | ??3855 | ??3995 | ??0.2 | ??60 |
| Comparative example 3 | ??5.0 | ??3870 | ??4545 | ??0.5 | ??30 |
Table 2
| The compendency of paper stock | Drainability (ml) | The texture uniformity | Foaming | |
| Comparative example 1 | ??◎ | ??70 | ??◎ | ????◎ |
| Embodiment 1 | ??◎ | ??65 | ??◎ | ????◎ |
| Embodiment 2 | ??◎ | ??65 | ??◎ | ????◎ |
| Embodiment 3 | ??◎ | ??70 | ??◎ | ????◎ |
| Embodiment 4 | ??○ | ??75 | ??◎ | ????◎ |
| Embodiment 5 | ??○ | ??75 | ??○ | ????◎ |
| Comparative example 2 | ??△ | ??85 | ??△ | ????◎ |
| Comparative example 3 | ??× | ??100 | ??× | ????◎ |
Shown in above table 1, table 2, in embodiment 1～5, contain the acrylamide based copolymer that ethene base system monomer with anionic property base and acrylamide are copolymerized into, the viscosity of the common salt aqueous solution of the salt of this acrylamide based copolymer and 4 quality %, than the viscosity height that in pure water, contains with the pure water solution of the acrylamide based copolymer of above-mentioned common salt aqueous solution same concentrations, compendency, the drainability that can obtain paper stock are low, the texture evenness of paper is good, and the adhesive for paper making that dissolution time is short, operability is also good.
On the other hand, do not have the comparative example 1 of anionic property base fully, its Papermaking Performance is good, but dissolution velocity is slow, the dissolving spended time and be difficult to the operation.In addition, in comparative example 2,3, contain the viscosity height of ratio of viscosities common salt aqueous solution of pure water solution of the acrylamide based copolymer in anionic property Quito, the compendency of paper stock, drainability height, the texture evenness of paper is bad.
(embodiment 6～10 and comparative example 4)
The acrylamide based copolymer that uses among polyethylene glycol oxide and the embodiment 2 mixed with the cooperation ratio shown in the table 3 and as adhesive for paper making, these adhesive for paper making are carried out similarly to Example 1 evaluation.Polyethylene glycol oxide uses commercially available A Lukekusi SW (ア Le コ Star Network ス sw) (trade name, bright one-tenth chemistry society system).
Table 3
| Cooperate ratio | The compendency of paper stock | Drainability (ml) | Texture evenness | Foaming | ||
| ????PEO | ????PAM | |||||
| Embodiment 2 | ????0 | ????100 | ??◎ | ??65 | ??◎ | ????○ |
| Embodiment 6 | ????25 | ????75 | ??◎ | ??56 | ??◎ | ????○ |
| Embodiment 7 | ????40 | ????60 | ??◎ | ??53 | ??◎ | ????○ |
| Embodiment 8 | ????50 | ????50 | ??◎ | ??50 | ??◎ | ????○ |
| Embodiment 9 | ????60 | ????40 | ??◎ | ??50 | ??◎ | ????○ |
| Embodiment 10 | ????75 | ????25 | ??◎ | ??51 | ??◎ | ????△ |
| Comparative example 4 | ????100 | ????0 | ??◎ | ??53 | ??◎ | ????× |
PEO: polyethylene glycol oxide
Acrylamide based copolymer described in PAM: the embodiment 2
As shown in table 3, in embodiment 6～10, contain acrylamide based copolymer among polyethylene glycol oxide and the embodiment 2 adhesive for paper making be the adhesive for paper making that the texture evenness of the compendency of paper stock, drainability, paper is good, foaminess reduces.
On the other hand, the comparative example 4 that constitutes by polyethylene glycol oxide only, its foaminess is poor.
As known from the above, the adhesive for paper making of embodiment 1～10 is compared with the adhesive for paper making that is obtained by comparative example 1～4, under the condition with amount, can give paper stock with higher dispersiveness, can realize good papermaking, and operability is good.
The possibility of utilizing on the industry
Adhesive for paper making of the present invention, be suitable for and use on polyethylene glycol oxide, polyacrylamide, the industry of anionic property acrylamide polymer as the tackifier purposes, particularly, even between the production kind of the toilet paper that uses a kind of adhesive for paper making difficulty and thin paper etc. in the past, also can be general. That is, when making thin paper, tissue, toilet paper etc., can be used in to give the paper stock fiber with dispersiveness. Adhesive for paper making is provided, it is when Production Example such as thin paper, tissue etc., even add cationic macromolecule or cationic medicament, also can give the paper stock fiber with dispersiveness, can improve papermaking stability, make efficient, inexpensive performance height and processing ease.
Claims (8)
1. an adhesive for paper making is characterized in that,
Contain the acrylamide based copolymer that the ethene base system monomer that has the anionic property base at least and acrylamide copolymerization form,
Satisfy following viscosities: contain the viscosity of the common salt aqueous solution of described acrylamide based copolymer and 4 quality % salt, than the viscosity height that contains with the pure water solution of the described acrylamide based copolymer of described common salt aqueous solution same concentrations.
2. adhesive for paper making according to claim 1 is characterized in that, with respect to the described acrylamide based copolymer of 100 moles of %, has the described ethene base system monomer of 0.1～1.5 mole of %.
3. adhesive for paper making according to claim 1 is characterized in that, described ethene base system monomer is at least a kind of acrylic acid, acrylates, acrylamide-2-methyl propane sulfonic acid and acrylamide-2-methyl propane sulfonic acid salt.
4. adhesive for paper making according to claim 1 is characterized in that, the viscosity of 1 quality % pure water solution that contains the described acrylamide based copolymer of 1 quality % in the pure water is 2000mPas or more than it.
5. adhesive for paper making according to claim 1 is characterized in that, also contains polyethylene glycol oxide, and described acrylamide based copolymer is 20～75 quality %, and polyethylene glycol oxide is 25～80 quality %.
6. adhesive for paper making according to claim 1, it is characterized in that, the viscosity that contains 1 quality % common salt aqueous solution of 1 quality % acrylamide based copolymer and 4 quality % salt is than the high 100mPas of viscosity of 1 quality % pure water solution of the acrylamide based copolymer that contains 1 quality % in the pure water or more than it.
7. adhesive for paper making according to claim 1 is characterized in that, with respect to 50 quality % of the whole monomers that constitute described acrylamide based copolymer or be acrylamide more than it.
8. adhesive for paper making according to claim 1 is characterized in that, described anionic property base is a carboxyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003398922A JP4522692B2 (en) | 2003-11-28 | 2003-11-28 | Paper making adhesive |
| JP2003398922 | 2003-11-28 |
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| CN1621614A true CN1621614A (en) | 2005-06-01 |
| CN100404755C CN100404755C (en) | 2008-07-23 |
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| JP (1) | JP4522692B2 (en) |
| KR (1) | KR101123548B1 (en) |
| CN (1) | CN100404755C (en) |
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| AU2006307310B2 (en) * | 2005-10-25 | 2010-09-23 | Sumitomo Seika Chemicals Co., Ltd. | Papermaking method and papermaking system |
| JP5118998B2 (en) * | 2008-02-18 | 2013-01-16 | ダイヤニトリックス株式会社 | Paper making adhesive aqueous solution, method for producing the paper making adhesive aqueous solution, and paper making method |
| JPWO2011122405A1 (en) * | 2010-03-29 | 2013-07-08 | Ｍｔアクアポリマー株式会社 | Polyacrylamide-based papermaking adhesive and process for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5215681B1 (en) * | 1970-08-07 | 1977-05-02 | ||
| JPS5227808A (en) * | 1975-08-29 | 1977-03-02 | Nitto Chemical Industry Co Ltd | Screening method of nonwoven article |
| JPS63309501A (en) * | 1987-06-11 | 1988-12-16 | Mitsubishi Rayon Co Ltd | Production of water-soluble polymer |
| JP2602724B2 (en) * | 1989-04-21 | 1997-04-23 | 東亞合成株式会社 | Acrylamide copolymer |
| EP0848770B1 (en) * | 1995-09-06 | 2001-10-24 | The Procter & Gamble Company | Tissue paper product comprising adhesively joined plies |
| WO1998024974A1 (en) * | 1996-12-04 | 1998-06-11 | Kimberly-Clark Worldwide, Inc. | Method for making wet strength paper |
| JP2002212895A (en) * | 2000-11-13 | 2002-07-31 | Hymo Corp | Viscous agent for paper making, method for producing the same, and method for paper making |
| JP5299935B2 (en) * | 2001-05-17 | 2013-09-25 | 三菱レイヨン株式会社 | Nonionic or anionic water-soluble acrylamide polymer and process for producing the same |
| MX270652B (en) * | 2001-12-07 | 2009-10-06 | Hercules Inc | ANIOIC COPOLYMERS PREPARED IN A REVERSE EMULSION MATRIX AND ITS USE WHEN PREPARING CELLULOSIC FIBER COMPOSITIONS. |
| JP3820164B2 (en) * | 2002-02-25 | 2006-09-13 | ダイヤニトリックス株式会社 | Method for producing water-soluble vinyl polymer |
| JP3942920B2 (en) * | 2002-03-05 | 2007-07-11 | ダイヤニトリックス株式会社 | Nonionic paper making adhesive |
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| KR20050052363A (en) | 2005-06-02 |
| JP2005154978A (en) | 2005-06-16 |
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