JPH093793A - Additive for papermaking and process for producing copolymer useful therefor - Google Patents

Abstract

(57) Abstract: A papermaking additive comprising a copolymer obtained by reacting a diallylamine compound with a (meth) acrylamide compound and having a relatively high molecular weight but an aqueous solution having a relatively low viscosity. And an industrially advantageous method for producing the copolymer. A papermaking additive containing a diallylamine-based compound, a (meth) acrylamide-based compound and a crosslinkable vinyl monomer, or a copolymer having an unsaturated carboxylic acid-based compound as a constituent monomer. This copolymer is prepared by continuously adding an acrylamide compound and a chain transfer agent to an aqueous solution containing a diallylamine compound, or further continuously adding an unsaturated carboxylic acid compound in the presence of a crosslinkable vinyl monomer. It is advantageous to produce by reacting with. [Effect] This papermaking additive achieves a high paper strength enhancing effect and drainage improving effect without disturbing the texture of the paper.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a papermaking additive. More specifically, it relates to a paper-making additive containing a poly (meth) acrylamide-based cationic or amphoteric copolymer as an active ingredient and a method for producing the copolymer.

[0002]

2. Description of the Related Art In recent years, papermaking additives, especially paper strength enhancers, have been regarded as important in the production of paper and paperboard.
This is because the use of high-quality pulp has been restricted due to the deterioration of the situation of supply of raw wood, and the necessity of reusing recycled paper has become stronger for the purpose of energy saving and resource saving. As a result, papermaking additives as paper and paperboard modifiers have become even more essential.

On the other hand, for the purpose of improving the productivity with the speeding up of paper machines or improving the quality according to the diversification of paper, the dependence on the drainage improver and the paper strength enhancer and the range of use thereof are further increased. It is widespread. Under such circumstances, poly (meth) acrylamide-based additives are predominantly used as papermaking additives.

The poly (meth) acrylamide-based papermaking additives can be classified into anionic type and cationic or amphoteric type according to their ionicity. Examples of the anion type include (meth) acrylamide and α, β-unsaturated monocarboxylic acid or α, which is an anionic vinyl monomer.
A copolymer with β-unsaturated dicarboxylic acid, a partial hydrolyzate of a (meth) acrylamide-based copolymer, and the like are known. On the other hand, the cation or amphoteric type includes a modified type and a copolymerized type based on the difference in the method of introducing an ionic functional group. Modification types include, for example, Huffman rearrangement products and Mannich modified products of (meth) acrylamide-based copolymers, while copolymerization types include, for example, cationic vinyl monomers and (meth) acrylamide, and, if necessary, Various copolymers obtained by copolymerizing an anionic vinyl monomer or other copolymerizable nonionic vinyl monomer are known (JP-A-60-94).
697 publication).

[0005]

However, in recent years, since the conditions for using papermaking additives have become more and more severe, the effect of the conventionally known poly (meth) acrylamide-based papermaking additives as an additive has been improved. Has come to the limit. Therefore, measures such as increasing the molecular weight are taken in order to improve the performance, but simply increasing the molecular weight causes an excessive increase in the viscosity of the aqueous copolymer solution, resulting in poor dispersibility during papermaking and There is a problem that the paper or paperboard to be used causes disorder of the formation. In such a situation, no satisfactory additive for papermaking has been obtained so far.

[0006] The present invention provides a papermaking additive containing a high-molecular weight (meth) acrylamide copolymer obtained by reacting a specific cationic monomer and forming an aqueous solution having a relatively low viscosity. With the goal.

Another object of the present invention is to provide a method for industrially advantageously producing a water-soluble copolymer useful as such a papermaking additive.

[0008]

Means for Solving the Problems That is, the present invention provides a papermaking additive containing a copolymer having at least the following three components (A), (B) and (X) as constituent monomers. Is.

(A) General formula (I)

[0010]

(In the formula, R ¹ and R ² each independently represent hydrogen or methyl, R ³ and R ⁴ each independently represent hydrogen, alkyl having 1 to 8 carbons, or aralkyl;
X ^- diallylamine compounds represented by represents an anion of an acid), (B) the general formula (II)

[0012]

(Wherein R ⁵ represents hydrogen or methyl, and R ^5
6 and R ⁷ each independently represent hydrogen or alkyl having 1 to 4 carbon atoms), and (X) a crosslinkable vinyl monomer.

This copolymer is essentially the above diallylamine compound (A) and acrylamide compound (B).
And a cross-linkable vinyl monomer (X), which is a copolymer of three components. In this case, a cationic copolymer is obtained. Further, these constituent monomers may further contain a fourth comonomer, for example, an unsaturated carboxylic acid selected from α, β-unsaturated monocarboxylic acid, α, β-unsaturated dicarboxylic acid and salts thereof. A system compound (C) can be contained. When an unsaturated carboxylic acid compound (C) is used in addition to the diallylamine compound (A), the acrylamide compound (B) and the crosslinkable vinyl monomer (X), an amphoteric copolymer is obtained.

The method for producing these copolymers is not particularly limited, and, for example, it is possible to charge all the constituent monomers and then polymerize. However, in the present invention,
It is preferable to polymerize while continuously supplying a part of the constituent monomers by the following method.

Therefore, the present invention also provides an aqueous solution containing the diallylamine compound (A) represented by the general formula (I), the acrylamide compound (B) represented by the general formula (II) and the chain transfer agent (E). ) Is continuously added and reacted in the presence of the crosslinkable vinyl monomer (X) to provide a method for producing a copolymer.

At this time, the crosslinkable vinyl monomer (X) is
It may be allowed to exist in an aqueous solution containing the diallylamine compound (A) or continuously added to the aqueous solution containing the diallylamine compound (A) together with the acrylamide compound (B) and the chain transfer agent (E). You can also do it. In addition, α, β-unsaturated monocarboxylic acid, α, β-
An unsaturated carboxylic acid compound (C) selected from unsaturated dicarboxylic acids and salts thereof can be further used as a part of the constituent monomers. In this case, the unsaturated carboxylic acid compound (C) is the diallylamine compound. It is preferable to continuously add to the aqueous solution containing the compound (A).

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the diallylamine compound (A) represented by the general formula (I), which is one of the essential constituent monomers, is a secondary amine salt, a tertiary amine salt or a It is a high-grade ammonium salt. In the general formula (I), R ¹ and R ² are each independently hydrogen or methyl, R ³ and R ⁴ are independently hydrogen, and have 1 to 1 carbon atoms.
8 alkyl or aralkyl, examples of alkyl include methyl, ethyl, propyl, butyl, hexyl and the like, and examples of aralkyl include benzyl and the like. The anion represented by X ⁻ may be an anion of inorganic acid or organic acid. Among the acids represented by HX and constituting the salt of the general formula (I), examples of inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, and the like, and organic acids include formic acid and acetic acid. , Oxalic acid,
Propionic acid etc. are illustrated. Therefore, in the general formula (I), the anion represented by X ⁻ is a chloride ion,
It may be bromide ion, sulfate ion, phosphate ion, nitrate ion, formate ion, acetate ion, oxalate ion, propionate ion and the like.

Of the diallylamine compounds (A) represented by the general formula (I), the secondary amine salt is specifically exemplified by an inorganic or organic acid salt of diallylamine or dimethallylamine. Specific examples of the tertiary amine salt include inorganic or organic acid salts such as diallylmethylamine, diallylethylamine and diallylbutylamine. Specific examples of the quaternary ammonium salt include diallyldimethylammonium chloride, diallyldimethylammonium sulfate, diallyldimethylammonium bromide, diallyldiethylammonium chloride, diallyldibutylammonium chloride and diallylmethylethylammonium chloride. These diallylamine compounds (A) can be used alone or in combination of two or more.

The above-mentioned general formula (II) representing the acrylamide compound (B) which is another essential constituent monomer.
Wherein R ⁵ is hydrogen or methyl, and R ⁶ and R ^{7 are}
Are each independently hydrogen or alkyl having 1 to 4 carbon atoms, and examples of alkyl include methyl, ethyl, propyl, butyl and the like. Specific examples of the acrylamide compound (B) represented by the general formula (II) include acrylamide, methacrylamide, N-methylacrylamide, N-ethylmethacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-butylacrylamide. , N, N-dimethylacrylamide and the like. These acrylamide compounds (B) can be used alone or in combination of two or more.

Further, of the unsaturated carboxylic acid compounds (C) which can optionally be constituent monomers, specific examples of unsaturated monocarboxylic acids are acrylic acid and methacrylic acid, and specific examples of unsaturated dicarboxylic acids are , Maleic acid, fumaric acid, itaconic acid and the like. Specific examples of salts include alkali metal salts such as sodium salts and potassium salts of these unsaturated carboxylic acids, and ammonium salts. When using these unsaturated carboxylic acid compounds (C), which are optional components, each compound may be used alone, or two or more kinds may be used in combination.

The crosslinkable vinyl monomer (X) used in the present invention is a compound having at least two polymerizable carbon-carbon double bonds in the molecule and having no cyclic structure during polymerization. As the bifunctional vinyl monomer having two polymerizable carbon-carbon double bonds, specifically, di (meth) acrylates such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, methylenebis ( (Meth) acrylamide, bis (meth) acrylamides such as ethylenebis (meth) acrylamide, divinyl adipate, divinyl esters such as divinyl sebacate, allyl methacrylate,
Examples include divinylbenzene. In addition, polymerizable carbon
Examples of the trifunctional vinyl monomer having three carbon double bonds include 1,3,5-triacryloylhexahydro-s.
-Triazine, triallyl isocyanurate, triallylamine, N, N-diallyl acrylamide, etc., and tetrafunctional vinyl monomers having four polymerizable carbon-carbon double bonds include tetramethylolmethane tetraacrylate and tetraallyl. Piromellitate, N,
Examples thereof include N, N ', N'-tetraallyl-1,4-diaminobutane and tetraallylammonium salt. Of these, triallylamine and N, N, N ', N'-
Amines such as tetraallyl-1,4-diaminobutane can be used in the form of a free amine or in the form of a salt, and the acid constituting the salt is the same as described above for the diallylamine compound (A). The acid used in the diallylamine-based compound (A) may be the same or different. These crosslinkable vinyl monomers (X) can be used alone or in combination of two or more. Among these,
Triallylamine or salts thereof, divinylbenzene and methylenebis (meth) acrylamide are preferred.

The papermaking additive according to the present invention comprises a diallylamine compound (A), an acrylamide compound (B) and a crosslinkable vinyl monomer (X) described above, or optionally a fourth comonomer such as an unsaturated carvone. The copolymer obtained by reacting the acid compound (C) is used as an active ingredient. In producing this copolymer, in addition to each of these constituent monomers, a chain transfer agent (E) is further added. Is preferably used. Specific examples of the chain transfer agent (E) include alcohols such as isopropanol, thiols such as butyl mercaptan,
In addition to low molecular weight compounds such as phosphorus compounds such as hypophosphite, high molecular weight compounds having at least two chain transfer functional groups in the molecule and having a weight average molecular weight of 1,000 or more can be mentioned. . The chain transfer functional group in the polymer chain transfer agent, refers to a functional group capable of chain transfer of radicals generated when polymerizing a vinyl monomer, for example, a hydroxyl group, an amino group, a carboxyl group, a carboxylic acid ester group, Carboxamide groups, epoxy groups and the like are included. Specific examples of the polymer chain transfer agent include polyethylene glycol, polypropylene glycol, polyethers such as polyglycerin, polyvinyl alcohol,
Polyvinylamine, polyacrylic acid or salts thereof, styrene / maleic acid copolymers or esters thereof, polysaccharides such as carboxymethyl cellulose, polyesters,
Examples thereof include polyamides such as polyamide polyamine and polyamide epoxy. The polyamide polyamine as used herein is a polymer having an amide bond and an amino group, and can be obtained, for example, by reacting a dibasic carboxylic acid, ureas and polyalkylene polyamines. Polyamide epoxy is a polymer having an amide bond and an epoxy group, and can be obtained, for example, by reacting a dibasic carboxylic acid, ureas and epihalohydrins. Among these chain transfer agents, low molecular weight compounds are preferably hypophosphite salts, and high molecular weight compounds are preferably polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyglycerin and polyamide epoxy. Of course, a low molecular weight chain transfer agent and a high molecular weight chain transfer agent can be used together.

In producing the copolymer according to the present invention, the total molar amount of the constituent monomers other than the crosslinkable vinyl monomer (X), that is, the diallylamine compound (A), the acrylamide compound (B), and the optional components Comonomers, such as unsaturated carboxylic acid compounds (C)
Based on the total molar amount of the diallylamine compound (A)
Is preferably 1 to 70 mol%, more preferably 5 to 50 mol%, and the ratio of the acrylamide compound (B) is preferably 30 mol% or more, especially 30 mol%.
To 99 mol%, more preferably 50 mol% or more, especially 5
It is 0 to 95 mol%. The unsaturated carboxylic acid compound (C) is preferably 0 to 20 mol% of the total of constituent monomers other than the crosslinkable vinyl monomer (X),
When the unsaturated carboxylic acid compound (C) is used, it is usually 1 mol% or more based on the total molar amount of the constituent monomers other than the crosslinkable vinyl monomer (X). The proportion of the crosslinkable vinyl monomer (X) is preferably 0.05 to 5 mol%, and more preferably 0.05 to 2 mol%, based on the total molar amount of the other constituent monomers. Further, when the chain transfer agent (E) is used, the proportion thereof is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total amount of the monomers. When the chain transfer agent (E) is a low molecular weight system such as hypophosphite, the crosslinkable vinyl monomer (X) is used in an amount of 0.005 to 1 based on the total molar amount of the other constituent monomers. It is preferably used in the range of 0.05 to 0.5 mol%, and when the chain transfer agent (E) is a polymer type, the crosslinkable vinyl monomer (X) is other than that. It is preferably used in the range of 0.01 to 5 mol%, more preferably 0.1 to 2 mol%, based on the total molar amount of the constituent monomers.

In carrying out the present invention, in addition to the above compounds (A), (B) and (X), or in addition to the compound (C), another monomer (D) copolymerizable with these compounds (D) is used. ) Can also be introduced. Examples of the monomer that can be the fourth component or the fifth component include (meth) acrylonitrile, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, styrene, nonionic monomers such as vinyl acetate, dimethylaminoethyl ( Examples thereof include cationic monomers such as (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and their quaternized products.

A usual initiator can be used in the polymerization. For example, persulfates such as ammonium persulfate and potassium persulfate, 2,2'-diamidino-2,2'-azodipropane dihydrochloride, azo compounds such as azobisisobutyronitrile, di-t-butyl peroxide. , Cumene hydroperoxide, peroxides such as hydrogen peroxide, and the like. Further, a known redox type initiator such as a combination of potassium persulfate and sodium bisulfite or a tertiary amine can be used.
The polymerization initiator is 0.01 to 5% by weight based on the total amount of the monomers.
It is preferably used, and more preferably 0.05 to 2% by weight. It is also possible to use a so-called chelating agent such as ethylenediaminetetraacetic acid or an alkali metal salt thereof as a scavenger of a transition metal existing or mixed in the polymerization system.

The polymerization is usually carried out at a temperature of 10 to 100 ° C., preferably 40 to 90 ° C. for about 1 to 15 hours. This polymerization reaction can be carried out in the presence of oxygen, but it is generally preferable to carry out in an atmosphere of an inert gas such as nitrogen gas.

In carrying out the copolymerization reaction of the present invention,
Prepare an aqueous solution containing the diallylamine compound (A),
An acrylamide compound (B) and a chain transfer agent (E) are continuously added thereto to form a crosslinkable vinyl monomer (X).
React in the presence of. At this time, the crosslinkable vinyl monomer (X) may be preliminarily present in the aqueous solution containing the diallylamine compound (A), or may be added to the aqueous solution containing the diallylamine compound (A) by adding the acrylamide compound ( It may be continuously added together with B) and the chain transfer agent (E). Of course, a part of the crosslinkable vinyl monomer (X) is allowed to exist in advance in an aqueous solution containing the diallylamine compound (A), and the rest is continuously added together with the acrylamide compound (B) and the chain transfer agent (E). It is also possible to adopt a mode in which it is added to.
The acrylamide compound (B) and the chain transfer agent (E), or the crosslinkable vinyl monomer (X), which are continuously added, are separately added to the aqueous solution containing the diallylamine compound (A). Alternatively, it may be added in the form of an aqueous solution containing any two or more of them. When the unsaturated carboxylic acid compound (C) is used, it is preferable that this compound (C) is also continuously added to the aqueous solution containing the diallylamine compound (A). Separately, or together with one or more other components, they can be added in the form of an aqueous solution.

The acrylamide compound (B) and the chain transfer agent (E), or the crosslinkable vinyl monomer (X) and / or the unsaturated carboxylic acid compound (C) may be added at a constant rate. However, it may be performed at different speeds. In addition, an appropriate time is selected from the range of about 30 minutes to 10 hours for each addition time.

The acrylamide compound (B), the chain transfer agent (E) and the unsaturated carboxylic acid compound (C) may be added in the form of each compound itself or in the form of an aqueous solution. Although good, it is generally used in the form of an aqueous solution.

Unless the purpose of the present invention is impaired,
A part of the acrylamide compound (B) and the chain transfer agent (E) and / or the unsaturated carboxylic acid compound (C) may be added to the system from the beginning of the polymerization reaction. Further, together with the diallylamine compound (A), the acrylamide compound (B) and the crosslinkable vinyl monomer (X), or with the diallylamine compound (A), the acrylamide compound (B), the crosslinkable vinyl monomer (X) and unsaturated. When another monomer (D) copolymerizable with them is used together with the carboxylic acid compound (C), this monomer (D) may be continuously added in the form of being mixed with all or part of other components. Alternatively, the components may be continuously added separately from the other components, or a part of them may be present in the system from the beginning of the polymerization reaction.

When any of the above-mentioned polymerization initiators and chelating agents is used, any of them may be added in advance to the aqueous solution containing the diallylamine compound (A), or other components. At the same time, it may be continuously added to the system. When a plurality of auxiliaries are used, the same addition method can be used for all auxiliaries, and of course, a separate addition method can be employed for each auxiliaries.

By the reaction as described above, the copolymer or the papermaking additive is obtained in the form of an aqueous solution. The copolymer or the additive for papermaking generally has a weight average molecular weight in the range of 10,000 to 10,000,000, and preferably in the range of 50,000 to 1,000,000.
More preferably, it is in the range of 100,000 to 500,000.

The copolymer or the additive for papermaking is used by adding it to the aqueous pulp slurry at the time of papermaking, and is usually added in an amount of about 0.01 to 3% by weight based on the weight of dry pulp. The papermaking itself is carried out according to a conventional method and can be applied to both so-called acidic papermaking and neutral papermaking. In papermaking, the papermaking additive of the present invention may be added to an aqueous pulp slurry and mixed well to make paper. At this time, agents used in ordinary papermaking, such as aluminum sulfate (so-called sulfuric acid band), A sizing agent, a size-fixing agent, a filler such as talc, titanium oxide, white carbon, calcium carbonate, other paper-strengthening agent, and a yield-improving agent may be added.

[0035]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples,% representing content or addition amount is
Unless otherwise particular, it is the weight%. The unreacted monomer was quantified by analysis using gas chromatography and liquid chromatography, and pH and viscosity were measured at 25 ° C.

Example 1 In a four-necked flask equipped with a thermometer, a stir bar and a reflux condenser, 29.2 g (0.1%) of a 50% diallylamine sulfate aqueous solution was added.
Mol), 0.8 g of a 35% triallylamine sulfate aqueous solution and 151 g of ion-exchanged water were charged, and the pH was adjusted to 3.0 with sulfuric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 65 ° C. 570 mg of ammonium persulfate was added, and the internal temperature was adjusted to 60-70.
While maintaining at ℃, 56.9g of 50% acrylamide aqueous solution
(0.4 mol) and 1% aqueous solution of sodium hypophosphite 5
0.5 g was added dropwise in parallel to the reaction system over 3 hours. Then, the temperature was kept at 60 to 70 ° C. for 5 hours to complete the reaction.

The reaction rate of diallylamine sulfate was 95% and the reaction rate of acrylamide was 99% or more according to the amount of unreacted monomer. The product was an aqueous solution containing 15% of a polymer component and had a pH of 3.1 and a viscosity of 32 ps.

Example 2 In the same apparatus as used in Example 1, 27.0 g (0.1 mol) of 60% diallyldimethylammonium chloride aqueous solution, 0.8 g of 35% triallylamine hydrochloride aqueous solution and 72 g of ion-exchanged water. Was charged and the pH was adjusted to 3.0 with hydrochloric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 65 ° C. 570 mg of ammonium persulfate was added, and the internal temperature was 60-70 ° C.
28.4 g (0.4 mol) of acrylamide while maintaining
And 79 g of an aqueous solution containing 370 mg of sodium hypophosphite
Was dropped into the reaction system over 4 hours. Then 60-7
The reaction was completed by incubating at 0 ° C for 5 hours.

The reaction rate of diallyldimethylammonium chloride was 99% and the reaction rate of acrylamide was 99% or more according to the quantification of unreacted monomers. The product was an aqueous solution containing 25% of a polymer component and had a pH of 3.2 and a viscosity of 68 ps.

Example 3 In the same apparatus as used in Example 1, 43.9 g (0.15 mol) of a 50% diallylamine sulfate aqueous solution, 0.8 g of a 35% triallylamine sulfate aqueous solution and 68 g of ion exchanged water.
Was charged and the pH was adjusted to 3.0 with sulfuric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 65 ° C. Ammonium persulfate 340
mg was added and 76 g of an aqueous solution containing 24.9 g (0.35 mol) of acrylamide and 850 mg of sodium hypophosphite was added dropwise to the reaction system while maintaining the internal temperature at 60 to 70 ° C. . Then, the temperature was kept at 60 to 70 ° C. for 5 hours to complete the reaction.

The reaction rate of diallylamine sulfate was 93% and the reaction rate of acrylamide was 99% or more according to the quantification of unreacted monomers. The product was an aqueous solution containing 25% of a polymer component and had a pH of 3.0 and a viscosity of 25 ps.

Example 4 In the same apparatus as used in Example 1, 40.4 g (0.15 mol) of 60% diallyldimethylammonium chloride aqueous solution, 0.8 g of 35% triallylamine hydrochloride aqueous solution and 56 g of ion-exchanged water. Was charged and the pH was adjusted to 3.0 with hydrochloric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 65 ° C. 340 mg of ammonium persulfate was added, and the internal temperature was 60-70 ° C.
Keeping at 50%, 50% acrylamide aqueous solution 49.8g
(0.35 mol) and a 1.3% aqueous solution of sodium hypophosphite (50.7 g) were added dropwise to the reaction system in parallel over 4 hours. Then, the temperature was kept at 60 to 70 ° C. for 5 hours to complete the reaction.

The reaction rate of diallyldimethylammonium chloride was 99% and the reaction rate of acrylamide was 99% or more according to the amount of unreacted monomer. The product was an aqueous solution containing 25% of a polymer component and had a pH of 3.4 and a viscosity of 33 ps.

Example 5 29.2 g (0.1 mol) of a 50% diallylamine sulfate aqueous solution and 36 g of ion-exchanged water were charged into the same apparatus as used in Example 1, and the pH was adjusted to 3.0 with sulfuric acid. Next, after replacing the air in the device with nitrogen gas to make it oxygen-free,
The temperature was raised until the internal temperature reached 75 ° C. Potassium persulfate 68
0 mg was added, 57 g of an aqueous solution containing 28.4 g (0.4 mol) of acrylamide and 230 mg of methylenebisacrylamide, and 50.5 g of a 1% aqueous sodium hypophosphite solution while maintaining the internal temperature at 70 to 80 ° C. In parallel, each was dropped into the reaction system over 5 hours. Then 70-80
The reaction was completed by incubating at 5 ° C for 5 hours.

According to the quantification of the unreacted monomers, the reaction rate of diallylamine sulfate was 94% and the reaction rate of acrylamide was 99% or more. The product was an aqueous solution containing 25% of a polymer component and had a pH of 2.9 and a viscosity of 74 ps.

Example 6 In the same apparatus as used in Example 1, 26.3 g (0.09 mol) of a 50% diallylamine sulfate aqueous solution, 1.0 g of a 35% triallylamine sulfate aqueous solution and 217 ion-exchanged water were added.
g, and adjusted to pH 2.0 with sulfuric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C. Ammonium persulfate 5
70 mg was added, and while maintaining the internal temperature at 60 to 70 ° C., 34.1 g (0.48 mol) of acrylamide, 2.2 g (0.03 mol) of acrylic acid and 64 parts of sodium hypophosphite were added.
87 g of an aqueous solution containing 0 mg was dropped into the reaction system over 3 hours. After that, keep the temperature at 60-70 ℃ for 5 hours and add sulfuric acid to adjust the pH.
Adjusted to 1.5 to complete the reaction.

According to the quantification of unreacted monomers, the reaction rate of diallylamine sulfate was 96%, the reaction rate of acrylamide was 99% or more, and the reaction rate of acrylic acid was 99% or more. The product is an aqueous solution containing 15% of a polymer component and has a pH of 1.
It had a viscosity of 74 ps.

Example 7 26.6 g (0.09 mol) of a 50% diallylmethylamine hydrochloride aqueous solution, 35% in the same equipment as used in Example 1
A triallylamine hydrochloride aqueous solution (1.0 g) and ion-exchanged water (218 g) were charged, and the pH was adjusted to 2.0 with hydrochloric acid. next,
After replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C. Ammonium persulfate (570 mg) was added, and while maintaining the internal temperature at 60 to 70 ° C, acrylamide (34.1 g, 0.48 mol), acrylic acid (2.2 g, 0.03 mol) and sodium hypophosphite (510 mg) were added. 87 g of the containing aqueous solution was dropped into the reaction system over 5 hours. After that, the temperature was kept at 60 to 70 ° C. for 5 hours, and the pH was adjusted to 1.5 with hydrochloric acid to complete the reaction.

According to the quantification of unreacted monomers, the reaction rate of diallylmethylamine hydrochloride was 95%, the reaction rate of acrylamide was 99% or more, and the reaction rate of acrylic acid was 99% or more. The product is a 15% aqueous polymer solution,
The pH was 1.5 and the viscosity was 56 ps.

Example 8 In the same apparatus as used in Example 1, 24.1 g (0.09 mol) of 50% diallylamine hydrochloride aqueous solution, 1.0 g of 35% triallylamine hydrochloride aqueous solution and 212 ion-exchanged water were added.
g was added and the pH was adjusted to 2.0 with hydrochloric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C. Ammonium persulfate 5
70 mg was added, and while maintaining the internal temperature at 60 to 70 ° C., 34.1 g (0.48 mol) of acrylamide, 2.2 g (0.03 mol) of acrylic acid and 64 parts of sodium hypophosphite were added.
87 g of an aqueous solution containing 0 mg was added dropwise to the reaction system over 4 hours. After that, keep the temperature at 60-70 ℃ for 5 hours, and add pH with hydrochloric acid.
Adjusted to 1.5 to complete the reaction.

The reaction rate of diallylamine hydrochloride was 95%, the reaction rate of acrylamide was 99% or more, and the reaction rate of acrylic acid was 99% or more according to the quantification of unreacted monomers. The product is an aqueous solution containing 15% of a polymer component and has a pH of 1.
It had a viscosity of 21 ps.

Example 9 In the same apparatus as used in Example 1, 14.6 g (0.05 mol) of 50% diallylamine sulfate aqueous solution, 0.8 g of 35% triallylamine sulfate aqueous solution and 60 g of ion-exchanged water.
Was charged and the pH was adjusted to 2.0 with sulfuric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C. Ammonium persulfate 340
28.4 g (0.4 mol) of acrylamide and 3.6 g of acrylic acid while maintaining the internal temperature at 60 to 70 ° C.
(0.05 mol) and sodium hypophosphite 1060 mg
83 g of the containing aqueous solution was dropped into the reaction system over 3 hours. After that, keep the temperature at 60-70 ℃ for 5 hours and add sulfuric acid to adjust the pH.
Adjusted to 1.5 to complete the reaction.

The reaction rate of diallylamine sulfate was 95%, the reaction rate of acrylamide was 99% or more, and the reaction rate of acrylic acid was 99% or more based on the quantification of unreacted monomers. The product is an aqueous solution containing 25% of a polymer component and has a pH of 1.
It had a viscosity of 79 ps.

Example 10 In the same equipment used in Example 1, 14.8 g (0.05 mol) of a 50% diallylmethylamine hydrochloride aqueous solution, 35%
A triallylamine hydrochloride aqueous solution (0.8 g) and ion-exchanged water (60 g) were charged, and the pH was adjusted to 2.0 with hydrochloric acid. Next, after replacing the air in the device with nitrogen gas to make it oxygen-free,
The temperature was raised until the internal temperature reached 60 ° C. While adding 340 mg of ammonium persulfate and keeping the internal temperature at 60 to 70 ° C,
Acrylamide 28.4 g (0.4 mol), acrylic acid 3.6 g (0.05 mol) and sodium hypophosphite 79
83 g of an aqueous solution containing 0 mg was dropped into the reaction system over 5 hours. After that, keep the temperature at 60-70 ℃ for 5 hours, and add pH with hydrochloric acid.
Adjusted to 1.5 to complete the reaction.

The reaction rate of diallylmethylamine hydrochloride was 98%, the reaction rate of acrylamide was 99% or more, and the reaction rate of acrylic acid was 99% or more according to the quantification of unreacted monomers. The product is a 25% aqueous polymer solution,
The pH was 1.5 and the viscosity was 45 ps.

Example 11 To the same apparatus as used in Example 1, 14.6 g (0.06 mol) of 50% diallylamine sulfate aqueous solution and 80 g of ion-exchanged water were charged, and the pH was adjusted to 2.0 with sulfuric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 70 ° C. 680 mg of potassium persulfate was added, and while maintaining the internal temperature at 70 to 80 ° C., 36.3 g (0.51 mol) of acrylamide, 2.2 g (0.03 mol) of acrylic acid, and sodium hypophosphite were added. 89 g of an aqueous solution containing 250 mg and 280 mg of methylenebisacrylamide was added dropwise to the reaction system over 5 hours.
After that, the temperature was kept at 60 to 70 ° C. for 5 hours, and the pH was adjusted to 1.5 with sulfuric acid to complete the reaction.

The reaction rate of diallylamine sulfate was 97%, the reaction rate of acrylamide was 99% or more, and the reaction rate of acrylic acid was 99% or more based on the quantification of unreacted monomers. The product is an aqueous solution containing 25% of a polymer component and has a pH of 1.
It had a viscosity of 31 ps.

Comparative Example 1 The same apparatus used in Example 1 was charged with 29.2 g (0.1 mol) of a 50% diallylamine sulfate aqueous solution and 144 g of ion-exchanged water, and the pH was adjusted to 3.0 with sulfuric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 65 ° C. 320 mg of ammonium persulfate was added, and while maintaining the internal temperature at 60 to 70 ° C, 25% acrylamide aqueous solution 113.7 g (0.4
Mol) was added dropwise into the reaction system over 3 hours. Then 6
The temperature was kept at 0 to 70 ° C. for 5 hours to complete the reaction.

The reaction rate of diallylamine sulfate was 94% and the reaction rate of acrylamide was 99% or more according to the quantification of unreacted monomers. The product was an aqueous solution containing 15% of a polymer component and had a pH of 3.3 and a viscosity of 25 ps.

COMPARATIVE EXAMPLE 2 In the same equipment used in Example 1, dimethylaminoethylmethacrylate quaternized with methyl chloride 12.5
g (0.06 mol), acrylamide 24.2 g (0.34)
Mol), 200 g of ion-exchanged water and 7.3 g of isopropyl alcohol were charged, the air in the apparatus was replaced with nitrogen gas to make it oxygen-free, and then the internal temperature was raised to 60 ° C. Add 210 mg of ammonium persulfate and add 4 at 60 ° C.
The reaction was completed by incubating for a time.

According to the quantification of unreacted monomers, the reaction rate of the quaternary product of dimethylaminoethyl methacrylate with methyl chloride was 99%, and the reaction rate of acrylamide was 99% or more. The product has a polymer content of 15% and a pH of 3.
2. The viscosity was 37 ps.

Comparative Example 3 The same apparatus used in Example 1 was charged with 14.4 g (0.05 mol) of a 50% diallylamine hydrochloride aqueous solution and 165 g of ion-exchanged water, and the pH was adjusted to 2.0 with hydrochloric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C. Ammonium persulfate (260 mg) was added, and while maintaining the internal temperature at 60 to 70 ° C, acrylamide (36.7 g, 0.52 mol), acrylic acid (2.2 g, 0.03 mol) and sodium hypophosphite (640 mg) were added. 127 g of the containing aqueous solution was dropped into the reaction system over 3 hours. After that, the temperature was kept at 60 to 70 ° C. for 5 hours, and the pH was adjusted to 1.5 with hydrochloric acid to complete the reaction.

The reaction rate of diallylamine hydrochloride was 93%, the reaction rate of acrylamide was 99% or more, and the reaction rate of acrylic acid was 99% or more according to the quantification of unreacted monomers. The product is an aqueous solution containing 25% of a polymer component and has a pH of 1.
It had a viscosity of 52 ps.

Comparative Example 4 In the same equipment used in Example 1, dimethylaminopropylmethacrylate quaternized with methyl chloride 4.4.
g (0.02 mol), acrylamide 25.6 g (0.36)
Mol), acrylic acid 1.4 g (0.02 mol), ion-exchanged water 171 g and isopropyl alcohol 6.9 g were charged, and after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was 60. The temperature was raised to ℃. 190 mg of ammonium persulfate was added, and the mixture was kept warm at 60 ° C. for 4 hours to complete the reaction.

The reaction rate of the quaternized product of dimethylaminopropyl methacrylate with methyl chloride was 99%, and the reaction rate of acrylamide was 99%.
%, And the reaction rate of acrylic acid was 99% or more.
The product is a polymer component 15%, pH 4.7, viscosity 42ps
Met.

The results of Examples 1 to 11 and Comparative Examples 1 to 4 described above are summarized in Table 1. The abbreviations used in the table have the following meanings.

A: diallylamine compound or cationic monomer DADMAC: diallyldimethylammonium chloride DAMAC: diallylmethylamine hydrochloride DAAC: diallylamine hydrochloride DAAS: diallylamine sulfate QDMM: quaternary product of dimethylaminoethyl methacrylate with methyl chloride QDMAPM: Quaternary product of dimethylaminopropyl methacrylate with methyl chloride B: Acrylamide compound AAm: Acrylamide C: Unsaturated carboxylic acid compound AA: Acrylic acid X: Crosslinkable vinyl monomer TAAS: Triallylamine sulfate TAAC: Triallylamine hydrochloride MBAm : Methylenebisacrylamide

[0068]

[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Main monomer Crosslinkable product Reaction rate (% ) (Mol%) Monomer ───── (Mol% ^* ) Concentration Viscosity A B C X (%) (ps) A B C ──────────────────────────────────── Implementation Example 1 DAAS (20) AAm (80) − TAAS (0.3) 15 32 95 ≧ 99 − 〃 2 DADMAC (20) AAm (80) − TAAC (0.3) 25 68 99 ≧ 99 − 〃 3 DAAS (30) AAm ( 70) − TAAS (0.3) 25 25 93 ≧ 99 − 〃 4 DADMAC (30) AAm (70) − TAAC (0.3) 25 33 99 ≧ 99 − 〃 5 DAAS (20) AAm (80) − MBAm (0.3) 25 74 94 ≧ 99 − 〃 6 DAAS (15) AAm (80) AA (5) TAAS (0.3) 15 74 96 ≧ 99 ≧ 99 〃 7 DAMAC (15) AAm (80) AA (5) TAAC (0.3) 15 56 95 ≧ 99 ≧ 99 〃 8 DAAC (15) AAm (80) AA (5) TAAC (0.3) 15 21 95 ≧ 99 ≧ 99 〃 9 DAAS (10) AAm (80) AA (10) TAAS (0.3) 25 79 95 ≧ 99 ≧ 99 〃 10 DAMAC (10) AAm (80) AA (10) TAAC (0.3) 25 45 98 ≧ 99 ≧ 99 〃 11 DAAS (10) AAm (85) AA (5) MBAm (0.3) 25 31 97 ≧ 99 ≧ 99 ──────────────────────────────────── Comparative Example 1 DAAS (20) AAm ( 80) − − 15 25 94 ≧ 99 − 〃 2 QDMM (15) AAm (85) − − 15 37 99 ≧ 99 − 〃 3 DAAC (9) AAm (86) AA (5) − 25 52 93 ≧ 99 ≧ 99 〃 4 QDMAPM (5) AAm (90) AA ( 5) − 15 42 99 ≧ 99 ≧ 99 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ^* Crosslinkable monomer Is the mol% based on the total of the main monomers A to C.

Application Example 1 0.5% of aluminum sulfate was added to an aqueous slurry containing 410 cc of Canadian Standard Freeness corrugated cardboard pulp at a concentration of 3%, and then mixed with Examples 1-1.
The copolymer aqueous solutions obtained in Example 1 and Comparative Examples 1 to 4 were added and mixed by 0.5% in terms of solid content. After stirring for 1 minute, dilute the pulp slurry concentration to 0.3% and use JIS P 812.
Freeness was measured using a Canadian Standard Freeness Tester according to 1. The results are shown in Table 2.

[0070]

Table 2 ━━━━━━━━━━━━ Copolymer Freeness (cc) ──────────── Example 1 580 Example 2 520 Example 3 540 Implementation Example 4 540 Example 5 525 Example 6 565 Example 7 560 Example 8 550 Example 9 550 Example 10 545 Example 11 545 ──────────── Comparative Example 1 510 Comparative Example 2 455 Comparative Example 3 480 Comparative Example 4 485 ──────────── Blank 430 ━━━━━━━━━━━━━

Application Example 2 0.5% of aluminum sulfate was added to the same pulp system as used in Application Example 1 and mixed, and then the aqueous copolymer solutions obtained in Examples 6 to 11 and Comparative Examples 2 to 4 were added. Each of them was added and mixed by 0.6% in terms of solid content. After stirring for 1 minute, the pulp slurry concentration was diluted to 1%, paper was made with a TAPPI standard type hand-making machine, dried at 110 ° C for 4 minutes, and then hand-made with a rice basis weight of 120 ± 2 g / m ² . I got a piece of paper. JI for each sample
The specific burst strength was measured according to SP 8112, and the specific compressive strength was measured according to JIS P 8126. The results are shown in Table 3.

[0072]

[Table 3] ━━━━━━━━━━━━━━━━━━ Copolymer Specific burst strength Specific compression strength ────────────────── -Example 6 4.05 17.0 Example 7 4.01 16.7 Example 8 3.99 16.6 Example 9 3.78 16.1 Example 10 3.72 15.9 Example 11 3 .72 16.0 ────────────────── Comparative Example 2 2.85 14.2 Comparative Example 3 3.63 15.9 Comparative Example 4 3.51 15.8 ────────────────── Blank 2.58 11.8 ━━━━━━━━━━━━━━━━━━━

Example 12 29.2 g (0.1 mol) of a 50% diallylamine sulfate aqueous solution, 0.2 g of divinylbenzene and 153 g of ion-exchanged water were charged into the same apparatus as used in Example 1, and sulfuric acid was added to p.
Adjusted to H3.0. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 65 ° C.
770 mg of ammonium persulfate was added and the internal temperature was adjusted to 60-7.
While maintaining at 0 ℃, 50% acrylamide aqueous solution 56.9
g (0.4 mol), 2 of polyamide epihalohydrin resin
1.7 g of 5% aqueous solution "Sumiraze Resin 675" (manufactured by Sumitomo Chemical Co., Ltd.) and 50.5 g of 1% aqueous sodium hypophosphite solution were placed in the reaction system in parallel for 3 hours each. Dropped. Then, the temperature was kept at 60 to 70 ° C. for 5 hours to obtain a resin aqueous solution having a polymer component concentration of 15%, a pH of 3.1 and a viscosity of 32 ps.

Example 13 In the same apparatus as used in Example 1, 27.0 g (0.1 mol) of 60% diallyldimethylammonium chloride aqueous solution, 0.3 g of divinylbenzene and 75 g of ion-exchanged water were added.
Was charged and the pH was adjusted to 3.0 with hydrochloric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 65 ° C. Ammonium persulfate 770 mg was added, and while maintaining the internal temperature at 60 to 70 ° C., 28.4 g (0.4 mol) of acrylamide, 0.5 g of “Sumirazed Resin 675” as a solid content and sodium hypophosphite were added. 370
79 g of an aqueous solution containing mg was dropped into the reaction system over 4 hours. Then, the temperature was kept at 60 to 70 ° C. for 5 hours to obtain a resin aqueous solution having a polymer component concentration of 25%, pH 3.2 and a viscosity of 68 ps.

Example 14 The same apparatus used in Example 1 was charged with 43.9 g (0.15 mol) of a 50% diallylamine sulfate aqueous solution, 0.7 g of divinylbenzene and 73 g of ion-exchanged water, and sulfuric acid was added to p.
Adjusted to H3.0. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 65 ° C.
540 mg of ammonium persulfate was added, and the internal temperature was adjusted to 60-7.
While maintaining the temperature at 0 ° C, 24.9 g (0.35 g) of acrylamide
Mol), 1.0 g of "PVA-105" (manufactured by Kuraray Co., Ltd.), which is polyvinyl alcohol having an average degree of polymerization of about 500, and 76 g of an aqueous solution containing 850 mg of sodium hypophosphite in the reaction system over 5 hours. Dropped. Then 5 at 60-70 ℃
After keeping the temperature for a while, an aqueous resin solution having a polymer component concentration of 25%, a pH of 3.0 and a viscosity of 25 ps was obtained.

Example 15 In the same apparatus used in Example 1, 40.4 g (0.15 mol) of a 60% diallyldimethylammonium chloride aqueous solution, 0.7 g of divinylbenzene and 53 g of ion-exchanged water were added.
Was charged and the pH was adjusted to 3.0 with hydrochloric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 65 ° C. Ammonium persulfate (540 mg) was added, and while maintaining the internal temperature at 60 to 70 ° C, 49.8 g (0.35 mol) of a 50% acrylamide aqueous solution, 10.0 g of a 10% aqueous solution of "PVA-105", and 1.3%. 50.7 g of an aqueous solution of sodium hypophosphite was dropped into the reaction system in parallel over 4 hours. After that, the temperature was kept at 60 to 70 ° C. for 5 hours to obtain a resin aqueous solution having a polymer component concentration of 25%, a pH of 3.4 and a viscosity of 33 ps.

Example 16 The same apparatus as used in Example 1 was charged with 29.2 g (0.1 mol) of a 50% diallylamine sulfate aqueous solution and 40 g of ion-exchanged water, and the pH was adjusted to 3.0 with sulfuric acid. Next, after replacing the air in the device with nitrogen gas to make it oxygen-free,
The internal temperature was raised to 75 ° C. An aqueous solution containing 28.4 g (0.4 mol) of acrylamide, 380 mg of methylenebisacrylamide and 0.9 g of "PVA-105" while maintaining the internal temperature at 70 to 80 ° C by adding 880 mg of potassium persulfate 5
7g and 50.5g of 1% sodium hypophosphite solution
Was added dropwise to the reaction system in parallel over 5 hours. Then, the temperature was kept at 70 to 80 ° C. for 5 hours to obtain a resin aqueous solution having a polymer component concentration of 25%, a pH of 2.9 and a viscosity of 74 ps.

Example 17 26.3 g (0.09 mol) of a 50% diallylamine sulfate aqueous solution, 0.2 g of divinylbenzene and 224 g of ion-exchanged water were charged in the same apparatus as used in Example 1, and sulfuric acid was added to p.
Adjusted to H2.0. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C.
570 mg of ammonium persulfate was added, and the internal temperature was adjusted to 60-7.
While keeping the temperature at 0 ° C, 34.1 g (0.48 g) of acrylamide
Mol), 2.2 g (0.03 mol) of acrylic acid, 1.0 g of "SUMIREZ RESIN 675" as a solid content, and 87 g of an aqueous solution containing 640 mg of sodium hypophosphite in a reaction system over 3 hours. Dropped. After that, keep the temperature at 60-70 ℃ for 5 hours, adjust the pH to 1.5 with sulfuric acid, and adjust the polymer component concentration to
A 5% aqueous resin solution having a viscosity of 74 ps was obtained.

Example 18 The same apparatus as used in Example 1 was charged with 26.6 g (0.09 mol) of a 50% diallylmethylamine hydrochloride aqueous solution, 0.4 g of divinylbenzene and 223 g of ion-exchanged water.
The pH was adjusted to 2.0 with hydrochloric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C. Ammonium persulfate (570 mg) was added, and while maintaining the internal temperature at 60 to 70 ° C, 34.1 g of acrylamide was added.
(0.48 mol), 2.2 g of acrylic acid (0.03 mol),
87 g of an aqueous solution containing 1.0 mg of "SUMIREZ RESIN 675" as a solid content and 510 mg of sodium hypophosphite was added to
It was dropped into the reaction system over time. After that, the mixture was kept at 60 to 70 ° C. for 5 hours and adjusted to pH 1.5 with hydrochloric acid to obtain a resin aqueous solution having a polymer component concentration of 15% and a viscosity of 56 ps.

Example 19 The same apparatus as used in Example 1 was charged with 24.1 g (0.09 mol) of a 50% diallylamine hydrochloride aqueous solution, 0.2 g of divinylbenzene and 218 g of ion-exchanged water, and p was added with hydrochloric acid.
Adjusted to H2.0. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C.
570 mg of ammonium persulfate was added, and the internal temperature was adjusted to 60-7.
While keeping the temperature at 0 ° C, 34.1 g (0.48 g) of acrylamide
Mol), 2.2 g of acrylic acid (0.03 mol), "PVA-10
87 g of an aqueous solution containing 1.0 g of 5 "and 640 mg of sodium hypophosphite was added dropwise to the reaction system over 4 hours. After that, the temperature was kept at 60 to 70 ° C for 5 hours and adjusted to pH 1.5 with hydrochloric acid. A resin aqueous solution having a polymer component concentration of 15% and a viscosity of 21 ps was obtained.

Example 20 To the same apparatus as used in Example 1, 14.6 g (0.05 mol) of a 50% diallylamine sulfate aqueous solution, 0.4 g of divinylbenzene and 63 g of ion-exchanged water were charged, and sulfuric acid was added to p.
Adjusted to H2.0. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C.
340 mg of ammonium persulfate was added and the internal temperature was adjusted to 60-7.
While maintaining the temperature at 0 ° C, 28.4 g (0.4
Mol), 3.6 g of acrylic acid (0.05 mol), 0.4 g of "SUMIREZ RESIN 675" as a solid content, and 83 g of an aqueous solution containing 1060 mg of sodium hypophosphite in a reaction system over 3 hours. Dropped. Then, the mixture was kept at 60 to 70 ° C. for 5 hours and adjusted to pH 1.5 with sulfuric acid to obtain a resin aqueous solution having a polymer component concentration of 25% and a viscosity of 79 ps.

Example 21 The same apparatus as used in Example 1 was charged with 14.8 g (0.05 mol) of a 50% diallylmethylamine hydrochloride aqueous solution and 63 g of ion-exchanged water, and the pH was adjusted to 2.0 with hydrochloric acid. did.
Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C. Ammonium persulfate (440 mg) was added, and while keeping the internal temperature at 60 to 70 ° C, 28.4 g (0.4 mol) of acrylamide, 3.6 g (0.05 mol) of acrylic acid and 0.8 g of methylenebisacrylamide. Then, 0.8 g of "SUMIREZ RESIN 675" as a solid content and 83 g of an aqueous solution containing 790 mg of sodium hypophosphite were dropped into the reaction system over 5 hours. After that, the mixture was kept at 60 to 70 ° C. for 5 hours and adjusted to pH 1.5 with hydrochloric acid to obtain a resin aqueous solution having a polymer component concentration of 25% and a viscosity of 45 ps.

Example 22 To the same apparatus as used in Example 1, 14.6 g (0.06 mol) of 50% diallylamine sulfate aqueous solution and 85 g of ion-exchanged water were charged, and the pH was adjusted to 2.0 with sulfuric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 70 ° C. Potassium persulfate 740
mg was added, and while maintaining the internal temperature at 70 to 80 ° C, 36.3 g (0.51 mol) of acrylamide and 2.2 of acrylic acid were added.
g (0.03 mol), methylenebisacrylamide 1.9
g, 1.0 g of "PVA-105" and 89 g of an aqueous solution containing 250 mg of sodium hypophosphite were added dropwise to the reaction system over 5 hours. After that, the temperature was kept at 60 to 70 ° C for 5 hours, and the pH was adjusted to 1.5 with sulfuric acid.
A 1 ps aqueous resin solution was obtained.

The results of Examples 12 to 22 above are summarized in Table 4. The abbreviations used in the table have the following meanings.

A: diallylamine compound or cationic monomer DADMAC: diallyldimethylammonium chloride DAMAC: diallylmethylamine hydrochloride DAAC: diallylamine hydrochloride DAAS: diallylamine sulfate QDMM: quaternized product of dimethylaminoethyl methacrylate with methyl chloride QDMAPM: Quaternary product of dimethylaminopropyl methacrylate with methyl chloride B: Acrylamide compound AAm: Acrylamide C: Unsaturated carboxylic acid compound AA: Acrylic acid X: Crosslinkable vinyl monomer DVB: Divinylbenzene MBAm: Methylenebisacrylamide E: Polymer Chain transfer agent SRZ675: “Sumiraz resin 675” [Sumitomo Chemical Co., Ltd., 25% aqueous solution of polyamide epihalohydrin resin, but shown as solid content in the table] PVA105: “PVA-105” [(share Kuraray Co., Ltd., degree of polymerization of about 50
0 polyvinyl alcohol]

[0086]

[Table 4] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Monomer composition Crosslinkable polymer-based product Monomer Chain transfer agent ─────(Mol%) (Mol% ^* ) (Wt% ^** ) Concentration Viscosity ABC X E (%) (ps) ──────────────────────────────────── Example 12 DAAS (20) AAm (80) DVB (0.3) SRZ675 (1.0) 15 32 Example 13 DADMAC (20) AAm (80) DVB (0.5) SRZ675 (1.0) 25 68 Example 14 DAAS (30) AAm ( 70) DVB (1.0) PVA105 (2.0) 25 25 Example 15 DADMAC (30) AAm (70) DVB (1.0) PVA105 (2.0) 25 33 Example 16 DAAS (20) AAm (80) MBAm (0.5) PVA105 ( 2.0) 25 74 Example 17 DAAS (15) AAm (80) AA (5) DVB (0.3) SRZ675 (2.0) 15 74 Example 18 DAMAC (15) AAm (80) AA (5) DVB (0.5) SRZ675 ( 2.0) 15 56 Example 19 DAAC (15) AAm (80) AA (5) DVB (0.3) PVA105 (2.0) 15 21 Example 20 DAAS (10) AAm (80) AA (10) DVB (0.5) SRZ675 ( 1.0) 25 79 Example 21 DAMAC (10) AAm (80) AA (10) MBAm (1.0) SRZ675 (2.0) 25 45 Example 22 DAAS (10) AAm (85) AA (5) MBAm (2.0) PVA105 ( 2.0) 25 31 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ^* The amount of the crosslinkable monomer is mol% based on the total of the main monomers A to C.^** The amount of chain transfer agent is% by weight based on the total amount of monomers

Application Example 3 The same experiment as in Application Example 1 was carried out using the aqueous copolymer solutions obtained in Examples 12 to 22 and Comparative Examples 1 to 4. Table 5 shows the results. The experiment using the copolymer aqueous solution obtained in each of Comparative Examples 1 to 4 and the blank experiment were performed at a different time from that of Application Example 1, and thus are slightly different from the values in Table 2.

[0088]

[Table 5] ━━━━━━━━━━━━ Copolymer Freeness (cc) ──────────── Example 12 565 Example 13 520 Example 14 515 Example Example 15 525 Example 16 540 Example 17 580 Example 18 575 Example 19 570 Example 20 550 Example 21 530 Example 22 525 ──────────── Comparative Example 1 495 Comparative Example 2 445 Comparative Example 3 475 Comparative Example 4 480 ──────────── Blank 420 ━━━━━━━━━━━━

Application Example 4 Rice grammage of 120 ± 2 g / m ^{2 was performed in the same} manner as in Application Example 2 except that the aqueous copolymer solutions obtained in Examples 17 to 22 and Comparative Examples 2 to 4 were used. A handmade paper was obtained. For each sample, specify the burst strength in accordance with JIS P 8112 and the JIS
Compressive strength was measured according to P 8126. The results are shown in Table 6. In addition, since the experiment using the respective copolymer aqueous solutions obtained in Comparative Examples 2 to 4 and the blank experiment were conducted at a time different from that of Application Example 2, it does not exactly correspond to the values in Table 3. Absent.

[0090]

[Table 6]

[0091]

The papermaking additive according to the present invention is a copolymer having a relatively high molecular weight, and the viscosity of its aqueous solution does not increase so much. Alternatively, the paperboard exhibits a high paper-strengthening effect without causing the formation disorder.
Further, this papermaking additive also exerts a high effect on improvement of drainage and retention of filler. Further, according to the present invention, a water-soluble copolymer useful as such a papermaking additive can be industrially advantageously produced.

Claims (12)

[Claims] 1. A general formula (I) (In the formula, R ¹ and R ² each independently represent hydrogen or methyl, and R ³ and R ⁴ are each independently hydrogen and have 1 carbon atom.
8 represents alkyl or aralkyl, X ^- diallylamine compound is represented by represents an anion of an acid) (A), the general formula (II) (In the formula, R ⁵ represents hydrogen or methyl, R ⁶ and R ⁷ each independently represent hydrogen or alkyl having 1 to 4 carbon atoms), and a crosslinkable vinyl monomer (B). A papermaking additive containing a copolymer having at least three components of X) as constituent monomers. 2. The copolymer is a crosslinkable vinyl monomer (X).
Based on the total molar amount of the constituent monomers other than, the diallylamine compound (A) is 1 to 70 mol%, the acrylamide compound (B) is 30 mol% or more, and the crosslinkable vinyl monomer (X) is 0.05 to 5 mol%. The additive according to claim 1, which is reacted by using 5 mol%. 3. The constituent monomers of the copolymer are further α, β
-The additive according to claim 1, which contains an unsaturated carboxylic acid compound (C) selected from the group consisting of unsaturated monocarboxylic acids, α, β-unsaturated dicarboxylic acids and salts thereof. 4. The copolymer is a crosslinkable vinyl monomer (X).
Based on the total molar amount of constituent monomers other than, the diallylamine compound (A) is 1 to 70 mol%, the acrylamide compound (B) is 30 mol% or more, and the unsaturated carboxylic acid compound (C) is 20 mol%. The additive according to claim 3, which is obtained by reacting the following and 0.05 to 5 mol% of the crosslinkable vinyl monomer (X). 5. The additive according to any one of claims 1 to 4, wherein the crosslinkable vinyl monomer (X) is triallylamine or a salt thereof, divinylbenzene, methylenebisacrylamide or methylenebismethacrylamide. 6. A copolymer having a weight average molecular weight of 10,000
Additive according to any of claims 1 to 5 in the range of 10,000,000. 7. General formula (I) (In the formula, R ¹ and R ² each independently represent hydrogen or methyl, and R ³ and R ⁴ are each independently hydrogen and have 1 carbon atom.
8 represents alkyl or aralkyl, X ^- diallylamine compound is represented by represents an anion of an acid) (A)
To an aqueous solution containing (In the formula, R ⁵ represents hydrogen or methyl, and R ⁶ and R ⁷ independently represent hydrogen or alkyl having 1 to 4 carbon atoms) and an acrylamide compound (B) and a chain transfer agent (E). Is continuously added and the reaction is carried out in the presence of the crosslinkable vinyl monomer (X). 8. The method according to claim 7, wherein the crosslinkable vinyl monomer (X) is present in an aqueous solution containing the diallylamine compound (A). 9. The method according to claim 7, wherein the crosslinkable vinyl monomer (X) is also continuously added to the aqueous solution containing the diallylamine compound (A). 10. An unsaturated carboxylic acid compound (C) selected from the group consisting of α, β-unsaturated monocarboxylic acids, α, β-unsaturated dicarboxylic acids and salts thereof is continuously added. The method according to claim 7. 11. The method according to claim 7, wherein the chain transfer agent (E) contains alcohol, thiol or hypophosphite. 12. The chain transfer agent (E) has at least two chain transfer functional groups in the molecule and has a weight average molecular weight of 1,000.
The method according to claim 7, which comprises a compound having the above.