CN1958947A - Method of manufacturing paper - Google Patents
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- CN1958947A CN1958947A CNA2006101379970A CN200610137997A CN1958947A CN 1958947 A CN1958947 A CN 1958947A CN A2006101379970 A CNA2006101379970 A CN A2006101379970A CN 200610137997 A CN200610137997 A CN 200610137997A CN 1958947 A CN1958947 A CN 1958947A
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Abstract
A method for paper-making is provided, wherein the balance of texture and drainability can be easily obtained, so that the paper intension can be enhanced and the dosage of paper strength agent can be reduced, the water removing performance is improved, and then the operation performance can be improved. The method is characterized in that: a nonionic polyacrylamides paper strength agent(A) and cationic polyacrylamides paper strength agent (B) having a larger difference of beating degree than that of nonionic polyacrylamides paper strength agent(A) measured according to JIS P 8121 before or after adding the paper strength agent, or anionic polyacrylamides paper strength agent (C) are used for paper-making.
Description
Technical field
The present invention relates to papermaking process.In more detail, relate to the papermaking process that has used polyacrylamide paper power reinforcing agent.
Background technology
Always when papermaking, all used paper power reinforcing agent with intensity, and considered that from aspects such as performances the paper power reinforcing agent of polyacrylamide has obtained using widely in order to give paper.Usually, in the occasion of using paper power reinforcing agent, be disposable or join among the paper stock a kind of paper power reinforcing agent in batches.Yet, with a kind of occasion of paper power reinforcing agent, be difficult to obtain the balance of quality and drainability only, therefore, have to use a lot of paper power reinforcing agents.
Thus, in order to solve such problem, proposed to use the method for several paper power reinforcing agents.For example, proposed to use the papermaking process of additive, this additive contains the polyacrylamide base polymer and cationic group and the polymer (with reference to patent documentation 1) different with described polyacrylamide base polymer is arranged, and then, proposed to use the polyacrylamide base polymer again, papermaking process (with reference to patent documentation 2) that cationic group and the polymer different with described polyacrylamide base polymer and aluminium compound copy paper etc. has been arranged.But, all these methods all are difficult to obtain the balance of quality and drainability.At this, the inventor has proposed to realize easily the papermaking process (with reference to patent documentation 3) of the balance of quality and drainability.Method thus though realize the balance of quality and drainability easily, if fine texture makes removing the water-based variation, take place to remove water-based variation and disconnected paper easily when copying paper sometimes, is brought harmful effect to transaction capabilities.
Patent documentation 1: the spy opens flat 5-78997 communique
Patent documentation 2: the spy opens flat 5-93393 communique
Patent documentation 3: the spy opens the 2004-162201 communique
Summary of the invention
The object of the present invention is to provide a kind of papermaking process, it can reach quality and drainability balance easily, thereby improves the intensity of paper, and the result can reduce the consumption of the paper power reinforcing agent that uses when papermaking, and then remove water-based when having improved papermaking, thereby can improve operating characteristics.
The inventor etc. just address the above problem and inquire into, discovery uses different types of specific polyacrylamide paper power reinforcing agent just can address the above problem by merging, and then find, can access significant paper power enhancing effect by add these different types of polyacrylamide paper power reinforcing agents respectively in specific place.
That is to say, the present invention relates to papermaking process (1), it is characterized in that, use the nonionic polyacrylamides paper strength agent (A) and the difference of the beating degree of before and after adding paper power reinforcing agent, measuring anionic polyacrylamides paper strength agent (B) or the anionic property polyacrylamide paper power reinforcing agent (C) bigger to copy paper than nonionic polyacrylamides paper strength agent (A) by JIS P 8121.
Also have, the present invention relates to papermaking process (2), it is characterized in that, use the anionic polyacrylamides paper strength agent (B-1) and the difference of the beating degree of before and after adding paper power reinforcing agent, the measuring anionic polyacrylamides paper strength agent (B-2) bigger to copy paper than anionic polyacrylamides paper strength agent (B-1) by JIS P 8121.
Owing to the balance that can keep quality and drainability according to the present invention easily, the effect that improves paper power is increased, the result is the use amount of the paper power reinforcing agent in the time of can reducing papermaking.
The specific embodiment
In papermaking process of the present invention (1), use nonionic polyacrylamides paper strength agent (A) (below be referred to as composition (A)) and adding before and after the paper power reinforcing agent by the difference of the beating degree of the JIS P 8121 mensuration anionic polyacrylamides paper strength agent (B) bigger (below be referred to as composition (B)) or anionic property polyacrylamide paper power reinforcing agent (C) (below be referred to as composition (C)) than composition (A).
Be again, the difference of the beating degree described in the present specification is meant, the beating degree of pulling an oar be wait to copy 30 seconds that add 1.0% aluminum sulfate in the paper stock of paper about 400mL after, add 0.5 weight % paper power reinforcing agent, the paper stock of copying paper with the drainage amount of the Canadian beating degree tester of being put down in writing among the JIS P 8121 and treating before adding paper power reinforcing agent when stirring 30 seconds uses drainage amount poor of Canadian beating degree tester.The adding of paper power reinforcing agent is by the paper stock 300g of the concentration of paper stock solid constituent about 1.0% is placed in the beaker of the stainless steel of 1L, the temperature of paper stock is 25 ℃, carries out with stirring with 300rpm with the paddle (paddle that has the flat oar of 4 2cm * 3cm) of 4 flat oars.
Be again, nonionic of the present invention is meant and is 0.85～1.1 by the ratio by anionic property vinyl monomer (mol% of composition (c))/cationic vinyl monomer (mol% of composition (b)) mode of (when composition (c) during for binary acid, using 2 times of values of the mol% of composition (c)) cooperates.
The composition that uses among the present invention (A) so long as do not show the polyacrylamide paper power reinforcing agent of anionic property and cationic, just has no particular limits, can use known material, but, consider especially, being to have the branched structure person serves as preferred from the effect this point that strengthens paper power.
Composition (A) contains the polyacrylamide analog copolymer, this copolymer is with (a) (methyl) acrylamide (below be referred to as composition (a)), (b) cationic vinyl monomer (below be referred to as composition (b)), (c) anionic property vinyl monomer (below be referred to as composition (c)) is for must composition, copolymerization as required (d) N-replaces (methyl) acrylamide (below be referred to as composition (d)), (e) (methyl) sodium allylsulfonate ((メ ) ア リ Le ス Le ホ Application acid Na ト リ ウ system)) in addition vinyl monomer (f) of (below be referred to as composition (e)) and composition (a)～(e) (below be referred to as composition (f)) obtains, using with composition (a)～(e) is the occasion of the necessary resulting polyacrylamide resinoid of composition, owing in the polyacrylamide resinoid, introduce branched structure easily, be preferred therefore.Also having, owing to use the composition (A) of difference below 50ml of beating degree, can further improve the intensity of paper, is preferred therefore.
As composition (b), so long as the compound of at least 1 cationic functional group and 1 vinyl is arranged, just have no particular limits, can use known material.That specifically enumerates has, for example, except allyl amine, also has (methyl) acrylic acid N, N-dimethyl aminoethyl ester, (methyl) acrylic acid N, N-diethylamino ethyl ester, N, N-dimethylaminopropyl (methyl) acrylamide, N, N-diethylamino propyl group (methyl) acrylamide etc. has the vinyl monomer of tertiary amine group or their hydrochloric acid, sulfuric acid, inorganic acid or organic acid salts such as acetate, or have the vinyl monomer and the chloromethanes of tertiary amine group by this, benzyl chlorine, dimethyl suflfate, the resulting vinyl monomers that contain quaternary ammonium salt of season reagent reacting such as epoxychloropropane etc.
As composition (c),, can use known substances so long as the compound with at least 1 anionic property functional group and 1 vinyl except that composition (e) just has no particular limits.Specifically enumerated, for example, monoacid such as (methyl) acrylic acid, crotonic acid; Binary acid such as maleic acid, fumaric acid, itaconic acid, muconic acid, citraconic acid; Vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-organic sulfonic acids such as 2-methyl propane sulfonic acid; Or these organic acid sodium salts, sylvite etc.
As composition (d), so long as composition (b) N-in addition replaces (methyl) acrylamide, just have no particular limits, can use known substances.Specifically enumerated, for example, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-diisopropyl (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-isopropyl (methyl) acrylamide, the N-tert-butyl group (methyl) acrylamide etc.
As composition (f),, can use known substances so long as composition (a)～(e) vinyl monomer in addition just has no particular limits.Specifically enumerated; for example; except (methyl) methyl acrylate; (methyl) ethyl acrylate; (methyl) alkyl-acrylates such as (methyl) butyl acrylate; allyl alcohols etc. contain allylic allylic monomers class; outside (methyl) acrylonitrile etc.; also has methylene two (methyl) acrylamide as two functional vinyl monomer classes; diacrylamine class monomer and two (methyl) acrylic acid glycol esters such as ethylene (methyl) acrylamide; diacrylate esters monomer classes such as two (methyl) acrylic acid binaryglycol ester; diallylamine; divinylbenzene etc.; and as 1 of the polyfunctional vinyl monomer class with 3 above vinyl; 3; 5-triacryl perhydro-s-triazine; the isocyanuric acid triallyl ester; triallylamine; tetrapropylene acid tetramethylol methane esters etc. can use one or more mixing in these to use separately.
In these compositions (a)～(e),, make move (chain transfer) of free radical take place easily, thereby the adjustment of molecular weight become easily owing to used composition (e), therefore preferred.Also have, owing to used, can make resulting crosslinked polymer and macromolecule quantizes as composition (d) or as diacrylamine class monomer, diacrylate esters monomer, divinylbenzene, the polyfunctional vinyl monomer of composition (f), therefore preferred.
Polymerization for above-mentioned monomer has no particular limits, and can adopt known method.Specifically, above-mentioned monomer class being mixed the back known radical polymerization initiator of adding carries out.Specifically be, for example, in the reaction vessel of regulation, add water as solvent, be warmed to set point of temperature, under agitation respectively they are splashed into the method for polymerization the reaction vessel from dropping funel that above-mentioned various monomer and water are housed and the dropping funel that polymerization initiator and water are housed, and above-mentioned various monomers are joined in the reaction vessel of regulation, adjust to the polymerization temperature of regulation, add polymerization initiator and the method for polymerization etc.Be as required, also can use isopropyl alcohol, amylalcohol etc. not to have allylic alcohols to adjust the molecular weight of resulting acrylamide resinoid as chain-transferring agent again.
For the consumption that obtains the composition (a)～(e) that composition (A) uses preferably, composition (a) is about 57～99.78mol%, with 63～97.8mol% for more preferably, composition (b) is about 0.1～15mol%, with 1～15mol% for more preferably, composition (c) is about 0.1～15mol%, with 1～15mol% for more preferably, under the situation of using composition (d), composition (d) is about 0.01～2mol%, with 0.1～1mol% for more preferably, under the situation of using composition (e), composition (e) is about 0.01～10mol%, with 0.1～5mol% for more preferably.When composition (b) uses less than 0.1mol%, the trend of fixed effect reduction, paper power deleterious is arranged, and when surpassing 15mol%, acrylamide composition in the polymer reduces, and makes paper power effect have a declining tendency, and then, price also uprises, and is therefore not preferred.When using less than 0.1mol% at composition (c), the trend of fixed effect reduction, paper power deleterious is arranged, and when surpassing 15mol%, acrylamide composition in the polymer reduces, and makes paper power effect have a declining tendency, and then, price also uprises, and is therefore not preferred.When composition (d) used less than 0.01mol%, the effect that macromolecule quantizes diminished, and consumption has the danger of gelation when surpassing 2.0mol%.Be again, when using composition (e), a little less than the chain transfer effect less than 0.01mol%, and, just make the branched structure inadequate tendency that becomes because the branch point that generates is few, when surpassing 10mol%, the chain transfer effect is strong excessively, and polymer chain shortens, and is difficult to generate high molecular weight polymers.Be again, in the occasion of using composition (f), serving as preferred below 1mol%.
The weight average molecular weight of the composition that obtains like this (A) is preferred more than about 1,000,000.Weight average molecular weight of the present invention is meant the weight average molecular weight that converts with polyoxyethylene with GPC-LALLS method or GPC-RALLS method, be meant with 0.5mol/L acetate buffer (0.5mol/L acetate+0.5mol/L aqueous sodium acetate solution, pH about 4.2) for solvent (elutriant), polymer concentration are 0.025%, 5 ° or the 90 ° values of measuring down (40 ℃ of temperature) in light scattering angle.The weight average molecular weight of composition (A) is less than can not get sufficient paper power effect at 1,000,000 o'clock.Composition (A) is adjusted to usually and contains the above nonvolatile matter of 5 weight %.Be that the viscosity when the nonvolatile matter of adjusting composition (A) is the aqueous solution of 5 weight % is preferred with 20 below the 000mPas again.Surpass 20 in viscosity, during 000mPas, the effect that improves paper power obviously descends.
The composition that uses among the present invention (B) is to add difference than composition (A) the big polyacrylamide paper power reinforcing agent of front and back by the beating degree of JIS P 8121 mensuration at paper power reinforcing agent, just have no particular limits so long as show the material of cationic, can use known substances, but consider that from the viewpoint of paper power enhancing effect the person serves as preferred there to be the branched structure especially.Being again, owing to used the difference of beating degree to surpass the polyacrylamide paper power reinforcing agent of 50mL, can further improving transaction capabilities, is preferred therefore.Be again, cationic described here be meant by the ratio of anionic property vinyl monomer (mol% of composition (c))/cationic vinyl monomer (mol% of composition (b)) less than 0.85 cooperate like that (here, when composition (c) is binary acid, use 2 times of values of the mol% of composition (c)).The same monomer of employed monomer when employed monomer specifically can use and modulate mentioned component (A) when modulation composition (B).
Though, the composition of enumerating (B) is for must composition and the polyacrylamide analog copolymer that obtains of composition (d), composition (e) and composition (f) copolymerization of adding as required by composition (a), composition (b) and composition (c), when but to use with composition (a)～(e) serve as must composition resulting polyacrylamide resinoid, preferably owing in the polyacrylamide resinoid, introduce branched structure easily.
The consumption of the composition (a)～(e) that uses in order to obtain composition (B) preferably, composition (a) is about 51～99.68mol%, with 66～96.8mol% for more preferably, composition (b) is about 0.2～20mol%, with 2～15mol% for more preferably, composition (c) is about 0.1～16.5mol%, with 1～12.5mol% for more preferably, under the situation of using composition (d), composition (d) is about 0.01～2mol%, with 0.1～1mol% for more preferably, under the situation of using composition (e), composition (e) is about 0.01～10mol%, with 0.1～5mol% for more preferably.When composition (b) uses less than 0.2mol%, the trend of fixed effect step-down, paper power effect step-down is arranged, and when surpassing 20mol%, the acrylamide composition in the polymer reduces, and make paper power effect downward trend, and then price uprises also, and is therefore not preferred.When composition (c) uses less than 0.1mol%, the trend of fixed effect step-down, paper power effect step-down is arranged, and when surpassing 16.5mol%, acrylamide composition in the polymer reduces, and makes paper power effect downward trend, and then, price also uprises, and is therefore not preferred.The polymerization that composition (B) can adopt and composition (A) is same is carried out polymerization, is adjusted into usually to contain the above nonvolatile matter of 5 weight %.Be again, in the occasion of using composition (f), serving as preferred below 0.5mol%.
Weight average molecular weight for these compositions (B) has no particular limits, and is generally 1,000,000 degree.Also have, the viscosity when the adjustment nonvolatile matter is 5 weight % is preferred with 20 below the 000mPas.Surpass 20 in viscosity, during 000mPas, the easy turmoil of quality makes paper power improve effect and obviously descends.
Be again, can use cation-modified polyacrylamide base polymer, it is to carry out modification to form after mentioned component (a)～(f) (wherein, composition (d)～(f) is arbitrarily used) is made polyacrylamide copolymer by the said method polymerization.As cation-modified polyacrylamide base polymer, what enumerate is, for example the material that is obtained by Huffman (Hoffman) decomposition method, Mannich (Mannich) reaction method.
The method of modulating cation-modified acrylamide copolymer with the Huffman decomposition method can adopt method same.For example, can in the aqueous solution of acrylamide copolymer, add hypohalite and base catalyst, under alkalescence, make after the reaction of acrylamide copolymer and hypohalite, add acid, pH is adjusted to 3.5～5.5.Among the present invention, except cation-modified acrylamide copolymer by above-mentioned Huffman decomposition reaction modulation, can the following material of example.Promptly can use the cation-modified thing of in the presence of Choline Chloride, polyacrylamide being modulated with the Huffman decomposition reaction (spy opens clear 53-109594 number), the season reactant and the cation-modified thing (spy public clear 58-8682 number) modulated that in the Huffman decomposition reaction, adds tertiary amine that hydroxyl is arranged and benzyl chlorine or derivatives thereof, in the Huffman decomposition reaction, add the cation-modified thing of being modulated as the organic multicomponent amine of stabilizing agent (special public clear 60-17322 number), the cation-modified thing that adding is modulated as the certain cationic compound of stabilizing agent in the Huffman decomposition reaction (special public clear 62-45884 number) etc.The polymer of being modulated by above-mentioned Huffman decomposition reaction can contain cationic monomer unit, 5～50mol% left and right sides, 60～95mol% left and right sides acrylamide unit.Also have, using the mean molecule quantity of the cation-modified acrylamide copolymer of Huffman decomposition reaction modulation serves as preferred with about 5～3,000,000.
The modulator approach of the cation-modified acrylamide copolymer by Mannich reaction modulation of the present invention can adopt method same.For example, can adopt in the aqueous solution of acrylamide copolymer, to add secondary amine such as formalin and dimethylamine, under 40～60 ℃ temperature, react the condition of 1～5h and carry out.Polymer by above-mentioned Mannich reaction modulation can contain the cationic monomer unit about 10～60mol%, the acrylamide unit about 40～90mol%.
The composition that uses among the present invention (C) is the difference polyacrylamide paper power reinforcing agent bigger than composition (A) with the beating degree of JIS P 8121 mensuration in the front and back that add paper power reinforcing agent, so long as show the compound of anionic property, just have no particular limits, can use known substances, particularly strengthen effect from paper power, the person serves as preferred there to be the branched structure.Being again, owing to used the difference of beating degree to surpass the polyacrylamide paper power reinforcing agent of 50mL, can further improving transaction capabilities, is preferred therefore.Anionic property described here be meant by the ratio of anionic property vinyl monomer (mol% of composition (c))/cationic vinyl monomer (mol% of composition (b)) surpass 1.1 cooperate like that (here, when composition (c) is binary acid, use 2 times of values of the mol% of composition (c)).The same monomer of employed monomer when employed monomer specifically can use and modulate mentioned component (A) when modulation composition (C).
Though the composition of enumerating (C) is by serving as must composition and the composition (d) that adds as required, composition (e) and the resulting polyacrylamide analog copolymer of composition (f) copolymerization with composition (a), composition (b) and composition (c), but using with composition (a)～(e) is the necessary resulting polyacrylamide resinoid of composition, preferred owing to introduce branched structure easily in the polyacrylamide resinoid.
The consumption of the composition (a)～(e) that uses in order to obtain composition (C) preferably, composition (a) is about 50～99.68mol%, with 65～96.8mol% for more preferably, composition (b) is about 0.1～17.5mol%, with 1～13.5mol% for more preferably, composition (c) is about 0.2～20mol%, with 2～15mol% for more preferably, under the situation of using composition (d), composition (d) is about 0.01～2mol%, with 0.1～1mol% for more preferably, under the situation of using composition (e), composition (e) is about 0.01～10mol%, with 0.1～5mol% for more preferably.Be when composition (b) uses less than 0.1mol%, the trend of fixed effect step-down, paper power effect step-down to be arranged again, and when surpassing 17.5mol%, the acrylamide composition in the polymer reduces, and makes paper power strengthen the effect downward trend, and then price also uprises, and is therefore not preferred.Be when composition (c) uses less than 0.2mol%, the trend of fixed effect step-down, paper power effect step-down to be arranged again, and when surpassing 20mol%, the acrylamide composition in the polymer reduces, and makes paper power effect downward trend, and then price also uprises, and is therefore not preferred.Composition (C) can be used with the same polymerization of composition (A) and carry out polymerization, is adjusted into usually to contain the above nonvolatile matter of 5 weight %.Be again, in the occasion of using composition (f), serving as preferred below 0.5mol%.
Weight average molecular weight for these compositions (C) has no particular limits, and is generally about 1,000,000.Also have, the viscosity when the adjustment nonvolatile matter is 5 weight % is preferred with 20 below the 000mPas.Surpass 20 in viscosity, during 000mPas, the easy turmoil of quality makes the raising effect of paper power obviously descend.
When adding mentioned component (A) and composition (B) or composition (C), have no particular limits for addition, usually, with respect to paper stock, composition (A) is scaled about 0.1～1.5 weight % with solid constituent weight, for more preferably, composition (B) or composition (C) are scaled about 0.05～0.75 weight % with solid constituent weight with 0.3～1.0 weight %, with 0.1～0.5 weight % for more preferably.The use amount of composition (A) converts with respect to paper stock during less than 0.1 weight % with solid constituent weight, and paper power effect is not enough, when surpassing 1.5 weight % then fixed performance descend, become and bring out pollution easily.The use amount of composition (B) or composition (C) converts with respect to paper stock during less than 0.05 weight % with solid constituent weight, and drainability is not enough, and the quality of paper is difficult to evenly when surpassing 0.75 weight %.
Because the consumption of composition (A) and composition (A)/consumption solid constituent weight ratio (A)/(B) or (A)/(C) more than 0.2, make paper power improve effect and become significantly, so preferably., there was quality to cause confusion easily, is difficult to improve the tendency of paper power effect less than 0.2 o'clock in the consumption solid constituent weight ratio of composition (A) and composition (B) or composition (C).The upper limit of the consumption solid constituent weight ratio of composition (A) and composition (B) or composition (C) has the situation that the chart speed degree descends of copying but surpass at 20 o'clock without limits.Be in the scope that does not influence effect of the present invention, can add size agent, pitch controlling agent, drainage agent etc. and copy the necessary additive of paper again.
Have no particular limits for the place that adds composition (A) and composition (B) or composition (C), place, composition (B) or the composition (C) of composition (A) more than paper stock concentration 2.0 weight % adds in the place of paper stock concentration less than 2.0 weight %, can significantly improve paper power, therefore preferred.Be again, be as what the place more than the paper stock concentration 2.0 weight % was enumerated, for example, blending bin, mechanical box, kind case etc.; Paper stock concentration has been enumerated less than the place of 2.0 weight %, for example, and fan pump, back flow water pump, screen cloth etc.In these,, can obtain significant especially paper power effect in mechanical box because composition (A) adds, composition (B) or composition (C) add at the fan pump place, thereby preferably.
Also have, in the papermaking process of the present invention (2), used anionic polyacrylamides paper strength agent (B-1) (hereinafter referred to as composition (B-1)) and added difference than composition (B-1) the big anionic polyacrylamides paper strength agent (B-2) (hereinafter referred to as composition (B-2)) of the front and back of paper power reinforcing agent by the beating degree of JIS P 8121 mensuration.Wherein, the difference of beating degree be with manufacture method (1) in explanation same.
For the composition (B-1) that the present invention uses, be polyacrylamide paper power reinforcing agent, so long as show just having no particular limits of cationic, can use known substances, especially strengthen effect and consider that the person serves as preferred there to be the branched structure from paper power.
Though composition (B-1) is the material that contains the polyacrylamide analog copolymer, this polyacrylamide analog copolymer is for example by with (a) (methyl) acrylamide (hereinafter referred to as composition (a)), (b) cationic vinyl monomer (hereinafter referred to as composition (b)) and composition (c) anionic property vinyl monomer (hereinafter referred to as composition (c)) are necessary composition, and (d) N-that adds as required replaces (methyl) acrylamide (hereinafter referred to as composition (d)), (e) (methyl) sodium allylsulfonate (hereinafter referred to as composition (e)) and (f) vinyl monomer (hereinafter referred to as composition (the f)) copolymerization outside the composition (c)～(e) obtain, but, when use serves as must composition resulting polyacrylamide resinoid with composition (a)～(e), in the polyacrylamide resinoid, introduce branched structure easily, therefore preferred.Have again, as previously mentioned, cationic described in the present invention is meant by the ratio of anion (mol% of composition (c))/cationic (mol% of composition (b)) less than 0.85 (when composition (c) is binary acid, the using 2 times of values of the mol% of composition (c) here) that cooperates like that.Also have,, can further improve the paper force intensity owing to use the composition (B-1) of difference below 50ml of beating degree, thus preferred.
Illustrated the same in composition (b), composition (c), composition (d), composition (f) and the top manufacture method (1).Also have, the polymerization of above-mentioned monomer also is that method illustrated in the manufacture method (1) with the front is the same.
For the consumption that obtains the employed composition of composition (B-1) (a)～(e) preferably, composition (a) is about 59.5～99.68mol%, with 65.5～96.8mol% for more preferably, composition (b) is about 0.2～15mol%, with 2～15mol% for more preferably, composition (c) is about 0.1～12.5mol%, with 1～12.5mol% for more preferably, under the situation of using composition (d), composition (d) is about 0.01～2mol%, with 0.1～1mol% for more preferably, under the situation of using composition (e), composition (e) is about 0.01～10mol%, with 0.1～5mol% for more preferably.Be when composition (b) uses less than 0.2mol%, the trend of fixed effect step-down, paper power effect step-down to be arranged again, and when surpassing 15mol%, the acrylamide composition in the polymer reduces, and makes paper power effect downward trend, and then price also uprises, and is therefore not preferred.Be when composition (c) uses less than 0.1mol%, the trend of fixed effect step-down, paper power effect step-down to be arranged again, and when surpassing 12.5mol%, the acrylamide composition in the polymer reduces, and makes paper power effect downward trend, and then price also uprises, thereby not preferred; Be again, when composition (d) used less than 0.01mol%, macromolecule quantized effect and diminishes, and the danger of gelation is arranged when surpassing 2.0mol%; Be when composition (e) uses less than 0.01mol%, a little less than the chain transfer effect, to also have again, the branch point that is generated is few, the branched structure inadequate trend that becomes, and when surpassing 10mol%, the chain transfer effect is strong excessively, and polymer chain is shortened, and is difficult to generate heavy polymer.Be again, under the situation of using composition (f), serving as preferred below the 1mol%.
In manufacture method (2), can use a mentioned component (a)～(f) (composition wherein (d)～(f) can use arbitrarily) to make after the polyacrylamide copolymer with foregoing method polymerization, with the same modification of manufacture method (1) cation-modified polyacrylamide base polymer.As cation-modified polyamide polymers, same with manufacture method (1), be the material that for example obtains with Huffman decomposition method, Mannich reaction method.
The weight average molecular weight of the composition that obtains like this (B-1) is serving as preferred more than about 1,000,000.The weight average molecular weight of composition (B-1) can not fully obtain paper power effect sometimes less than 1,000,000 o'clock.Composition (B-1) is adjusted into usually and contains the above nonvolatile matter of 5 weight %.Be again, the viscosity the when nonvolatile matter of composition (B-1) is adjusted into the aqueous solution of 5 weight % is with 20, and the 000mPas degree is following to be preferred.Surpass 20 in viscosity, during 000mPas, the easy turmoil of quality, paper power improves effect and obviously descends.
The composition (B-2) that the present invention uses is the difference polyacrylamide paper power reinforcing agent bigger than composition (B-1) with the beating degree of JIS P 8121 mensuration in the front and back that add paper power reinforcing agent, so long as show the compound of cationic, just have no particular limits, can use known substances, particularly strengthen effect from paper power, the person serves as preferred there to be the branched structure.Being again, owing to use the difference of beating degree to surpass the polyacrylamide paper power reinforcing agent of 50mL, can further improving transaction capabilities, is preferred therefore.The same monomer of employed monomer when employed monomer specifically can use and modulate mentioned component (B-1) when modulation composition (B-2).
For composition (B-2), though what enumerate is by serving as must composition and the polyacrylamide analog copolymer that obtains of the composition (d), composition (e) and composition (f) copolymerization that add as required with composition (a), composition (b) and composition (c), but when to use with composition (a)～(e) serve as must composition resulting polyacrylamide resinoid, preferably owing in the polyacrylamide resinoid, introduce branched structure easily.
For the consumption that obtains the employed composition of composition (B-2) (a)～(e) preferably, composition (a) is about 51～99.68mol%, with 66～96.8mol% for more preferably, composition (b) is about 0.2～20mol%, with 2～15mol% for more preferably, composition (c) is about 0.1～16.5mol%, with 1～12.5mol% for more preferably, under the situation of using composition (d), composition (d) is about 0.01～2mol%, with 0.1～1mol% for more preferably, under the situation of using composition (e), composition (e) is about 0.01～10mol%, with 0.1～5mol% for more preferably.Be when composition (b) uses less than 0.2mol%, the trend of fixed effect step-down, paper power effect step-down to be arranged again, and when surpassing 20mol%, the acrylamide composition in the polymer reduces, and makes paper power effect downward trend, and then price also uprises, and is therefore not preferred.Be when composition (c) uses less than 0.1mol%, the trend of fixed effect step-down, paper power effect step-down to be arranged again, and when surpassing 16.5mol%, the acrylamide composition in the polymer reduces, and makes paper power effect downward trend, and then price also uprises, thereby not preferred.Composition (B-2) can be used with the same polymerization of composition (B-1) and come polymerization, is adjusted to usually to contain the above nonvolatile matter of 5 weight %.In the occasion of using composition (f), serving as preferred below 0.5mol%.(B-1) is the same with composition, can use through cation-modified material.
The weight average molecular weight of these compositions (B-2) has no particular limits, and is generally about 1,000,000.Viscosity when nonvolatile matter is adjusted into the aqueous solution of 5 weight % is with 20, and 000mPas is following to be preferred.Surpass 20 in viscosity, during 000mPas, the easy turmoil of quality, paper power improves effect and obviously descends.
Quantity when adding mentioned component (B-1) and composition (B-2) has no particular limits, usually, with respect to paper stock, composition (B-1) is scaled with solid constituent weight and adds 0.1～1.5 weight %, with 0.3～1.0 weight % for more preferably, composition (B-2) is scaled with solid constituent weight and adds 0.05～0.75 weight %, with 0.1～0.5 weight % for more preferably.The use amount of composition (B-1) is when converting with respect to paper stock less than 0.1 weight % with solid constituent weight, paper power effect is insufficient, when surpassing 1.5 weight % then fixed performance descend, become and bring out pollution easily.The use amount of composition (B-2) is when converting with respect to paper stock less than 0.05 weight % with solid constituent weight, drainability is not enough, and the quality of paper is difficult to evenly when surpassing 0.75 weight %.
Because the solid constituent weight ratio (B-1)/(B-2) of the consumption of composition (B-1) and the consumption of composition (B-2) more than 0.2, makes paper power improve effect and becomes significantly, and is therefore preferred.Consumption solid constituent weight ratio at composition (B-1) and composition (B-2) causes confusion easily less than 0.2 o'clock quality, and the tendency that is difficult to improve paper power effect is arranged.The upper limit of the consumption solid constituent weight ratio of composition (B-1) and composition (B-2) has the situation that the chart speed degree descends of copying but surpass at 20 o'clock without limits.Be in the scope that does not influence effect of the present invention, can add size agent, pitch controlling agent, drainage agent etc. and copy the necessary additive of paper again.
Have no particular limits for the place that adds composition (B-1) and composition (B-2), the place of composition (B-1) more than paper stock concentration 2.0 weight % adds, composition (B-2) adds in the place of paper stock concentration less than 2.0 weight %, can significantly improve the paper force intensity, therefore preferred.Be again, be as what the place more than the paper stock concentration 2.0 weight % was enumerated, for example, blending bin, mechanical box, kind case etc.; Paper stock concentration has been enumerated less than the place of 2.0 weight %, for example, and fan pump, back flow water pump, screen cloth etc.In these, because composition (B-1) adds at mechanical box, composition (B-2) can obtain significant especially paper power effect in the adding of fan pump place, thereby preferred.
Embodiment
Illustrate in greater detail the present invention with embodiment below, but the present invention is not limited to these.Part and % among the embodiment represent weight portion and weight % separately.Test method among the embodiment is as follows.
(1) beating degree
Measure with above-mentioned method according to JIS P 8121 standards.The paper stock that uses in the mensuration is L-UKP, use pull an oar to 400mL and material.
(2) rupture strength
According to JIS P 8131 standard tests, with than rupture strength (kPam
2/ g) expression.
(3) weight average molecular weight
Measure by following condition:
The GPC body: eastern Cao (strain) makes
Post: guard column PWXL1 root and GMPWXL2 root (40 ℃ of temperature) that eastern Cao (strain) makes
Elutriant: 0.5mol/L acetate buffer (0.5mol/L acetate (company produces with the pure pharmaceutical worker's industry of light)+0.5mol/L sodium acetate (production of the Kishida chemical company) aqueous solution, pH about 4.2)
Flow velocity: 0.8mL/min
Detector: concentration detector (RI-8010) and light scattering detector (LS-8000) (room temperature) LALLS method that eastern Cao company makes
Viscotech company makes TDAMODEL301 (concentration detector and 90 ° of light scattering detectors and viscosity detector (temperature)) RALLS method
Abbreviation title among the embodiment is as follows:
(a) AA: acrylic acid IA: itaconic acid
(b) DM: dimethylaminoethyl acrylate methyl amino-ethyl ester DMAEA-BQ: the season thing Mn of the benzyl chlorine of the season thing DML:DM of the benzyl chlorine of dimethylaminoethyl acrylate methyl amino-ethyl ester: Mannich modifier Hf: Huffman modifier
(c) DMAA: DMAA
(d) SMAS: methallylsulfonic acid sodium
(e) AM: acrylamide
(f) MBAA: methylene diacrylamine AN: acrylonitrile
Be example with papermaking process (1) below.Monomer component and the ratio used in each Production Example are as described in Table 1, and the performance number of resulting aqueous copolymers solution is as shown in table 2.
Production Example 1-1
In the reaction unit that has mixer, thermometer, reflux condensing tube, nitrogen ingress pipe and 2 dropping funels, add 338 parts of ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, be heated to 90 ℃, add 179 parts of 166 parts of acrylamides, 10 part of 62.5% sulfuric acid, 10.9 part of 80% acrylic acid aqueous solution, 2.1 parts of methallylsulfonic acid sodium, 20.6 parts of dimethylaminoethyl acrylate methyl base amino-ethyl esters, 2.6 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters in a dropping funel, regulating pH by sulfuric acid is 3.In another dropping funel, add 0.3 part of ammonium persulfate and 180 parts of ion exchange waters.Then, in reaction system, splash into monomer and catalyst with about 3h by two dropping funels.After dripping off, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h adds 80 parts of ion exchange waters, obtains solid constituent 20.1%, viscosity (25 ℃) is 8, the aqueous copolymers solution of 000mPas.
Production Example 1-2
With the same reaction unit of Production Example 1-1 in, add 338 parts of ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, be heated to 90 ℃, in a dropping funel, add 168 parts of acrylamides, 10 part of 62.5% sulfuric acid, 7.7 parts of itaconic acids, 1.4 179 parts of part methallylsulfonic acid sodium, 20 parts of dimethylaminoethyl acrylate methyl base amino-ethyl esters, 2.6 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters, regulating pH by sulfuric acid is 3.In another dropping funel, add 0.3 part of ammonium persulfate and 180 parts of ion exchange waters.Then, in reaction system, splash into monomer and catalyst with about 3h by two dropping funels.After dripping off, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h adds 80 parts of ion exchange waters, obtains solid constituent 20.3%, viscosity (25 ℃) is 8, the aqueous copolymers solution of 000mPas.
Production Example 1-3
With the same reaction unit of Production Example 1-1 in, add 666 parts of the season thing aqueous solution of 155 parts of acrylamides, 56.5 part of 60% dimethylaminoethyl acrylate methyl base amino-ethyl ester, 7.2 parts of itaconic acids, 1.5 parts of methallylsulfonic acid sodium, 2.4 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making becomes 55 ℃ in the system, under agitation add 0.3 part of polymerization initiator ammonium persulfate and 10 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 80 parts of ion exchange waters, obtain solid constituent 20.1%, viscosity (25 ℃) is 8, the aqueous copolymers solution of 000mPas.
Production Example 1-4
With the same reaction unit of Production Example 1-1 in, add 541 parts of 84.3 parts of acrylamides, 5 part of 62.5% sulfuric acid, 10.2 parts of dimethylaminoethyl acrylate methyl base amino-ethyl esters, 3.9 parts of itaconic acids, 0.3 part of methallylsulfonic acid sodium, 1.3 parts of DMAAs and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making becomes 55 ℃ in the system, under agitation add 0.14 part of polymerization initiator ammonium persulfate and 20 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.2 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 320 parts of ion exchange waters, obtain solid constituent 10.2%, viscosity (25 ℃) is 10, the aqueous copolymers solution of 000mPas.
Production Example 1-5
With the same reaction unit of Production Example 1-1 in, add 167 parts of ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, be heated to 90 ℃, in a dropping funel, add 85.4 parts of acrylamides, 5.1 part of 62.5% sulfuric acid, 3.9 parts of itaconic acids, 10.2 300 parts of part dimethylaminoethyl acrylate methyl base amino-ethyl ester and ion exchange waters, regulating pH by sulfuric acid is 3.In another dropping funel, add 0.14 part of ammonium persulfate and 180 parts of ion exchange waters.Then, in reaction system, splash into monomer and catalyst with about 3h by two dropping funels.After dripping off, add 0.2 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h adds 320 parts of ion exchange waters, obtains solid constituent 10.2%, viscosity (25 ℃) is 10, the aqueous copolymers solution of 000mPas.
Production Example 1-6
With the same reaction unit of Production Example 1-1 in, add 670 parts of the season thing aqueous solution of 148.1 parts of acrylamides, 58.9 part of 75% dimethylaminoethyl acrylate methyl base amino-ethyl ester, 6.3 part of 80% acrylic acid aqueous solution, 1.5 parts of methallylsulfonic acid sodium, 1.2 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making becomes 55 ℃ in the system, under agitation add 0.28 part of polymerization initiator ammonium persulfate and 20 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 48 parts of ion exchange waters, obtain solid constituent 20.2%, viscosity (25 ℃) is 8, the aqueous copolymers solution of 000mPas.
Production Example 1-7
With the same reaction unit of Production Example 1-1 in, add 660 parts of the season thing aqueous solution of 146.8 parts of acrylamides, 76.6 part of 60% dimethylaminoethyl acrylate methyl base amino-ethyl ester, 6.3 part of 80% acrylic acid aqueous solution, 1.1 parts of methallylsulfonic acid sodium, 1.2 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, add 0.28 part of ammonium persulfate and 20 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 380 parts of ion exchange waters, obtain solid constituent 15.2%, viscosity (25 ℃) is 10, the aqueous copolymers solution of 000mPas.
Production Example 1-8
With the same reaction unit of Production Example 1-1 in, add 540 parts of 82.6 parts of acrylamides, 7 part of 62.5% sulfuric acid, 14.1 parts of dimethylaminoethyl acrylate methyl base amino-ethyl esters, 2.5 parts of itaconic acids, 0.2 part of methallylsulfonic acid sodium, 0.6 part of DMAA, 0.02 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making becomes 55 ℃ in the system, under agitation add 0.14 part of ammonium persulfate and 20 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.2 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 330 parts of ion exchange waters, obtain solid constituent 10.2%, viscosity (25 ℃) is 10, the aqueous copolymers solution of 000mPas.
Production Example 1-9
With the same reaction unit of Production Example 1-1 in, add 430 parts of 41.3 parts of acrylamides, 3.5 part of 62.5% sulfuric acid, 7 parts of dimethylaminoethyl acrylate methyl base amino-ethyl esters, 1.3 parts of itaconic acids, 0.05 part of methallylsulfonic acid sodium, 0.3 part of DMAA, 0.01 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making becomes 55 ℃ in the system, under agitation add 0.07 part of polymerization initiator ammonium persulfate and 10 parts of ion exchange waters and 0.03 part of sodium hydrogensulfite and 10 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.1 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 490 parts of ion exchange waters, obtain solid constituent 5.2%, viscosity (25 ℃) is 15, the aqueous copolymers solution of 000mPas.
Production Example 1-10
With the same reaction unit of Production Example 1-1 in, add 340 parts of 33.1 parts of acrylamides, 2.8 part of 62.5% sulfuric acid, 5.6 parts of dimethylaminoethyl acrylate methyl base amino-ethyl esters, 1.0 parts of itaconic acids, 0.01 part of methallylsulfonic acid sodium, 0.3 part of DMAA, 0.01 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making becomes 55 ℃ in the system, under agitation add 0.06 part of polymerization initiator ammonium persulfate and 10 parts of ion exchange waters and 0.02 part of sodium hydrogensulfite and 10 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.08 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 910 parts of ion exchange waters, obtain solid constituent 3.2%, viscosity (25 ℃) is 15, the aqueous copolymers solution of 000mPas.
Production Example 1-11
With the same reaction unit of Production Example 1-1 in, add 760 parts of 150.5 parts of acrylamides, 14.1 part of 62.5% sulfuric acid, 28.4 parts of dimethylaminoethyl acrylate methyl base amino-ethyl esters, 23.2 part of 80% acrylic acid aqueous solution, 1.2 parts of methallylsulfonic acid sodium, 1.3 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making becomes 55 ℃ in the system, under agitation add 0.28 part of polymerization initiator ammonium persulfate and 20 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 350 parts of ion exchange waters, obtain solid constituent 15.2%, viscosity (25 ℃) is 10, the aqueous copolymers solution of 000mPas.
Production Example 1-12
With the same reaction unit of Production Example 1-1 in, add 745 parts of the aqueous solution of the quaternized thing of 135.1 parts of acrylamides, 76.5 part of 60% dimethylaminoethyl acrylate methyl base amino-ethyl ester, 20.8 part of 80% acrylic acid aqueous solution, 1.1 parts of methallylsulfonic acid sodium, 1.2 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making becomes 55 ℃ in the system, under agitation add 0.28 part of polymerization initiator ammonium persulfate and 20 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 290 parts of ion exchange waters, obtain solid constituent 15.2%, viscosity (25 ℃) is 10, the aqueous copolymers solution of 000mPas.
Production Example 1-13
With the same reaction unit of Production Example 1-1 in, add 745 parts of the season thing aqueous solution of 140.1 parts of acrylamides, 76.6 part of 60% dimethylaminoethyl acrylate methyl base amino-ethyl ester, 14.6 part of 80% acrylic acid aqueous solution, 1.1 parts of methallylsulfonic acid sodium, 1.2 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making becomes 55 ℃ in the system, under agitation add 0.28 part of polymerization initiator ammonium persulfate and 20 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 290 parts of ion exchange waters, obtain solid constituent 15.2%, viscosity (25 ℃) is 10, the aqueous copolymers solution of 000mPas.
Production Example 1-14
With the same reaction unit of Production Example 1-1 in, add 650 parts of 124 parts of acrylamides, 22 part of 80% acrylic acid aqueous solution, 26 parts of acrylonitrile and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making becomes 40 ℃ in the system, under agitation add 0.23 part of polymerization initiator ammonium persulfate and 10 parts of ion exchange waters and 0.09 part of sodium hydrogensulfite and 10 parts of ion exchange waters.Be incubated 2h after being warming up to 90 ℃.After polymerization is over, add 270 parts of ion exchange waters, obtain solid constituent 15.2%, viscosity (25 ℃) is 5, the aqueous copolymers solution of 000mPas.
Production Example 1-15
With the same reaction unit of Production Example 1-1 in, add 440 parts of 73 parts of acrylamides, 10 part of 80% acrylic acid aqueous solution and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making becomes 40 ℃ in the system, under agitation add 0.1 part of polymerization initiator ammonium persulfate and 10 parts of ion exchange waters and 0.1 part of sodium hydrogensulfite and 10 parts of ion exchange waters.Be incubated 1h after being warming up to 90 ℃.Be cooled to 40 ℃ after adding 360 parts of ion exchange waters, add 0.4 part of 48% NaOH, 49 part of 50% dimethylamine, 37 part of 37% formalin, insulation 1h.After polymerization is over, add 180 parts of ion exchange waters, obtain solid constituent 10.2%, viscosity (25 ℃) is 10, the aqueous copolymers solution of 000mPas.
Production Example 1-16
With the same reaction unit of Production Example 1-1 in, add 393 parts of 1.7 parts of acrylamides and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making becomes 40 ℃ in the system, under agitation add 0.15 part of polymerization initiator ammonium persulfate and 10 parts of ion exchange waters and 0.15 part of sodium hydrogensulfite and 10 parts of ion exchange waters.Be incubated 1h after being warming up to 90 ℃.Be cooled to after 20 ℃, adding 251.7 part of 12% clorox and 33.8 part of 48% NaOH, insulation 30min.After polymerization is over, add 395 parts of ion exchange waters, obtain pH4.0, active ingredient 5.0%, viscosity (25 ℃) and be the aqueous copolymers solution of 20mPas.
[table 1]
| Composition (a) | Composition (b) | Composition (c) | Composition (d) | Composition (e) | Composition (f) | Anion/cation ratio | |
| Production Example 1-1 | AM 88.89 | DM 5 | AA 4.6 | 1 | 0.50 | MBAA 0.01 | 0.92 |
| Production Example 1-2 | AM 91.34 | DM 5 | IA 2.3 | 1 | 0.35 | MBAA 0.01 | 0.92 |
| Production Example 1-3 | AM 91.29 | DML 5 | IA 2.3 | 1 | 0.40 | MBAA 0.01 | 0.92 |
| Production Example 1-4 | AM 91.55 | DM 5 | IA 2.3 | 1 | 0.15 | - | 0.92 |
| Production Example 1-5 | AM 92.70 | DM 5 | IA 2.3 | - | - | - | 0.92 |
| Production Example 1-6 | AM 89.09 | DMAEA-BQ 7 | AA 3.0 | 0.5 | 0.40 | MBAA 0.01 | 0.43 |
| Production Example 1-7 | AM 89.19 | DML 7 | AA 3.0 | 0.5 | 0.30 | MBAA 0.01 | 0.43 |
| Production Example 1-8 | AM 90.89 | DM 7 | IA 1.5 | 0.5 | 0.10 | MBAA 0.01 | 0.43 |
| Production Example 1-9 | AM 90.94 | DM 7 | IA 1.5 | 0.5 | 0.05 | MBAA0.01 | 0.43 |
| Production Example 1-10 | AM 90.98 | DM 7 | IA 1.5 | 0.5 | 0.01 | MBAA 0.01 | 0.43 |
| Production Example 1-11 | AM 82.19 | DM 7 | AA 10 | 0.5 | 0.30 | MBAA 0.01 | 1.43 |
| Production Example 1-12 | AM 82.19 | DML 7 | AA 10 | 0.5 | 0.30 | MBAA 0.01 | 1.43 |
| Production Example 1-13 | AM 85.19 | DML 7 | AA 7.0 | 0.5 | 0.30 | MBAA 0.01 | 1.00 |
| Production Example 1-14 | AM 70 | - | AA 10 | - | - | AN 20 | - |
| Production Example 1-15 | AM 50 | Mn 40 | AA 10 | - | - | - | 0.25 |
| Production Example 1-16 | AM 60 | Hf 40 | - | - | - | - | - |
Numeral in the table is all represented mol%
[table 2]
| Beating degree (ml) | Nonvolatile matter (%) | Viscosity (mPas) | 5% viscosity (mPas) | Weight average molecular weight | |
| Production Example 1-1 | 10 | 20 | 8000 | 40 | 3,000,000 |
| Production Example 1-2 | 30 | 20 | 8000 | 40 | 3,000,000 |
| Production Example 1-3 | 80 | 20 | 8000 | 40 | 2,000,000 |
| Production Example 1-4 | 50 | 10 | 10000 | 500 | 1,500,000 |
| Production Example 1-5 | 40 | 10 | 10000 | 500 | 500,000 |
| Production Example 1-6 | 30 | 20 | 8000 | 40 | 2,000,000 |
| Production Example 1-7 | 80 | 15 | 10000 | 250 | 1,000,000 |
| Production Example 1-8 | 120 | 10 | 10000 | 500 | 1,500,000 |
| Production Example 1-9 | 180 | 5 | 15000 | 15000 | 1,700,000 |
| Production Example 1-10 | 250 | 3 | 15000 | 70000 | 2,000,000 |
| Production Example 1-11 | 30 | 15 | 10000 | 250 | 1,000,000 |
| Production Example 1-12 | 80 | 15 | 10000 | 250 | 1,000,000 |
| Production Example 1-13 | 80 | 15 | 10000 | 250 | 1,000,000 |
| Production Example 1-14 | - | 15 | 5000 | 120 | 400,000 |
| Production Example 1-15 | - | 10 | 10000 | 500 | 1,000,000 |
| System 14+ system 15 | 100 | - | - | - | - |
| Production Example 1-16 | 80 | 5 | 20 | 20 | 500,000 |
Viscosity gauge is shown in 25 ℃ measured value.
The nonvolatile matter of Production Example 1-16 is represented active ingredient, and weight average molecular weight is the measured value of the polymer before the modification.
The mixture of system 14+ system 15 expression Production Example 1-14 and Production Example 1-15, mixing ratio is Production Example 1-14/ Production Example 1-15=2/1 (weight ratio).
Embodiment 1-1
Old corrugated board is pulled an oar in the formula beater of Niagara, in the paper stock that is adjusted into canadian standard freeness (C.S.F.) 350mL, add 1.0% aluminum sulfate, pH is adjusted to 6.5.When this paper stock slurry is copied paper, copy paper in the following manner: making paper stock concentration is 3.0%, adding with respect to the paper stock solid weight 0.35% as paper power reinforcing agent by the resulting aqueous solutions of polymers of Production Example 1-1, then, making paper stock concentration is 1.5%, adding with respect to paper stock 0.15% as paper power reinforcing agent by the resulting aqueous solutions of polymers of Production Example 1-7, in latch needles jacquard weave gear piece machine dehydration, at 5kg/cm
2Press down 2min, make the level ground amount be 150g/m
2Then, at 105 ℃ of dry 4min, damping 24h under 23 ℃, 50% relative humidity condition measures it and compares rupture strength with rotary drier.
Embodiment 1-2～9, comparative example 1-1～6
Except employed paper power reinforcing agent, paper stock concentration when adding paper power reinforcing agent by changing like that shown in the table 3, carry out mensuration equally with embodiment 1-1 than rupture strength, the results are shown in table 3.
[table 3]
| At the use paper power reinforcing agent that adds place 1 | Adding rate is (%) 1. | At the use paper power reinforcing agent that adds place 2 | Adding rate is (%) 2. | Adding rate is than (1./2.) | Drainage amount (ml) | Compare rupture strength | |
| Embodiment 1-1 | Production Example 1-1 | 0.35 | Production Example 1-7 | 0.15 | 2.33 | 405 | 2.97 |
| Embodiment 1-2 | Production Example 1-2 | 0.35 | Production Example 1-7 | 0.15 | 2.33 | 413 | 2.95 |
| Embodiment 1-3 | Production Example 1-4 | 0.40 | Production Example 1-9 | 0.10 | 4.00 | 421 | 2.93 |
| Embodiment 1-4 | Production Example 1-4 | 0.35 | Production Example 1-12 | 0.15 | 2.33 | 410 | 2.96 |
| Embodiment 1-5 | Production Example 1-5 | 0.40 | Production Example 1-9 | 0.10 | 4.00 | 419 | 2.88 |
| Embodiment 1-6 | Production Example 1-1 | 0.05 | Production Example 1-7 | 0.45 | 0.11 | 447 | 2.84 |
| Embodiment 1-7 | Production Example 1-2 | 0.35 | Production Example 1-10 | 0.15 | 2.33 | 461 | 2.84 |
| Embodiment 1-8 | Production Example 1-1 | 0.35 | System 14+ system 15 | 0.15 | 2.33 | 423 | 2.87 |
| Embodiment 1-9 | Production Example 1-1 | 0.35 | Production Example 1-16 | 0.15 | 2.33 | 411 | 2.89 |
| Embodiment 1-10 | Production Example 1-7 | 0.15 | Production Example 1-1 | 0.35 | 0.43 | 423 | 2.85 |
| Comparative example 1-1 | Production Example 1-2 | 0.35 | Production Example 1-13 | 0.15 | 2.33 | 400 | 2.75 |
| Comparative example 1-2 | Production Example 1-6 | 0.35 | Production Example 1-13 | 0.15 | 2.33 | 397 | 2.77 |
| Comparative example 1-3 | Production Example 1-2 | 0.35 | Production Example 1-6 | 0.15 | 2.33 | 367 | 2.78 |
| Comparative example 1-4 | Production Example 1-3 | 0.35 | Production Example 1-7 | 0.15 | 2.33 | 439 | 2.69 |
| Comparative example 1-5 | Production Example 1-2 | 0.35 | Production Example 1-11 | 0.15 | 2.33 | 371 | 2.75 |
| Comparative example 1-6 | Production Example 1-3 | 0.35 | Production Example 1-12 | 0.15 | 2.33 | 436 | 2.70 |
In the table, the system 14+ system 15 expression Production Example 1-14 of embodiment 1-8 and the mixture of Production Example 1-15, Production Example 1-14/ Production Example 1-15=2/1 (weight ratio).
Being again, is 3.0% in the paper stock concentration that adds place 1, is 1.5% in the paper stock concentration that adds place 2.
Embodiment 1-10
L-UKP is pulled an oar in the formula beater of Niagara, in the paper stock that is adjusted into canadian standard freeness (C.S.F.) 450mL, add 1.0% aluminum sulfate, pH is adjusted to 6.5.When this paper stock slurry is copied paper, copy paper in the following manner: making paper stock concentration is 2.0%, add pressing with respect to 1.0% of paper stock solid weight as paper power reinforcing agent by the resulting aqueous solutions of polymers of Production Example 1-1, then, making paper stock concentration is 1.0%, add pressing with respect to 0.2% of paper stock as paper power reinforcing agent, in latch needles jacquard weave gear piece machine, dewater, at 5kg/cm by the resulting aqueous solutions of polymers of Production Example 1-8
2Press down 2min, make the level ground amount be 150g/m
2Then, at 105 ℃ of dry 4min, damping 24h under 23 ℃, 50% relative humidity condition measures it and compares rupture strength with rotary drier.Embodiment 1-11～20, comparative example 7～12
The paper stock concentration change as shown in table 4 during except employed paper power reinforcing agent, adding paper power reinforcing agent, measure than rupture strength the same with embodiment 1-10 the results are shown in table 4.
[table 4]
| At the use paper power reinforcing agent that adds place 1 | Adding rate is (%) 1. | At the use paper power reinforcing agent that adds place 2 | Adding rate is (%) 2. | Adding rate is than (1./2.) | Drainage amount (ml) | Compare rupture strength | |
| Embodiment 1-11 | Production Example 1-1 | 1.00 | Production Example 1-8 | 0.20 | 5.00 | 477 | 4.05 |
| Embodiment 1-12 | Production Example 1-2 | 1.00 | Production Example 1-8 | 0.20 | 5.00 | 486 | 4.00 |
| Embodiment 1-13 | Production Example 1-4 | 1.05 | Production Example 1-9 | 0.15 | 7.00 | 502 | 3.97 |
| Embodiment 1-14 | Production Example 1-2 | 1.00 | Production Example 1-12 | 0.20 | 5.00 | 481 | 4.02 |
| Embodiment 1-15 | Production Example 1-5 | 1.05 | Production Example 1-9 | 0.15 | 7.00 | 494 | 3.88 |
| Embodiment 1-16 | Production Example 1-1 | 0.15 | Production Example 1-8 | 1.05 | 0.14 | 543 | 3.84 |
| Embodiment 1-17 | Production Example 1-2 | 1.00 | Production Example 1-10 | 0.20 | 5.00 | 520 | 3.92 |
| Embodiment 1-18 | Production Example 1-2 | 1.00 | System 14+ system 15 | 0.20 | 5.00 | 495 | 3.88 |
| Embodiment 1-19 | Production Example 1-2 | 1.00 | Production Example 1-16 | 0.20 | 5.00 | 483 | 3.91 |
| Embodiment 1-20 | Production Example 1-8 | 0.20 | Production Example 1-1 | 1.00 | 0.20 | 485 | 3.89 |
| Comparative example 1-7 | Production Example 1-2 | 1.00 | Production Example 1-13 | 0.20 | 5.00 | 488 | 3.67 |
| Comparative example 1-8 | Production Example 1-6 | 1.00 | Production Example 1-13 | 0.20 | 5.00 | 485 | 3.69 |
| Comparative example 1-9 | Production Example 1-2 | 1.00 | Production Example 1-6 | 0.20 | 5.00 | 475 | 3.70 |
| Comparative example 1-10 | Production Example 1-3 | 1.00 | Production Example 1-7 | 0.20 | 5.00 | 550 | 3.64 |
| Comparative example 1-11 | Production Example 1-2 | 1.00 | Production Example 1-11 | 0.20 | 5.00 | 463 | 3.73 |
| Comparative example 1-12 | Production Example 1-3 | 1.00 | Production Example 1-12 | 0.20 | 5.00 | 485 | 3.68 |
In the table, the system 14+ system 15 expression Production Example 1-14 of embodiment 1-17 and the mixture of Production Example 1-15, Production Example 1-14/ Production Example 1-15=2/1 (weight ratio).
Being again, is 2.0% in the paper stock concentration that adds place 1, is 1.0% in the paper stock concentration that adds place 2.
By table 3 and table 4 as can be known, with the difference of the beating degree that adds nonionic polyacrylamides paper strength agent and before and after the paper stock reinforcing agent adds, measure according to JIS P 8121 than the prescription of the big nonionic polyacrylamides paper strength agent of nonionic polyacrylamides paper strength agent or add anionic polyacrylamides paper strength agent and the difference of the beating degree measured according to JIS P8121 is compared than the prescription of the big nonionic polyacrylamides paper strength agent of anionic polyacrylamides paper strength agent before and after the paper stock reinforcing agent adds, use the present invention, can easily make the high paper of paper delivery force intensity (embodiment 1-1～20, comparative example 1-1,2,7,8).Be again, at the ratio of composition (A)/composition (B) or composition (C) less than 0.2 o'clock, because its paper power effect has a little downward trend, therefore 0.2 or more to serve as preferably (embodiment 1-1 and 6,11 and 16).And then, composition (A) is added more than 2.0% in paper stock concentration less than 2.0% o'clock adding, composition (B) or composition (C) in paper stock concentration, can make paper power effect that a little downward trend is arranged, therefore, to be incorporated as preferred (embodiment 1-1 and 10,11 and 20) in paper stock concentration more than 2.0%, composition (B) or composition (C) in paper stock concentration less than 2.0% at composition (A).The weight average molecular weight of composition (A) can make paper power effect that a little downward trend is arranged less than 1,000,000 o'clock, so the weight average molecular weight of composition (A) is more than 1,000,000 to serve as preferred (embodiment 1-3 and 5,13 and 15).5 weight % viscosity in aqueous solution of composition (B) or composition (C) surpass 20, during 000mPas, cause the quality confusion easily, and make its paper power effect that a little downward trend be arranged, therefore 5 weight % viscosity in aqueous solution of composition (B) or composition (C) with 20 below the 000mPas are preferred (embodiment 1-2 and 7,12 and 17).Even different composition (A) is added more than 2.0% and is not also obtained sufficient paper power effect (embodiment 1-1～20, comparative example 3 and 5,9 and 11) adding less than 2.0% o'clock of paper stock concentration in paper stock concentration.Also have, even different composition (B) or composition (C) are added 2.0% or more and also do not obtain sufficient paper power effect (embodiment 1-1～20, comparative example 4 and 6,10 and 12) in the adding in 2.0% o'clock less than paper stock concentration in paper stock concentration.
Provide the example of papermaking process (2) below.The monomer component ratio of using in each Production Example sees Table 5, and the performance number of resulting aqueous copolymers solution is shown in Table 6.
Production Example 2-1
In the reaction unit that has mixer, thermometer, reflux condensing tube, nitrogen ingress pipe and 2 dropping funels, add 340 parts of ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, be heated to 90 ℃, add 180 parts of 169 parts of acrylamides, 10.3 part of 62.5% sulfuric acid, 7.1 part of 80% acrylic acid aqueous solution, 2.1 parts of methallylsulfonic acid sodium, 20.6 parts of dimethylaminoethyl acrylate methyl base amino-ethyl esters, 2.6 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters from dropping funel, regulating pH by sulfuric acid is 3.Add 0.3 part of ammonium persulfate and 180 parts of ion exchange waters from another dropping funel.Then, in reaction system, splash into monomer and catalyst with about 3h from 2 dropping funels.After dripping off, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h adds 80 parts of ion exchange waters, obtains solid constituent 20.2%, viscosity (25 ℃) is 8, the aqueous copolymers solution of 000mPas.
Production Example 2-2
With the same reaction unit of Production Example 2-1 in, add 340 parts of ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, be heated to 90 ℃, add 170 parts of acrylamides, 10.2 part of 62.5% sulfuric acid, 5.1 parts of itaconic acids from a dropping funel, 1.6 180 parts of part methallylsulfonic acid sodium, 20.4 parts of dimethylaminoethyl acrylate methyl base amino-ethyl esters, 2.6 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters, regulating pH by sulfuric acid is 3.Each and every one dropping funel adds 0.3 part of ammonium persulfate and 180 parts of ion exchange waters from another.Then, in reaction system, splash into monomer and catalyst with about 3h by 2 dropping funels.After dripping off, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h adds 80 parts of ion exchange waters, obtains solid constituent 20.3%, viscosity (25 ℃) is 8, the aqueous copolymers solution of 000mPas.
Production Example 2-3
With the same reaction unit of Production Example 2-1 in, add 665 parts of the season thing aqueous solution of 157.3 parts of acrylamides, 56.8 part of 60% dimethylaminoethyl acrylate methyl base amino-ethyl ester, 4.7 parts of itaconic acids, 1.5 parts of methallylsulfonic acid sodium, 2.4 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making in the system is 55 ℃, under agitation adds 0.3 part of polymerization initiator ammonium persulfate and 20 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 50 parts of ion exchange waters, obtain solid constituent 20.1%, viscosity (25 ℃) is 8, the aqueous copolymers solution of 000mPas.
Production Example 2-4
With the same reaction unit of Production Example 2-1 in, add 540 parts of 85.6 parts of acrylamides, 5.1 part of 62.5% sulfuric acid, 10.3 parts of dimethylaminoethyl acrylate methyl base amino-ethyl esters, 2.5 parts of itaconic acids, 0.3 part of methallylsulfonic acid sodium, 1.3 parts of DMAAs and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making in the system is 55 ℃, under agitation adds 0.14 part of polymerization initiator ammonium persulfate and 20 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 320 parts of ion exchange waters, obtain solid constituent 10.2%, viscosity (25 ℃) is 10, the aqueous copolymers solution of 000mPas.
Production Example 2-5
With the same reaction unit of Production Example 2-1 in, add 270 parts of ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, be heated to 90 ℃, add 86.7 parts of acrylamides, 5.1 part of 62.5% sulfuric acid, 2.5 parts of itaconic acids from a dropping funel, 10.3 115 parts of part dimethylaminoethyl acrylate methyl base amino-ethyl ester and ion exchange waters, regulating pH by sulfuric acid is 3.Add 0.14 part of ammonium persulfate and 180 parts of ion exchange waters at another dropping funel.Then, in reaction system, splash into monomer and catalyst with about 3h by 2 dropping funels.After dripping off, add 0.2 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h adds 320 parts of ion exchange waters, obtains solid constituent 10.2%, viscosity (25 ℃) is 10, the aqueous copolymers solution of 000mPas.
Production Example 2-6
With the same reaction unit of Production Example 2-1 in, add 680 parts of 167.9 parts of acrylamides, 10.1 part of 62.5% sulfuric acid, 20.3 parts of dimethylaminoethyl acrylate methyl base amino-ethyl esters, 7.7 parts of itaconic acids, 1.4 parts of methallylsulfonic acid sodium, 2.6 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making in the system is 55 ℃, under agitation adds 0.28 part of polymerization initiator ammonium persulfate and 20 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 80 parts of ion exchange waters, obtain solid constituent 20.2%, viscosity (25 ℃) is 8, the aqueous copolymers solution of 000mPas.
Production Example 2-7
With the same reaction unit of Production Example 2-1 in, add 570 parts of the season thing aqueous solution of 148.1 parts of acrylamides, 58.9 part of 75% dimethylaminoethyl acrylate methyl base amino-ethyl ester, 6.3 part of 80% acrylic acid aqueous solution, 1.5 parts of methallylsulfonic acid sodium, 1.2 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, add 0.28 part of ammonium persulfate and 20 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 50 parts of ion exchange waters, obtain solid constituent 20.2%, viscosity (25 ℃) is 8, the aqueous copolymers solution of 000mPas.
Production Example 2-8
With the same reaction unit of Production Example 2-1 in, add 660 parts of the season thing aqueous solution of 146.8 parts of acrylamides, 76.6 part of 60% dimethylaminoethyl acrylate methyl base amino-ethyl ester, 6.3 part of 80% acrylic acid aqueous solution, 1.1 parts of methallylsulfonic acid sodium, 1.2 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making in the system is 55 ℃, under agitation adds 0.28 part of polymerization initiator ammonium persulfate and 20 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 400 parts of ion exchange waters, obtain solid constituent 15.2%, viscosity (25 ℃) is 10, the aqueous copolymers solution of 000mPas.
Production Example 2-9
With the same reaction unit of Production Example 2-1 in, add 540 parts of 82.6 parts of acrylamides, 7 part of 62.5% sulfuric acid, 14.1 parts of dimethylaminoethyl acrylate methyl base amino-ethyl esters, 2.5 parts of itaconic acids, 0.2 part of methallylsulfonic acid sodium, 0.6 part of DMAA, 0.02 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making in the system is 55 ℃, under agitation adds 0.14 part of polymerization initiator ammonium persulfate and 10 parts of ion exchange waters and 0.06 part of sodium hydrogensulfite and 10 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.2 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 330 parts of ion exchange waters, obtain solid constituent 10.2%, viscosity (25 ℃) is 10, the aqueous copolymers solution of 000mPas.
Production Example 2-10
With the same reaction unit of Production Example 2-1 in, add 430 parts of 41.3 parts of acrylamides, 3.5 part of 62.5% sulfuric acid, 7 parts of dimethylaminoethyl acrylate methyl base amino-ethyl esters, 1.3 parts of itaconic acids, 0.05 part of methallylsulfonic acid sodium, 0.3 part of DMAA, 0.01 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making in the system is 55 ℃, under agitation adds 0.07 part of polymerization initiator ammonium persulfate and 10 parts of ion exchange waters and 0.03 part of sodium hydrogensulfite and 10 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.1 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 490 parts of ion exchange waters, obtain solid constituent 5.2%, viscosity (25 ℃) is 15, the aqueous copolymers solution of 000mPas.
Production Example 2-11
With the same reaction unit of Production Example 2-1 in, add 340 parts of 33.1 parts of acrylamides, 2.8 part of 62.5% sulfuric acid, 5.6 parts of dimethylaminoethyl acrylate methyl base amino-ethyl esters, 1 part of itaconic acid, 0.01 part of methallylsulfonic acid sodium, 0.3 part of DMAA, 0.01 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making in the system is 55 ℃, under agitation adds 0.06 part of polymerization initiator ammonium persulfate and 10 parts of ion exchange waters and 0.02 part of sodium hydrogensulfite and 10 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.08 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 910 parts of ion exchange waters, obtain solid constituent 3.2%, viscosity (25 ℃) is 15, the aqueous copolymers solution of 000mPas.
Production Example 2-12
With the same reaction unit of Production Example 2-1 in, add 740 parts of the season thing aqueous solution of 140.1 parts of acrylamides, 76.6 part of 60% dimethylaminoethyl acrylate methyl base amino-ethyl ester, 14.6 part of 80% acrylic acid aqueous solution, 1.1 parts of methallylsulfonic acid sodium, 1.2 parts of DMAAs, 0.04 part of methylene diacrylamine and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making in the system is 55 ℃, under agitation adds 0.28 part of polymerization initiator ammonium persulfate and 20 parts of ion exchange waters.Be incubated 30min after being warming up to 90 ℃, add 0.4 part of ammonium persulfate and 10 parts of ion exchange waters, insulation 1h.After polymerization is over, add 290 parts of ion exchange waters, obtain solid constituent 15.2%, viscosity (25 ℃) is 10, the aqueous copolymers solution of 000mPas.
Production Example 2-13
With the same reaction unit of Production Example 2-1 in, add 650 parts of 124 parts of acrylamides, 22 part of 80% acrylic acid aqueous solution, 26 parts of acrylonitrile and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making in the system is 40 ℃, under agitation adds 0.23 part of polymerization initiator ammonium persulfate and 10 parts of ion exchange waters and 0.09 part of sodium hydrogensulfite and 10 parts of ion exchange waters.Be incubated 2h after being warming up to 90 ℃.After polymerization is over, add 270 parts of ion exchange waters, obtain solid constituent 15.2%, viscosity (25 ℃) is 5, the aqueous copolymers solution of 000mPas.
Production Example 2-14
With the same reaction unit of Production Example 2-1 in, add 440 parts of 73 parts of acrylamides, 10 part of 80% acrylic acid aqueous solution and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making in the system is 40 ℃, under agitation adds 0.1 part of polymerization initiator ammonium persulfate and 10 parts of ion exchange waters and 0.1 part of sodium hydrogensulfite and 10 parts of ion exchange waters.Be incubated 1h after being warming up to 90 ℃.Be cooled to 40 ℃ after adding 360 parts of ion exchange waters, add 0.4 part of 48% NaOH, 49 part of 50% dimethylamine, 37 part of 37% formalin, insulation 1h.After polymerization is over, add 180 parts of ion exchange waters, obtain solid constituent 10.2%, viscosity (25 ℃) is 10, the aqueous copolymers solution of 000mPas.
Production Example 2-15
With the same reaction unit of Production Example 2-1 in, add 393 parts of 71.7 parts of acrylamides and ion exchange waters, after logical nitrogen is removed oxygen in the reaction system, making in the system is 40 ℃, under agitation adds 0.15 part of polymerization initiator ammonium persulfate and 10 parts of ion exchange waters and 0.15 part of sodium hydrogensulfite and 10 parts of ion exchange waters.Be incubated 1h after being warming up to 90 ℃.Be cooled to after 20 ℃, adding 251.7 part of 12% clorox and 33.8 part of 48% NaOH, insulation 30min.After polymerization is over, add 395 parts of ion exchange waters, obtain pH4.0, active ingredient 5.0%, viscosity (25 ℃) and be the aqueous copolymers solution of 20mPas.
[table 5]
| Composition (a) | Composition (b) | Composition (c) | Composition (d) | Composition (e) | Composition (f) | Anion/cation ratio | |
| Production Example 2-1 | AM 90.49 | DM 5 | AA 3 | 1 | 0.5 | MBAA 0.01 | 0.60 |
| Production Example 2-2 | AM 92.09 | DM 5 | IA 1.5 | 1 | 0.4 | MBAA 0.01 | 0.60 |
| Production Example 2-3 | AM 92.09 | DML 5 | IA 1.5 | 1 | 0.4 | MBAA 0.01 | 0.60 |
| Production Example 2-4 | AM 92.35 | DM 5 | IA 1.5 | 1 | 0.15 | - | 0.60 |
| Production Example 2-5 | AM 93.50 | DM 5 | IA 1.5 | - | - | - | 0.60 |
| Production Example 2-6 | AM 91.34 | DM 5 | IA 2.3 | 1 | 0.35 | MBAA 0.01 | 0.92 |
| Production Example 2-7 | AM 89.09 | DMAEA-BQ 7 | AA 3 | 0.5 | 0.4 | MBAA 0.01 | 0.43 |
| Production Example 2-8 | AM 89.19 | DML 7 | AA 3 | 0.5 | 0.3 | MBAA0.01 | 0.43 |
| Production Example 2-9 | AM 90.89 | DM 7 | IA 1.5 | 0.5 | 0.1 | MBAA 0.01 | 0.43 |
| Production Example 2-10 | AM 90.94 | DM 7 | IA 1.5 | 0.5 | 0.05 | MBAA 0.01 | 0.43 |
| Production Example 2-11 | AM 90.98 | DM 7 | IA 1.5 | 0.5 | 0.01 | MBAA 0.01 | 0.43 |
| Production Example 2-12 | AM 85.19 | DML 7 | AA 7 | 0.5 | 0.3 | MBAA 0.01 | 1.00 |
| Production Example 2-13 | AM 70.00 | - | AA 10 | - | - | AN 20 | - |
| Production Example 2-14 | AM 50.00 | Mn 40 | AA 10 | - | - | - | 0.25 |
| Production Example 215 | AM 60.00 | Hf 40 | - | - | - | - | - |
Numeral in the table is mol%, and the Mn of Production Example 2-14 represents the Mannich degree of modification, and the Hf of Production Example 2-15 represents the Huffman degree of modification.
[table 6]
| Beating degree (ml) | Nonvolatile matter (%) | Viscosity (mPas) | 5% viscosity (mPas) | Weight average molecular weight | |
| Production Example 2-1 | 10 | 20 | 8000 | 40 | 3,000,000 |
| Production Example 2-2 | 30 | 20 | 8000 | 40 | 3,000,000 |
| Production Example 2-3 | 80 | 20 | 8000 | 40 | 2,000,000 |
| Production Example 2-4 | 50 | 10 | 10000 | 500 | 1,500,000 |
| Production Example 2-5 | 50 | 10 | 10000 | 500 | 500,000 |
| Production Example 2-6 | 30 | 20 | 8000 | 40 | 3,000,000 |
| Production Example 2-7 | 30 | 20 | 8000 | 40 | 1,000,000 |
| Production Example 2-8 | 80 | 15 | 10000 | 250 | 1,000,000 |
| Production Example 2-9 | 120 | 10 | 10000 | 500 | 1,500,000 |
| Production Example 2-10 | 180 | 5 | 15000 | 15000 | 1,700,000 |
| Production Example 2-11 | 250 | 3 | 15000 | 70000 | 2,000,000 |
| Production Example 2-12 | 80 | 15 | 10000 | 250 | 1,000,000 |
| Production Example 2-13 | - | 15 | 5000 | 120 | 400,000 |
| Production Example 2-14 | - | 10 | 10000 | 500 | 1,000,000 |
| System 13+ system 14 | 100 | - | - | - | - |
| Production Example 2-15 | 80 | 5 | 20 | 20 | 500,000 |
Viscosity gauge is shown in 25 ℃ measured value.
The nonvolatile matter of Production Example 2-15 is represented active ingredient, and weight average molecular weight is the measured value of the polymer before the modification.
The mixture of system 13+ system 14 expression Production Example 2-13 and Production Example 2-14.Production Example 2-13/ Production Example 2-14=2/1 (weight ratio).
Embodiment 2-1
Old corrugated board is pulled an oar in the formula beater of Niagara, in the paper stock that is adjusted into canadian standard freeness (C.S.F.) 350mL, add 1.0% aluminum sulfate, pH is adjusted to 6.5.When this paper stock slurry is copied paper, copy paper in the following manner: making paper stock concentration is 3.0%, adding with respect to the paper stock solid weight 0.35% as paper power reinforcing agent by the resulting aqueous solutions of polymers of Production Example 2-1, then, making paper stock concentration is 1.5%, adding with respect to paper stock weight 0.15% as paper power reinforcing agent by the resulting aqueous solutions of polymers of Production Example 2-8, in latch needles jacquard weave gear piece machine, dewater, at 5kg/cm
2Press down 2min, make the level ground amount be 150g/m
2Then, at 105 ℃ of dry 4min, damping 24h under 23 ℃, 50% relative humidity condition measures it and compares rupture strength with rotary drier.
Embodiment 2-2～8, comparative example 2-1～4
Except employed paper power reinforcing agent, paper stock concentration when adding paper power reinforcing agent press change shown in the table 7, carry out mensuration equally with embodiment 2-1 than rupture strength, the results are shown in table 7.
[table 7]
| At the use paper power reinforcing agent that adds place 1 | Adding rate is (%) 1. | At the use paper power reinforcing agent that adds place 2 | Adding rate is (%) 2. | Adding rate is than (1./2.) | Drainage amount (ml) | Compare rupture strength | |
| Embodiment 2-1 | Production Example 2-1 | 0.35 | Production Example 2-8 | 0.15 | 2.33 | 385 | 2.95 |
| Embodiment 2-2 | Production Example 2-1 | 0.40 | Production Example 2-10 | 0.10 | 4.00 | 405 | 2.90 |
| Embodiment 2-3 | Production Example 2-4 | 0.35 | Production Example 2-8 | 0.15 | 2.33 | 398 | 2.92 |
| Embodiment 2-4 | Production Example 2-5 | 0.35 | Production Example 2-8 | 0.15 | 2.33 | 377 | 2.86 |
| Embodiment 2-5 | Production Example 2-1 | 0.05 | Production Example 2-8 | 0.45 | 0.11 | 427 | 2.84 |
| Embodiment 2-6 | Production Example 2-1 | 0.40 | Production Example 2-11 | 0.10 | 4.00 | 419 | 2.89 |
| Embodiment 2-7 | Production Example 2-1 | 0.35 | System 13+ system 14 | 0.15 | 2.33 | 388 | 2.87 |
| Embodiment 2-8 | Production Example 2-1 | 0.35 | Production Example 2-15 | 0.15 | 2.33 | 383 | 2.89 |
| Embodiment 2-9 | Production Example 2-8 | 0.15 | Production Example 2-1 | 0.35 | 0.43 | 395 | 2.85 |
| Comparative example 2-1 | Production Example 2-6 | 0.35 | Production Example 2-12 | 0.15 | 2.33 | 397 | 2.72 |
| Comparative example 2-2 | Production Example 2-2 | 0.35 | Production Example 2-12 | 0.15 | 2.33 | 399 | 2.71 |
| Comparative example 2-3 | Production Example 2-2 | 0.35 | Production Example 2-7 | 0.15 | 2.33 | 371 | 2.77 |
| Comparative example 2-4 | Production Example 2-3 | 0.35 | Production Example 2-8 | 0.15 | 2.33 | 447 | 2.62 |
In the table, the system 13+ system 14 expression Production Example 2-13 of embodiment 2-15 and the mixture of Production Example 2-14, Production Example 2-13/ Production Example 2-14=2/1 (weight ratio).
Being again, is 3.0% in the paper stock concentration that adds place 1, is 1.5% in the paper stock concentration that adds place 2.
Embodiment 2-9
Old corrugated paper is pulled an oar in the formula beater of Niagara, in the paper stock that is adjusted into canadian standard freeness (C.S.F.) 305mL, add 1.0% aluminum sulfate, pH is adjusted to 6.5.When this paper stock slurry is copied paper, copy paper in the following manner: making paper stock concentration is 2.0%, adding with respect to the paper stock solid weight 1.0% as paper power reinforcing agent by the resulting aqueous solutions of polymers of Production Example 2-1, then, making paper stock concentration is 1.0%, adding with respect to paper stock weight 0.2% as paper power reinforcing agent by the resulting aqueous solutions of polymers of Production Example 2-9, in latch needles jacquard weave gear piece machine, dewater, at 5kg/cm
2Press down 2min, make the level ground amount be 150g/m
2Then, at 105 ℃ of dry 4min, damping 24h under 23 ℃, 50% relative humidity condition measures it and compares rupture strength with rotary drier.
Embodiment 2-10～18, comparative example 2-5～8
Except employed paper power reinforcing agent, paper stock concentration when adding paper power reinforcing agent press change shown in the table 8, carry out mensuration equally with embodiment 2-9 than rupture strength, the results are shown in table 8.
[table 8]
| At the use paper power reinforcing agent that adds place 1 | Adding rate is (%) 1. | At the use paper power reinforcing agent that adds place 2 | Adding rate is (%) 2. | Adding rate is than (1./2.) | Drainage amount (ml) | Compare rupture strength | |
| Embodiment 2-10 | Production Example 2-2 | 1.00 | Production Example 2-9 | 0.20 | 5.00 | 340 | 4.03 |
| Embodiment 2-11 | Production Example 2-2 | 1.05 | Production Example 2-10 | 0.15 | 7.00 | 359 | 3.99 |
| Embodiment 2-12 | Production Example 2-4 | 1.00 | Production Example 2-9 | 0.20 | 5.00 | 357 | 3.96 |
| Embodiment 2-13 | Production Example 2-5 | 1.00 | Production Example 2-9 | 0.20 | 5.00 | 332 | 3.89 |
| Embodiment 2-14 | Production Example 2-2 | 0.15 | Production Example 2-9 | 1.05 | 0.14 | 385 | 3.85 |
| Embodiment 2-15 | Production Example 2-2 | 1.05 | Production Example 2-11 | 0.15 | 7.00 | 361 | 3.88 |
| Embodiment 2-16 | Production Example 2-2 | 1.00 | System 13+ system 14 | 0.20 | 5.00 | 350 | 3.85 |
| Embodiment 2-17 | Production Example 2-2 | 1.00 | Production Example 2-15 | 0.20 | 5.00 | 344 | 3.87 |
| Embodiment 2-18 | Production Example 2-9 | 0.20 | Production Example 2-2 | 1.00 | 0.20 | 356 | 3.86 |
| Comparative example 2-5 | Production Example 2-6 | 1.00 | Production Example 2-12 | 0.20 | 5.00 | 345 | 3.70 |
| Comparative example 2-6 | Production Example 2-4 | 1.00 | Production Example 2-12 | 0.20 | 5.00 | 347 | 3.69 |
| Comparative example 2-7 | Production Example 2-2 | 1.00 | Production Example 2-7 | 0.20 | 5.00 | 321 | 3.77 |
| Comparative example 2-8 | Production Example 2-3 | 1.00 | Production Example 2-8 | 0.20 | 5.00 | 403 | 3.60 |
In the table, the system 13+ system 14 expression Production Example 2-13 of embodiment 2-15 and the mixture of Production Example 2-14, Production Example 2-13/ Production Example 2-14=2/1 (weight ratio).
Being again, is 2.0% in the paper stock concentration that adds place 1, is 1.0% in the paper stock concentration that adds place 2.
By table 7 and table 8 as can be known, with the difference of the beating degree that adds nonionic polyacrylamides paper strength agent and before and after the paper stock reinforcing agent adds, measure according to JIS P 8121 than the prescription of the big nonionic polyacrylamides paper strength agent of nonionic polyacrylamides paper strength agent or add anionic polyacrylamides paper strength agent and the difference of the beating degree measured according to JIS P8121 is compared than the prescription of the big nonionic polyacrylamides paper strength agent of anionic polyacrylamides paper strength agent before and after the paper stock reinforcing agent adds, use the present invention, can make the high paper of paper force intensity (embodiment 2-1～18 easily, comparative example 2-1,2,5,6).Be that the ratio of composition (B-1)/composition (B-2) has further improved paper power effect (embodiment 2-1 and 5,10 and 14) 0.2 when above again.And then, composition (B-1) is added during in paper stock concentration less than 2.0% at paper stock concentration more than 2.0%, composition (B-2), make paper power effect obtain bigger raising (embodiment 2-1 and 9,10 and 18).The weight average molecular weight of composition (B-1) has improved paper power and has strengthened effect (embodiment 2-1 and 5,10 and 13) 1,000,000 when above.5 weight % viscosity in aqueous solution of composition (B-2) when 000mPas is following, can reduce the quality confusion 20, improve paper power effect (embodiment 2-1 and 6,10 and 15).Even different composition (B-1) is added more than 2.0% and adds less than 2.0% o'clock in paper stock concentration in paper stock concentration, also do not obtain sufficient paper power effect (embodiment 2-1～18, comparative example 2-3,7).Also have, even different composition (B-2) is added 2.0% or more and do not obtain sufficient paper power effect (embodiment 2-1～18, comparative example 2-4,8) in paper stock concentration less than adding in 2.0% o'clock in paper stock concentration.
Claims (14)
1. papermaking process, it is characterized in that, use the nonionic polyacrylamides paper strength agent (A) and the difference of the beating degree of before and after adding paper power reinforcing agent, measuring anionic polyacrylamides paper strength agent (B) or the anionic property polyacrylamide paper power reinforcing agent (C) bigger to copy paper than nonionic polyacrylamides paper strength agent (A) by JIS P 8121.
2. the papermaking process described in the claim 1, wherein, described nonionic polyacrylamides paper strength agent (A) is to be material below the 50mL in the difference that adds the beating degree of measuring by JIS P 8121 before and after the paper power reinforcing agent, and described anionic polyacrylamides paper strength agent (B) or anionic property polyacrylamide paper power reinforcing agent (C) are the materials that surpasses 50mL in the difference that adds the beating degree of measuring by JISP 8121 before and after the paper power reinforcing agent.
3. the papermaking process described in the claim 1, wherein, the weight average molecular weight of described nonionic polyacrylamides paper strength agent (A) is more than 1,000,000.
4. the papermaking process described in the claim 1, wherein, described nonionic polyacrylamides paper strength agent (A) is that place more than the 2.0 weight % adds and described anionic polyacrylamides paper strength agent (B) or anionic property polyacrylamide paper power reinforcing agent (C) add in the place of paper stock concentration less than 2.0 weight % in paper stock concentration.
5. the papermaking process described in the claim 1, wherein, the solid constituent weight ratio (A) of the consumption of the consumption of described nonionic polyacrylamides paper strength agent (A) and described anionic polyacrylamides paper strength agent (B) or anionic property polyacrylamide paper power reinforcing agent (C)/((B) or (C)) is more than 0.2.
6. the papermaking process described in the claim 1, wherein, viscosity when described nonionic polyacrylamides paper strength agent (A) contains the above nonvolatile matter of 5 weight % and its aqueous solution that is modulated into 5 weight % with described anionic polyacrylamides paper strength agent (B) or anionic property polyacrylamide paper power reinforcing agent (C) is 20, below the 000mPas.
7. each described papermaking process in the claim 1～6, wherein, described nonionic polyacrylamides paper strength agent (A) and described anionic polyacrylamides paper strength agent (B) or anionic property polyacrylamide paper power reinforcing agent (C) all contain polymer, and this polymer is by with (a) (methyl) acrylamide, (b) cationic vinyl monomer, (c) anionic property vinyl monomer, (d) N-replaces (methyl) acrylamide, (e) (methyl) sodium allylsulfonate obtains for (a)～(e) composition vinyl monomer (f) copolymerization in addition of must composition and being added as required.
8. papermaking process, it is characterized in that, use the anionic polyacrylamides paper strength agent (B-1) and the difference of the beating degree of before and after adding paper power reinforcing agent, the measuring anionic polyacrylamides paper strength agent (B-2) bigger to copy paper than nonionic polyacrylamides paper strength agent (B-1) by JIS P 8121.
9. the papermaking process described in the claim 8, wherein, described anionic polyacrylamides paper strength agent (B-1) is to be material below the 50mL in the difference that adds the beating degree of measuring by JIS P 8121 before and after the paper power reinforcing agent, and described anionic polyacrylamides paper strength agent (B-2) is the material that surpasses 50mL in the difference that adds the beating degree of measuring by JIS P 8121 before and after the paper power reinforcing agent.
10. the papermaking process described in the claim 8, wherein, the weight average molecular weight of described anionic polyacrylamides paper strength agent (B-1) is more than 1,000,000.
11. the papermaking process described in the claim 8, wherein, be that place more than the 2.0 weight % adds and described anionic polyacrylamides paper strength agent (B-2) adds in the place of paper stock concentration less than 2.0 weight % at described anionic polyacrylamides paper strength agent (B-1) in paper stock concentration.
12. the papermaking process described in the claim 8, wherein, the solid constituent weight ratio (B-1)/(B-2) of the consumption of the consumption of described anionic polyacrylamides paper strength agent (B-1) and described anionic polyacrylamides paper strength agent (B-2) is more than 0.2.
13. the papermaking process described in the claim 8, wherein, viscosity when described anionic polyacrylamides paper strength agent (B-1) contains the above nonvolatile matter of 5 weight % and its aqueous solution that is modulated into 5 weight % with described anionic polyacrylamides paper strength agent (B-2) is 20, below the 000mPas.
14. each described papermaking process in the claim 8～13, wherein, described anionic polyacrylamides paper strength agent (B-1) and described anionic polyacrylamides paper strength agent (B-2) all contain polymer, this polymer by replace with (a) (methyl) acrylamide, (b) cationic vinyl monomer, (c) anionic property vinyl monomer, (d) N-(methyl) acrylamide, (e) (methyl) sodium allylsulfonate serve as must composition and (a)～(e) composition vinyl monomer (f) copolymerization in addition of being added as required obtain.
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| JP2005319270A JP4817109B2 (en) | 2005-11-02 | 2005-11-02 | Paper manufacturing method |
| JP2005319271A JP4784857B2 (en) | 2005-11-02 | 2005-11-02 | Paper manufacturing method |
| JP2005319271 | 2005-11-02 | ||
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| JP5709043B2 (en) * | 2010-03-31 | 2015-04-30 | 荒川化学工業株式会社 | Water-soluble polymer dispersion, paper strength enhancer, paper drainage improver and paper yield improver |
| CN104452455B (en) | 2013-09-12 | 2019-04-05 | 艺康美国股份有限公司 | The method that paper making auxiliary agent composition and increase are stayed at paper ash code insurance |
| CN104452463B (en) | 2013-09-12 | 2017-01-04 | 艺康美国股份有限公司 | Papermaking process and compositions |
| JP6268519B2 (en) * | 2013-12-12 | 2018-01-31 | 荒川化学工業株式会社 | Surface paper strength enhancer for papermaking and surface coated paper |
| FI126610B (en) | 2015-01-27 | 2017-03-15 | Kemira Oyj | Particulate polymer product and its use |
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| US6168686B1 (en) * | 1998-08-19 | 2001-01-02 | Betzdearborn, Inc. | Papermaking aid |
| JP2001020198A (en) * | 1999-07-09 | 2001-01-23 | Seiko Kagaku Kogyo Co Ltd | Papermaking additive |
| JP4232189B2 (en) * | 2002-11-12 | 2009-03-04 | 荒川化学工業株式会社 | Paper manufacturing method |
| JP2004300629A (en) * | 2003-03-31 | 2004-10-28 | Arakawa Chem Ind Co Ltd | Additive for papermaking and paper using additive for papermaking |
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