JP2794413B2 - Cationic polyacrylamide, Z-axis paper strength and interlayer paper strength Paper strength enhancer and drainage improver - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cationic polyacrylamide produced by reacting an acrylamide-based copolymer with a hypohalite in an alkaline region, and a Z-axis paper strength comprising the same as an active ingredient. And a paper strength enhancer and drainage improver of interlayer paper strength.

[0002]

2. Description of the Related Art At present, paper recycling is progressing, and the amount of waste paper in the raw materials for production tends to increase. The recovery rate of waste paper in Japan is, for example, 19
In 1983, it reached 49%, the highest level in the world. The varieties with the highest recovery rate among waste paper
Newspaper, then cardboard. Under these circumstances, the paper strength tends to decrease due to factors such as the progress of finer fibers with the increase in the use of waste paper as a raw material and the incorporation of fillers and sizing agents. Therefore, in order to maintain the quality of the paper while suppressing the reduction in the paper strength, it is necessary to rely on the use of a paper strength enhancer (paper strength agent). In particular, corrugated cardboard and newsprint, which have a high recovery rate of waste paper, have a serious problem of raw materials, but not only that, but also excellent paper strength agents, especially Z
A paper strength agent excellent in axial paper strength and interlayer paper strength has been desired. For example, in the case of corrugated cardboard, the bonding method at the time of molding processing has been changed from a conventional method using a fastener such as a stapler to a method using hot-melt bonding, and problems such as surface turning are easily caused. In order to prevent such troubles, a paper strengthening agent for internal addition that improves Z-axis strength and interlayer paper strength is essential.

[0003] On the other hand, in the multilayer papermaking method and the like, the Z-axis strength and the interlaminar paper strength tend to decrease with the speeding up of the papermaking machine, and problems such as peeling between layers easily occur. Strength is required.

[0004] In addition, in order to cope with offset printing in newsprint, development of an excellent paper strength agent for increasing the strength of the Z-axis paper strength has been desired.

A primary amino group can be introduced into an acrylamide polymer at a relatively low cost by performing a so-called Hoffman transfer reaction in which an acrylamide or methacrylamide polymer is reacted with a hypohalite in an alkaline region. The Hoffman transfer reaction product of the acrylamide polymer is used as a paper strength enhancer, and is superior in improving the Z-axis paper strength and drainage as compared with other, for example, Mannich-modified polyacrylamide. Therefore, paper having improved Z-axis paper strength can be made by using a Hoffman transition reaction product of an acrylamide-based polymer. However, one of the drawbacks of the Hoffman rearrangement reaction is that a large amount of inorganic salts may be generated during the reaction, and the concentration of inorganic salts in white water increases, particularly when used as a paper strength enhancer that is frequently used. Is generated. Therefore, it is necessary to reduce the amount of the Hoffman rearrangement product as much as possible while the white water is being closed as it is now. In other words, although the Hoffman transition product of the acrylamide polymer exhibits excellent Z-axis paper strength, it has problems such as containing a large amount of inorganic salts, and it is necessary to further improve the performance in the sense of suppressing the amount of use. is there. However, the correlation between the strength of the Z-axis paper or the strength of the interlayer paper and the strength of the paper is often unclear, and no guideline for improving the strength has been known.

[0006]

Means for Solving the Problems In order to solve these problems, the present inventor has attempted to use a polyacrylamide copolymerized with acrylonitrile which has undergone a Huffman rearrangement reaction at a constant temperature for a predetermined time to obtain a Z-axis. The present inventors have found that the paper strength, interlayer paper strength, and drainage are significantly improved, and completed the present invention.

That is, the objects of the present invention are: (a) 97 to 60 mol% of a group containing a carbamoyl group;
(B) an acrylamide-based copolymer containing 3 to 40 mol% of a nitrile group and a hypohalite, at least p
A cationic polyacrylamide obtained by performing a reaction at a temperature (T) in a range of 50 to 110 ° C. within a short time (t) specified below under alkaline conditions of H11 or more. e ^{15,150 / (273 + T)} × 2.5 × 10 ⁻²⁰
≦ t (sec) ≦ e ^{15,150 / (273 + T)} ×
10 ⁻¹⁸ +30 (T is a reaction temperature (° C.)) 2. A Z-axis paper strength and interlayer paper strength paper strength enhancer containing the cationic polyacrylamide described in 1 above as an active ingredient. 3. A drainage improver containing the cationic polyacrylamide as described in 1 above as a main component. Is achieved by each of

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The acrylamide-based copolymer used in the present invention is an acrylamide-based copolymer containing 3 to 40 mol%, preferably 5 to 30 mol% of a nitrile group. It is a Hoffman rearrangement reaction product reacted with a halogenite. When the amount of the nitrile group is less than 3 mol%, the effect of acrylonitrile copolymerization is insufficient, that is, C.I. S. F value is not large enough,
Further, the strength of the Z-axis paper strength is completely insufficient. On the other hand, if it exceeds 40 mol%, the solubility in water is impaired. S. There are inconveniences such as the F value and the strength of the Z-axis paper strength being further deteriorated.

Further, the following monomers can be copolymerized. Examples of the copolymerizable monomer include a hydrophilic monomer, an ionic monomer, and a lipophilic monomer, and one or more of these monomers can be used. Specifically, examples of the hydrophilic monomer include methacrylamide, diacetone acrylamide, N-ethyl methacrylamide, N-ethylacrylamide, N, N-diethylacrylamide, N-propylacrylamide, N-acryloylpyrrolidine, N-acryloyl Examples thereof include piperidine, N-acryloylmorpholine, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, various methoxypolyethylene glycol (meth) acrylates, and N-vinyl-2-pyrrolidone.

Examples of the ionic monomer include acrylic acid, methacrylic acid, vinyl sulfonic acid, allyl sulfonic acid, methacryl sulfonic acid, styrene sulfonic acid,
Acrylamide-2-phenylpropanesulfonic acid, 2
Acids such as acrylamide-2-methylpropanesulfonic acid and salts thereof, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate;
N, N-dimethylaminopropyl methacrylamide,
Examples include amines such as N, N-dimethylaminopropylacrylamide and salts thereof.

As the lipophilic monomer, for example, N, N-di-n-propylacrylamide, Nn-butylacrylamide, Nn-hexylacrylamide, Nn-
Hexyl methacrylamide, Nn-octyl acrylamide, Nn-octyl methacrylamide, N-te
N-alkyl (meth) acrylamide derivatives such as rt-octylacrylamide, N-dodecylacrylamide, Nn-dodecylmethacrylamide, N, N-diglycidylacrylamide, N, N-diglycidylmethacrylamide, N- (4- N- (ω-) such as glycidoxybutyl) acrylamide, N- (4-glycidoxybutyl) methacrylamide, N- (5-glycidoxypentyl) acrylamide, and N- (6-glycidoxyhexyl) acrylamide Glycidoxyalkyl) (meth) acrylamide derivative, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
(Meth) acrylate derivatives such as lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and glycidyl (meth) acrylate; olefins such as methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, ethylene, propylene, and butene; styrene,
Divinylbenzene, α-methylstyrene, butadiene,
And isoprene. The amount of the unsaturated monomer used for the copolymerization varies depending on the type of the unsaturated monomer and the combination thereof, and cannot be determined unconditionally, but is generally in the range of 0 to 30% by weight.

Next, the above-mentioned monomers are polymerized to produce polyacrylamide. The polymerization method is preferably radical polymerization, and a polar solvent such as water, alcohol, dimethylformamide or the like can be used as a polymerization solvent. However, since the Hoffman decomposition reaction is performed in an aqueous solution, aqueous solution polymerization is preferable. The monomer concentration at that time is 2 to 30% by weight, preferably 5 to 30% by weight. The polymerization initiator is not particularly limited as long as it is water-soluble, and is usually used after being dissolved in an aqueous monomer solution. Specifically, in the case of peroxides, for example, ammonium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl peroxide and the like can be mentioned. In this case, it can be used alone, but can also be used as a redox polymerizer in combination with a reducing agent. Examples of the reducing agent include salts of lower ionization such as sulfite, hydrogen sulfite, iron, copper, and cobalt; organic amines such as N, N, N ', N'-tetramethylethylenediamine; and aldose and ketose. And the like.

The azo compounds include 2,2'-azobis-2-amidinopropane hydrochloride, 2,2'-azobis-2,4-dimethylvaleronitrile, and 4,4'-azobis-4-cyanovaleic acid. And its salts and the like. Further, two or more of the above-mentioned polymerization initiators can be used in combination. The amount of the initiator added is 0.1 to 10% by weight, preferably 0.2 to 8% by weight, based on the monomer. In the case of a redox system, the amount of the reducing agent added to the initiator is 0.1 to 10.0% on a molar basis,
Preferably it is 0.2-8.0%.

The redox initiator used in the present invention is not limited as long as it has the ability to initiate radical polymerization. For example, inorganic peroxides, organic peroxides, and those peroxides and reducing agents are used. Cerium nitrate (I
V) Ammonium and azo compounds. Specific examples include ammonium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl peroxide, benzoyl peroxide, cumene hydroxy peroxide, tert-butyl peroxy-2-ethylhexanoate, butyl perbenzoate and the like. Examples of the reducing agent used in combination therewith include sulfites, bisulfites, salts of lower ionic values such as iron, copper, and cobalt; organic amines such as aniline; and reducing sugars such as aldose and ketose. . As the azo compound, azobisisobutyronitrile, 2,2
2′-azobis-2-amidinopropane hydrochloride, 2,
2'-azobis-2,4-dimethylvaleronitrile,
4,4'-azobis-4-cyanovaleic acid and the like can be used. It is also possible to use two or more of the above-mentioned polymerization initiators in combination. The range in which the initiator concentration is used is usually from 0.1 to 5.
Use in the range of 0% by weight.

The polymerization temperature is lower in the case of a single polymerization initiator and is generally about 30 to 90 ° C., and in the case of a redox-based polymerization initiator it is lower and is generally about 5 to 50 ° C. Further, it is not necessary to keep the same temperature during the polymerization, and the temperature may be appropriately changed as the polymerization proceeds. Generally, the temperature is raised by polymerization heat generated as the polymerization proceeds. The atmosphere in the polymerization vessel at that time is not particularly limited, but it is preferable to replace the atmosphere with an inert gas such as a nitrogen gas in order to promptly carry out the polymerization. Although the polymerization time is not particularly limited, it is generally 1 to 20 hours.

The acrylamide copolymer thus obtained is a water-soluble polymer containing 97 to 60 mol% of acrylamide groups and 3 to 40 mol% of nitrile groups. The Brookfield viscosity at 20 ° C. of a 10% aqueous solution of this copolymer is from 100 to 100,000 cps, but is usually preferably in the range from 100 to 80,000 cps. That is, it is preferably 100 cps or more in terms of obtaining sufficient performance, while 80,000 cp is used in order to prevent a decrease in operability and a tendency to cause gelation.
s or less is preferred.

The Hoffman decomposition reaction is carried out by allowing a hypohalite to act on an amide group of polyacrylamide in the presence of an alkaline substance. Examples of hypohalous acid include hypochlorous acid, hypobromite, and hypohalous acid. And iodic acid.
Examples of the hypochlorite include metal hypochlorite or alkaline earth metal salts, and specifically, sodium hypochlorite, potassium hypochlorite, lithium hypochlorite, and hypochlorous acid. There are calcium, magnesium hypochlorite, barium hypochlorite and the like. Similarly, hypobromite and hypoiodite include alkali metal or alkaline earth metal salts of hypobromite and hypoiodite. It is also possible to generate a hypohalite by blowing a halogen gas into an alkaline solution. On the other hand, examples of the alkaline substance include an alkali metal hydroxide, an alkaline earth metal hydroxide, and an alkali metal carbonate. Among them, an alkali metal hydroxide is preferable, and sodium hydroxide, potassium hydroxide, and hydroxide are preferable. Lithium and the like. In the case of hypohalous acid, the addition amount of the above substances to polyacrylamide is 0.05 to
The amount is 2.0 mol, preferably 0.1 to 1.5 mol, and 0.05 to 4.0 mol, preferably 0.1 to 3.0 mol, based on the amide group in an alkaline substance. P at that time
H is generally in the range of 11-14. The concentration of the polyacrylamide at that time is generally 0.1 to 17.5% by weight. However, when the reaction concentration becomes high, stirring becomes difficult and gelation easily occurs. Preferably it is in the range of weight%. Further, when the reaction concentration is less than 1%, there is a problem that the reaction rate becomes slow.
More preferably, it is 0% by weight.

On the other hand, the reaction temperature is in the range of 0 to 110 ° C., and the Hoffman decomposition reaction is performed within this temperature range. Since the reaction time depends on the reaction temperature and the polymer concentration in the reaction solution, it cannot be said unconditionally. For example, when the polymer concentration is 1% by weight, it is within 30 to 40 hours at 0 ° C. and 3 to 4 hours at 20 ° C. Within 50 ° C., within several minutes, at 65 ° C., within several minutes, and at 80 ° C., within several tens of seconds. Further, the higher the polymer concentration, the shorter the reaction time.

Further, as in the present invention, the reaction temperature is set at 50 ° C.
When the reaction is completed in a short time at about 110 ° C., it is possible to produce a cationic polyacrylamide having properties equivalent to or higher than that of Hoffman-decomposed polyacrylamide produced by a low-temperature reaction, and further, it is possible to produce a polyacrylamide on-site by shortening the reaction time. This makes it possible to avoid the problem of deterioration of Hoffman-decomposed polyacrylamide with time, and to obtain other effects. From this point, in the present invention, 50 ° C.
The reaction is carried out in a temperature range of 〜110 ° C. In this case, the relationship between the reaction time and the reaction temperature may be approximately within the range between the following two relational expressions, and a favorable result can be obtained by performing the reaction within that range.

[0020]

(Equation 1)

The cationic polyacrylamide produced under the above conditions has a cation equivalent measured by colloid titration at pH 2 in the range of about 0 to 10.0 meq / g, and the cationic polyacrylamide varies depending on the amount of hypohalite added. The cation equivalent can be controlled. Further, since the reaction is carried out in an alkaline region, the amide group is hydrolyzed and a carboxyl group is by-produced. The amount of the by-product is represented by an anion equivalent measured by colloid titration at pH 10, and is approximately 0 to 10.0.
It is in the range of meq / g. The amount of the by-product can be controlled by the amount of the added alkaline substance.

Next, after carrying out the reaction under the above conditions, it is preferable to stop the reaction in order to suppress the progress of side reactions. However, when used immediately after the reaction, it may not be necessary to stop the reaction.

As a method for terminating the reaction, methods such as (1) adding a reducing agent, (2) cooling, and (3) lowering the pH of the solution by adding an acid can be used alone or in combination. . (1) is a method of inactivating remaining hypohalite and the like by reaction with a reducing agent.
Examples of the reducing agent used include sodium sulfite, sodium thiosulfate, ethyl malonate, thioglycerol, triethylamine and the like. The amount of the reducing agent used is usually 0.005 to 0.005 based on the amount of hypohalous acid used in the reaction.
It is 0.15 times mol, preferably 0.01 to 0.10 times mol. Generally, at the end of the Hoffman decomposition reaction, a compound having active chlorine such as unreacted hypohalite remains. If such a reaction solution is used as a paper strengthening agent, it may cause rust in a paper machine. Therefore, a reducing agent is usually used to deactivate active chlorine. However, the hypohalite reacts at an equimolar or less relative to the acrylamide unit mole number of the polymer, and when the reaction is performed at a high temperature, almost no unreacted hypohalite remains at the end of the reaction. . Therefore, it can be used as a paper strength agent without deactivating active chlorine by using a reducing agent. (2) is a method of suppressing the progress of the reaction by cooling,
As such a method, there is a method of cooling using a heat exchanger or diluting with cold water. The temperature at that time is usually 50 ° C. or lower, preferably 45 ° C. or lower, more preferably 40 ° C. or lower. In (3), the Huffman decomposition reaction is stopped by lowering the pH of the solution at the end of the reaction, which usually shows an alkaline pH of 12 to 13 using an acid, and at the same time, the progress of the hydrolysis reaction is suppressed. The pH at that time may be neutral or lower, and is preferably in the range of pH 4 to 6. Examples of the acid used for pH adjustment include mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, and organic acids such as formic acid, acetic acid, and citric acid. The reaction termination method can be appropriately selected from (1) to (3) depending on the reaction conditions, and these methods may be combined.

Next, the reaction solution stopped by the above method can be used as it is as an aqueous solution of cationic polyacrylamide, or the aqueous solution is poured into a solvent such as methanol which does not dissolve cationic polyacrylamide to precipitate a polymer. And then dried to form a powder. Further, the cationic polyacrylamide aqueous solution can be stored in a tank and used as needed. The storage temperature at this time may be a low temperature that does not freeze the aqueous solution, and is preferably 10 to 15 ° C.
However, when used within a relatively short period of time, it can be stored at room temperature and can be stored for about one month.

In the present invention, the Hoffman transition reaction product of the acrylamide polymer is used as a paper strength enhancer for Z-axis paper strength or a drainage improver. The method of using the Hoffman transfer reaction product of the acrylamide polymer for the above purpose may be performed according to a conventionally known method, and papermaking is performed in combination with a sulfate band, an anionic resin or the like as necessary.
The addition site may be anywhere before the wet sheet is formed, and the order of addition may be any order or may be simultaneous. Further, it can be added after mixing the cationic polyacrylamide and the anionic resin at pH 9 or more. The addition ratio of the cationic polyacrylamide and the anionic resin can be arbitrarily selected, and is preferably in the range of 100: 0 to 10:90 in terms of the weight of the solid content. The amount of addition is 0.01 to 5% by weight, preferably 0.05 to 2% by weight, based on the dry solid weight of the pulp. The addition site is added before the wet sheet is formed. However, even after the wet sheet is formed, especially in the case of producing a laminated paper, the addition can be performed by spray coating or roll coater coating. Further, in the present invention, when polyacrylamide is subjected to a Hoffman decomposition reaction at a high temperature in a short time to produce a cationic polyacrylamide, the same reaction is performed at a low temperature for a long time, and is superior to a cationic polyacrylamide obtained by performing the same reaction for a long time. Paper strength. Although the reason for this is not necessarily clear, the effect was remarkable when added to pulp slurry or the like without performing a reaction stopping operation.
It is considered that the N-chloro group as a reaction intermediate and other functional groups generated due to high temperature directly or indirectly contribute to the development of paper strength. Therefore, it is more desirable to add the compound without performing the reaction stopping operation. However, if the reaction is not stopped, the deterioration occurs over time, so it is necessary to add the compound immediately after the reaction. Immediately here means that the aqueous solution after the reaction is taken out of the pipe, transported in the same pipe without being transferred to the outside, and added to the pulp slurry. More specifically, the aqueous solution after the reaction may be directly added to the pulp slurry through a pipe, or a stock tank may be provided between them to temporarily stay there, and then the amount may be adjusted and added. The residence time of the reaction solution in the pipe may be within a range where the aqueous solution after the reaction does not deteriorate. However, if the length is too long, the device for retaining the liquid becomes large, and the features of the present invention cannot be utilized. Therefore, in order to carry out the present invention suitably, it is preferable to add it within 5 hours after the reaction, more preferably within 1 hour, even more preferably within 10 minutes. Further, at that time, it may be diluted with water and added depending on the concentration of the cationic polyacrylamide after the reaction. It varies depending on the type of pulp, the speed of papermaking, and the like, and is not explicitly described, but the concentration of the cationic polyacrylamide when added is generally about 0.1.
It is 1 to 10% by weight, preferably 0.5 to 5% by weight, and more preferably 0.8 to 2% by weight.

The paper produced by the above-described method is excellent in paper strength, specifically, burst strength, Z-axis strength, compressive strength and the like. Therefore, when the method of the present invention is applied, when used for a material such as corrugated cardboard or newsprint in which waste paper occupies a high proportion, the effect is very large, and paper with high paper strength can be produced. Further, by applying the present invention not only to corrugated paper and newsprint but also to paper requiring strength, it becomes possible to produce paper having excellent paper strength.

[0027]

The present invention will be described below with reference to examples. In the following,% means weight% unless otherwise specified.

Reference Examples 1 to 3 Acrylamide containing 10 mol% of nitrile groups
100 parts by weight of a 5% aqueous solution of an acrylonitrile copolymer (Brookfield viscosity of a 10% aqueous solution at 20 ° C .; 177 cps) is added with 21.44 parts by weight of a 12.5% aqueous sodium hypochlorite solution and 30% aqueous sodium hydroxide solution 3 A mixture of 0.85 parts by weight (corresponding to twice the molar amount of sodium hypochlorite) was added dropwise over 20 minutes while maintaining the temperature at 20 ° C, and the mixture was reacted at the same temperature for 3 hours. Using toluidine blue as an indicator of the degree of cationization at this point,
When measured by a colloid titration method using a 1/400 N-potassium polyvinyl sulfonate aqueous solution, 2.69 me was measured.
q. / G. The anionization degree is 1/200
A predetermined amount of N-methyl glycol chitosan is added,
Using toluidine blue as an indicator in
When measured by a reverse titration method using a 00N-polyvinyl sulfonate aqueous solution, 1.08 meq. / G. A solution prepared by dissolving 0.14 parts by weight of sodium sulfite in a small amount of water was added to inactivate unreacted sodium hypochlorite, and the pH was adjusted to 4.5 with concentrated hydrochloric acid.
This solution was poured into about 10 times the volume of methanol for reprecipitation, filtered, dried and stored. This had a 1% aqueous solution viscosity at 20 ° C. of 32.5 cps. An acrylamide-acrylonitrile copolymer having the same composition and containing 10 mol% of nitrile groups having different viscosities was reacted in the same manner to obtain a white powdery Hoffman transfer product. These are referred to as Reference Examples 1 to 3, and the results are shown in Table 1.

Reference Example 4 Acrylamide containing 20 mol% of nitrile groups
A white powdered Hoffman transition product was obtained in the same manner as in Reference Example 1 except that an acrylonitrile copolymer (Brookfield viscosity of a 10% aqueous solution at 20 ° C .; 9,400 cps) was used.

Reference Example 5 Acrylamide containing 30 mol% of nitrile groups
A white powdered Hoffman transition product was obtained in the same manner as in Reference Example 1, except that an acrylonitrile copolymer (Brookfield viscosity of a 10% aqueous solution at 20 ° C .; 19,000 cps) was used.

Reference Example 6 Acrylamide containing 40 mol% of nitrile groups
A white powdered Hoffman transition reaction product was obtained in the same manner as in Reference Example 1 except that an acrylonitrile copolymer (Brookfield viscosity of a 10% aqueous solution at 20 ° C .; 2,650 cps) was used.

Example 1 Acrylamide containing 10 mol% of nitrile groups
5 of acrylonitrile copolymer (Brookfield viscosity of 10% aqueous solution at 20 ° C .; 9,400 cps)
While maintaining 100 parts by weight of a 1% aqueous solution at 80 ° C.
21.44 parts by weight of a 30% aqueous sodium hypochlorite solution and 30
A mixture of 3.85 parts by weight of an aqueous sodium hydroxide solution (corresponding to twice the molar amount of sodium hypochlorite) was added all at once. After reacting at 80 ° C. for 10 seconds, a predetermined amount of cold water was added to make the polymer solid content concentration 1%. When the degree of cationization and the degree of anionization were determined in the same manner as in Reference Examples 1 to 3, 2.61 meq. / G, 1.1
5meq. / G. This was used for papermaking experiments within 5 minutes after production.

Comparative Examples 1 to 4 The viscosity of a 10% aqueous solution at 20 ° C. was 355, 2, 0, respectively.
The same procedure as in Reference Example 1 was carried out except for using a homopolymer of acrylamide of 00, 3,400, 51,800 cps to obtain a white powdered Hoffman transition reaction product. The above production results are summarized in Table 1.

[0034]

[Table 1]

Example 2, Reference Examples 7 to 12 To a 1% slurry of corrugated paper pulp having a beating degree of 450 ml csf, 0.5% (on a dry weight basis) of a sulfuric acid band was added to the pulp and stirred for 1 minute. Anionic polyacrylamide (15% product, Hopron 3150B,
Mitsui Toatsu Chemical Co., Ltd.)
4% (dry weight basis) was added and stirring continued for an additional minute. Then, 0.16% (based on dry weight) of the 1% aqueous solution of the Huffman transfer reaction product of Reference Examples 1 to 6 and Example 1 was added to the pulp, and the mixture was further stirred for 1 minute.
According to IS P8121, C.I. S. F. Was measured, and the rest was made with a TAPPI square sheet machine. Then 11
Dry for 2 hours in a blow dryer at 0 ° C, and the grammage is 125 ± 3.
g / m ² of handmade paper was obtained. Regarding the evaluation of handmade paper, [specific burst strength] was determined according to JIS P8112.
[Z-axis strength] was measured with an internal bond tester manufactured by Kumagai Riki.

Comparative Examples 5 to 8 Except for using the Huffman rearrangement reactants of Comparative Examples 1 to 4, the same procedures as in Example 2 and Reference Examples 7 to 12 were carried out, and the basis weight was 125 ± 3.
g / m ² of handmade paper was obtained. [Specific burst strength] and [Z-axis strength] were measured in the same manner as in Example 1 and Reference Examples 7 to 12. Table 2 summarizes the above results.

[0037]

[Table 2]

REFERENCE EXAMPLE 13 A wet paper before drying was produced in the same manner as in Example 2 and Reference Examples 7 to 12 using the Huffman transfer product of Reference Example 1. Two sheets of handmade paper were stacked in a wet state, rolled several times with a stainless steel roll, and then pressed at 3.5 kg / m ² for 2 minutes. Subsequently, it was dried for 2 hours by a blow dryer at 110 ° C. to obtain a handmade paper having a basis weight of 250 ± 6 g / m ² . Regarding the evaluation of handmade paper, [interlayer paper strength] was measured by an internal bond tester manufactured by Kumagai Riki.

Comparative Example 9 A hand-made paper having a basis weight of 250 ± 6 g / m ² was obtained in the same manner as in Reference Example 13 except that the Hoffman rearrangement reaction product of Comparative Example 3 was used. Reference Example 13 for evaluation of handmade paper
The measurement was performed in the same manner as described above.

Comparative Example 10 A hand-made paper having a basis weight of 250 ± 6 g / m ² was obtained in the same manner as in Reference Example 13 except that no paper strength agent was used.
Regarding the evaluation of the handmade paper, the measurement was performed in the same manner as in Reference Example 13. Table 3 summarizes the above results.

[0041]

[Table 3]

[0042]

According to the present invention, the use of the novel polyacrylamide achieves a significant improvement in the strength of the Z-axis paper and the strength of the interlayer paper, which can not be achieved by the prior art, and furthermore, the drainage. Although the reason is not necessarily clear, it has not been heretofore known that such an effect is brought about by the presence of the nitrile group, and it is possible to produce paper having excellent Z-axis strength and interlayer strength. became.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-56-4606 (JP, A) JP-A-55-152896 (JP, A) JP-B-52-29796 (JP, B2) (58) Field (Int.Cl. ⁶ , DB name) D21H 11/00-27/42

Claims (3)

(57) [Claims] (1) a group having a carbamoyl group:
Mol%, (b) an acrylamide-based copolymer containing 3 to 40 mol% of a nitrile group and a hypohalite, under alkaline conditions of at least pH 11 or more, from 50 to 11
A cationic polyacrylamide obtained by performing a reaction in a temperature (T) range of 0 ° C. within a short time (t) specified below. e ^{15,150 / (273 + T)} × 2.5 × 10 ⁻²⁰
≦ t (sec) ≦ e ^{15,150 / (273 + T)} ×
10 ⁻¹⁸ +30 (T is the reaction temperature (° C.)) 2. A paper strength enhancer comprising the cationic polyacrylamide according to claim 1 as an active ingredient. 3. A drainage improver comprising the cationic polyacrylamide according to claim 1 as a main component.