JPS5945797B2 - Kamikakoshiyorizai - Google Patents

Description

[Detailed description of the invention] The present invention relates to paper processing agents.

Specifically, it is an excellent resin made of a water-soluble or water-dispersible resin containing a cationic group obtained by aminoesterifying an anionic vinyl polymer containing a carboxyl group and/or a carboxylate group, a polyamine, and an epihalohydrin. This paper relates to a paper processing agent that exhibits high performance. When producing paper, the cationic nature of the agents used has numerous advantages.

For example, it has the advantage of being self-fixing, does not require a fixing agent such as aluminum sulfate, and can itself act as a fixing agent for other drugs. Therefore, various drugs have been proposed that are made of water-soluble or water-dispersible resins having cationic groups. However, the performance of such known drugs has been unsatisfactory. For example, Japanese Patent Publication No. 43-14165 discloses a chemical based on a reaction product of polyethyleneimine and epihalohydrin, but since it is a wet paper strength enhancer, there are problems in recovering waste paper. Japanese Patent Publication No. 41-184013 also discloses a method of using a complex of an acrylamide polyanion and polyethyleneimine as a paper processing agent, but since the bond in the complex is a simple one-on bond, It is greatly influenced by the conditions of use and is effective only under limited conditions. It is also ineffective unless an anionic polymer with a fairly high molecular weight is used, and there are many problems such as poor storage stability. Furthermore, JP-A No. 47-38585 discloses tertiary carboxylic acid which is a polymer obtained by reacting carboxylic acid polyphenylene with glycidyl tertiary amine.
grade aminohydroxyalkyl esters are shown.

Although high molecular weight ones are recognized to be useful as flocculation agents, they are insufficiently effective as paper strength agents. As a result of intensive research in order to overcome the drawbacks of conventionally known paper processing agents, the present inventors have discovered that the present invention contains a polyaminohydroxyalkyl ester obtained by subjecting a specific anionic polymer, polyamine, and epihalohydrin to an aminoesterification reaction. We discovered that water-soluble or water-dispersible resins exhibit excellent performance as paper processing agents.
This completes the present invention.

Therefore, one object of the present invention is to provide a paper processing agent suitable for improving the paper strength of paper when it is dried.

Another objective is to provide a paper processing agent suitable for improving the yield of sizing agents and various fillers used in paper manufacturing, improving the water content of pulp, and clarifying pulp waste liquid and white water. It is something that is in . The anionic polymer in the present invention contains 60.0 to 98.0% by weight of acrylamide and/or methacrylamide and 2.0 to 200% of a copolymerizable unsaturated monomer containing a carboxyl group and/or canuboxylate group. % by weight and other copolymerizable neutral unsaturated monomers from 0 to 38.0% by weight (however, the total amount is 100%)
), which is a copolymerization reaction! This makes it easy to adjust.

Acrylamide and/or methacrylamide are essential components for improving the quality of paper and for imparting hydrophilicity to anionic polymers, and if the amount used is small, less than 60% by weight, the preparation Even if this polymer is used as a paper processing agent by reacting it with a polyamine or epihalohydrin, this agent is only unsatisfactory in terms of paper quality improvement performance. The copolymerizable unsaturated monomer containing a carboxyl group and/or a carboxylate group is a monomer necessary for imparting anionic properties to the polymer, and is also a monomer necessary for the following reaction between a polyamine and epihalohydrin. It is also a necessary functional group.

The amount of this monomer is within the range mentioned above; if it is too small outside of this range, the reaction with polyamines and epihalohydrin will be insufficient, whereas if it is too large, those groups will remain unreacted. A large amount may remain in some cases, and in either case, it is not preferable because the object of the present invention cannot be achieved. Specific examples include acrylic acid, methacrylic acid, tarotonic acid, fumaric acid, maleic acid, and ammonia and/or alkali metal salts of these acids. Other copolymerizable unsaturated monomers are effective in improving paper quality, introducing hydrophobicity, adjusting solution viscosity, etc., depending on the case, and can be used in amounts within the above range. Examples include lower alkyl acrylates such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and lower alkyl methacrylates; acrylonitrile, methacrylonitrile, vinyl chloride, etc. Ethylenically unsaturated monomers; ring-containing vinyl compounds such as styrene, vinyltoluene, square restyrene, chloromethylstyrene; hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate,
Examples include acrylic esters and methacrylic esters containing a hydroxyl group or an embossed group such as glycidyl methacrylate; vinyl esters such as vinyl acetate and vinyl propionate. The anionic polymer contains 62.0 to 100.0% by weight of acrylamide and/or methacrylamide and 0 to 38.0% by weight of other copolymerizable neutral unsaturated monomers as described above (however, the total amount It can also be obtained by hydrolyzing a homopolymer or copolymer consisting of 100%).

In this case, one carboxyl group and/or one carboxylate group can be imparted to the polymer through a hydrolysis reaction. Then, the amount of hydrolysis is the hydrolysis reaction l
The amount of carboxyl groups and/or carboxylate groups thus produced is in the range of 2.8.times.10@-4 molar equivalents to 2.7.times.10@-3 molar equivalents per gram of polymer. The polyamine used in the present invention contains two or more primary amines, secondary amines and/or tertiary amines in one molecule, and preferably has a molecular weight of about 500 or more.

If a low molecular weight polyamine having a molecular weight of less than about 500 is used, the effect as a paper processing agent will be unsatisfactory, which is not preferable. Specific examples of such polyamines include homopolymers and copolymers of aziridine compounds such as polyethyleneimine, polypropyleneimine, and derivatives of these polymers; ammonia or lower amines such as methylamine, dimethylamine, and ethylenediamine. Polyamide polyamines prepared by condensation of low molecular weight polyamines such as lydiethylenetriamine, triethylenetetramine, etc. and dibasic carboxylic acids such as adipic acid etc. etc. can be mentioned.
The epihalohydrin used in the present invention is a compound such as epibromohydrin, epichlorohydrin, epiiodohydrin, and the like. Among these compounds, epichlorohydrin is advantageously used in industrial applications. Of course, as shown in formula (1), it is also possible to use compounds such as dihalohydrin which produces epihalohydrin by reaction.

The ratio of each component used when synthesizing the paper processing agent of the present invention is within the following range.

First, the ratio of the polyamine to the anionic polymer is 0.5 to 5 amino groups in the polyamine per carboxyl group and/or carboxylate group in the polymer.
, preferably 0.7 to 4. If the amount of polyamine used relative to the anionic polymer exceeds the above ratio range, this agent will cause problems in the recovery of waste paper, even if the resulting resin is considered to have been processed into paper. . Next, the usage ratio of epihalohydrin is 0.2 to 3.0 per amino group in the polyamine.
The amount corresponds to molar equivalents, preferably 0.8 to 2.0 molar equivalents. The reaction between these components is an aminoesterification reaction between a carboxyl group and/or a carboxy root group, a polyamine, and an epihalohydrin, as shown by the following formula. (3) Formula [However, A in each formula represents hydrogen, ammonium, or an alkali metal, B represents a polyamene residue, and X represents a halogen.

] Depending on the order in which the anionic polymer, polyamine, and epihalohydrin are used, the above-mentioned reactions occur, that is, the neutralization of the anionic polymer by the polyamine, which is shown in formula (1) where the epihalohydrin reacts. The reaction represented by formula (2) in which epihalohydrin and polyamine react with carboxyl groups and/or carboxylate groups, carboxyl? and/or a reaction represented by formula (3) in which evihalohydrin is added to a carboxylate group, and then a cationization reaction with a polyamine occurs;
Epihalohydrin adduct of polyamine reacts with carpoxyl group and/or carboxylate group (4)
Each of the reactions shown in the formula occurs.

In either reaction, a polyaminohydroxyalkyl ester is produced, and a cationic group is introduced into the anionic polymer. This indicates that when the amount of carboxyl groups and carboxylate groups is measured by conductivity titration, colloid titration, etc., it decreases with time, and that the amount of polyaminohydroxyalkyl ester groups increases as the reaction progresses. This is evidenced by the fact that the amount of ionic halogen increases along with this, and that the pH value of the precipitate of the diluted resin solution decreases. Moreover, these reactions proceed more favorably when the carboxyl group in the anionic polymer is reacted as an alkali metal salt, and the more the amount of epihalohydrin is large. This reaction was carried out at 75°C.
The temperature below, generally 30-75°C, preferably 40-75°C
It is carried out at a temperature in the range of 70°C.

What must be noted during the reaction is the hydrolysis reaction of the amide group. This reaction is carried out in water under alkaline conditions, and if the reaction temperature exceeds 75°C, an indiscriminate hydrolysis reaction will proceed, making it impossible to obtain the desired reaction product. It is preferable to do it below. Examples of the reaction medium include an aqueous medium, an organic medium, a mixed medium, and the like, but from an industrial perspective, it is advantageous to use a water medium. The paper processing shavings of the present invention can be produced by various methods, but specific methods include:
1) After mixing the anionic polymer and polyamine,
2) A method of mixing the anionic polymer, a polyamine, and epihalohydrin and then reacting the mixture. 3) A method of reacting the anionic polymer with epihalohydrin and then adding a polyamine. 4) Methods such as a method in which an anionic polymer is reacted with a reaction product of a polyamine and epihalohydrin can be mentioned.

Among these methods, methods 1) and 2) are preferred because they can most effectively convert the carboxyl group and/or carboxylate group of the anionic polymer into an aminohydroxyalkyl ester group. It's a method. The paper processing agent of the present invention obtained through such reaction C does not require any pH adjustment after the reaction,
It is extremely stable in neutral conditions, and no change is observed in its effectiveness as a paper processing agent even after long-term storage.

Rather, they are unstable in both acidic and alkaline environments. This is a characteristic point 5 when compared to the fact that conventionally known cationic resins are stabilized in acidic conditions. In addition, since the resin in the present invention has a cationic group, it has self-fixing properties on cellulose fibers, and is effective even at a low viscosity compared to conventionally known anionic resin treatment, and is effective in drying paper. When used as a paper strength agent, a sufficient effect can be expected with a small amount used. Moreover, since the wet paper strength enhancing effect is small, it exhibits several excellent effects such as no problem in recovering waste paper generated in the paper manufacturing process. How to use the paper processing agent of the present invention (there are no special restrictions on this), and it may be used alone or in combination with other paper processing agents.

In use, the same method as in the case of conventionally known paper processing and cutting can be adopted. For example, when used as a paper strength enhancer (in this case, the paper processing agent of the present invention is diluted to about 1% by weight and added to a paper stock suspension in an amount of 0.01 to 1% per paper stock). 5% by weight, preferably 0.1 to 2% by weight (f) (can be used based on the so-called internal addition method, which is a method of continuously adding it to a suitable place before the papermaking process. , methods such as dipping, coating, and spraying are adopted after the papermaking process.In the internal addition method, the paper processing agent of the present invention has extremely excellent fixing properties, so the pH value of the paper stock suspension is It can be effectively used under a wide range of conditions from 9 to 4.And, by such a method,
Dryness of paper, such as bursting strength, tensile strength, compressive strength,
Surface strength etc. can be improved. In some cases, it may also be used in combination with other paper strength agents such as starch, vegetable gums, and anionic acrylamide paper strength agents. The present invention will be explained in more detail below using Examples and Comparative Examples, but of course the present invention is not limited to the Examples. In addition, parts in each example indicate parts by weight, and %
indicates weight %. Example 1 80% acrylamide, 10% styrene, 1 acrylic acid
A solution viscosity of 20% polymer concentration at a temperature of 25° C. was derived using a ratio of 0%. The degree is 240 centipoise (hereinafter referred to as Cps).

) and 302 parts of water were charged into a reactor. Then, at a temperature of 25°C, 12 parts of a 50% strength aqueous solution of polyethyleneimine having a number average molecular weight of about 5000 were added, mixed and the temperature was increased to 50°C. When a temperature of 50°C was reached, 19 parts of epichlorohydrin was added over 5 minutes.

After reacting at the same temperature for 2 hours, the mixture was cooled to obtain an aqueous dispersion of the desired resin. This dispersion has a resin content of 15% and 25% resin content.
Viscosity at a temperature of °C. The temperature was 445 cps. The aqueous dispersion of the resin thus obtained was used as the paper processing agent of the present invention (hereinafter referred to as processing "A").

) Example 2 A polymer concentration of 20 (Fb solution viscosity of 210 cps) was derived using a ratio of 80% acrylamide, 15% acrylonitrile, 5% acrylic acid,
1000 parts of a 20% aqueous solution of an anionic polymer in which the amount of carboxyl groups and carboxylate groups in the polymer is 9.7 x 10-4 m0I equivalent per 1 g of polymer and 44 parts of water.
2 parts and 5.8 parts of sodium hydroxide were charged to the reactor.

Next, 21 parts of a polyethylene t-imine aqueous solution having a concentration of 30 Cf and having a number average molecular weight of about 50,000 and 21 parts of copichlorohydrin were added, heated to a temperature of 60°C, and reacted at the same temperature for 1 hour and 30 minutes. . After cooling, resin content 15.1%, 25
An aqueous resin solution was obtained having a viscosity of 320 cps at a temperature of .degree. 1 The aqueous resin solution thus obtained was used as a paper processing agent of the present invention (hereinafter referred to as processing agent "B"). Example 3 In Example 2, instead of the polyethyleneimine aqueous solution, a solution having a number average molecular weight of about 5000 was prepared by dehydration condensation of diethylenetriamine 1m01e and adipic acid 1m01e.
Polyamide polyamine aqueous solution 62 with a concentration of 50% having
The reaction temperature was 55°C, the reaction time was 1 hour, and the other conditions were the same as in Example 2.
An aqueous resin solution having a viscosity of 200 cps at a temperature of 5° C. was obtained.

The aqueous resin solution thus obtained was used as the paper processing agent of the present invention (hereinafter referred to as processing [C]).

). Example 4 85% acrylamide, 10% methyl acrylate, 50% metatallylic acid! ), the solution viscosity at a polymer concentration of 20% at a temperature of 25°C is 105 cps, and the carboxyl and carboxylate groups in the polymer are 7.0XI0-4 per 19 of the polymer.
A reactor was charged with 1,000 parts of a 20% aqueous solution of an anionic polymer equivalent to m01e, 413 parts of water, and 6 parts of potassium hydroxide.

Next, ammonia 1m01e and epihalohydrin 0.6
r1)) 30% aqueous solution of condensed polyamine with a number average molecular weight of about 950 obtained by condensation reaction with the juice of 1e 27
．． 5 parts were added, mixed and the temperature was increased to 50°C. 20 parts of epichlorohydrin was added over 10 minutes and reacted at the same temperature for 4 hours, resulting in a resin content of 15.30! ), a slightly opaque aqueous resin solution having a viscosity of 130 cps at 25° C. was obtained. The aqueous resin solution thus obtained was used as the paper processing agent of the present invention (hereinafter referred to as processing "D").

). Example 5 A ratio of acrylamide 95 (Fbl ethyl acrylate 501) was used to obtain a solution with a viscosity of 20% polymer concentration of 160 cps at a temperature of 25°C.
A reactor was charged with 1000 parts of a 20% aqueous solution of the following polymer.

Next, 1000 g of water containing 5 parts of sodium hydroxide dissolved therein
After adding 50% of the mixture and straining it uniformly, it was heated to a temperature of 80°C.
The hydrolysis reaction was carried out at a temperature of 80°C for 3 hours.

The amount of carboxylate groups per polymer 19 is 6.2 × 10
-4m01e equivalent. A 50% aqueous solution of polyethyleneimine having a molecular weight of approximately 10,000 3
0 parts were added and the mixture was heated to a temperature of 55°C. Next, add 30 parts of epichlorohydrin at once, keep it at the same temperature for 0.5 hours, then adjust the pH to 6.8 using formic acid, and adjust the resin content to 12.0% and the viscosity at 25°C. 300cp
An aqueous resin solution of s was obtained. The aqueous resin solution thus obtained was used as the paper processing agent of the present invention (hereinafter referred to as the processing agent "E").
”.

). Example 6 The carboxylate groups and carboxyl groups in the polymer were derived using a ratio of 95% methacrylamide and 5 (fl) acrylic acid, and the solution viscosity at 20% polymer concentration at 25° C. was 100 cps. The base weight is 7.2 x 10-4 m0 per 19 polymers! 1000 parts of a 20% aqueous solution of a polymer, equivalent to e, was charged into a reactor.

15 parts of a 60% aqueous solution of polyethyleneimine having a number average molecular weight of about 1000 and 136 parts of water were added and heated to a temperature of 50°C. Next, 29 ends of epibromohydrin were added at once, kept at the same temperature for 1 hour, and then cooled, resulting in a resin content of 20! ), an aqueous resin solution having a viscosity of 350 cps at a temperature of 25° C. was obtained. The aqueous resin solution obtained by straining I was used as the paper processing agent of the present invention (hereinafter referred to as the processing agent "F").
It is written as

). τ Example 7 Derived using 85% acrylamide, 10% acrylonitrile, and 5% acrylic acid, with 1.5% carboxyl and carboxylate groups per 19% polymer.
Contains 05 x 10-3 m01e equivalent, 02 at a temperature of 25°C
One reactor was charged with 560 parts of a 20% aqueous solution of a polymer having a 0% strength aqueous solution of 98 cps.

Next, 6.5 parts of a 48% sodium hydroxide aqueous solution was charged and heated to a temperature of 50°C. 50C of polyethyleneimine with a molecular weight of approximately 15,000! ) 8.8 parts of aqueous solution, 9.0 parts of epichlorohydrin and 41.6 parts of water were added, and 50 parts of aqueous solution was added.
After reacting for 5 hours at a temperature of °C and cooling, the resin content was 20
(f) An aqueous resin solution having a pH of 6.7 and a solution viscosity of 240 cps at a temperature of 25° C. was obtained. The aqueous resin solution thus obtained was used as a paper processing agent of the present invention (hereinafter referred to as processing agent "G"). Processing agent “G” is 1 part resin.
% with water to obtain a diluting agent "G".
Regarding dilution processing agent [G], 560m against PH change
The transmittance of μ wavelength light was measured.

For comparison, a simple mixture of the anionic polymer of this example, polyethyleneimine, and epihalohydrin was also measured in the same manner. The results were as shown in FIG. From FIG. 1, it can be seen that the diluent treatment agent "G" is stable throughout the range without turbidity, whereas a simple mixture is unstable and becomes turbid in the PFi range of 4 to 5.

This indicates that the treated part [G'' does not contain an ionic complex. In addition, processing agent "G" is extremely stable and has a rating of 6.
Even after being left at room temperature for several months, there was no change in appearance, and no change in performance was observed. Comparative example
1 Same as Example 7 except that 3.1 parts of ethylenediamine was used instead of the polyethyleneimine aqueous solution.The resin content was 20(f) and the melting viscosity at 25°C was 98 cps. An aqueous resin solution was obtained.

2. The aqueous resin solution thus obtained was used as a comparative paper processing agent (hereinafter referred to as comparative processing agent "I").

). Comparative Example 2 Same as in Example 7 (an anionic polymer was prepared by straining, and then the polymer had a molecular weight of about 15,000
A comparative paper processing agent was obtained by mixing a 50% aqueous solution of polyethyleneimine having 1,000 ml of polyethyleneimine in the same ratio as in Example 7 (hereinafter referred to as "comparative processing agent").

). A solution prepared by diluting the comparative treatment agent ``'' with water to a resin content of 1% became cloudy in the pH range of 3 to 5, and exhibited the properties of a simple ionic complex.

Example 8 In order to clarify the effects of each of processing agents "A" to "G", handmade paper was prepared according to the following procedure, and various tests were conducted on the paper.

Canadian. Standard. A treatment agent was added to a 1% slurry of L-UKP (hardwood UKP) beaten to 475 ml of freeness at a ratio of 0.6 (:f) to the dry pulp weight, and then the treatment agent was added to a 1% slurry of L-UKP (hardwood UKP) beaten to 475 ml of freeness. The paper is made by hand using a standard sheet machine, and the resulting sheet is dried at a temperature of 105° C. for 5 minutes to produce handmade paper.

Note that the basis weight is 809/TI. Each of the obtained handmade papers was then subjected to various tests shown in Table 1. The results were as shown in Table 1. As is clear from Table 1, it is understood that processing agent "AJ" and processing agent "G" have excellent self-fixing properties, increase the strength of paper, and are extremely advantageous in recovering waste paper. can.

Furthermore, it can be understood that it is advantageous to use a polyamine with a large molecular weight, and that it is advantageous compared to a composite such as IonFflex. Example 9 Kaolin clay was added in an amount of 20% based on the weight of L-BKPI fibers with a freeness of 450 ml (C.S.F.).

While stirring, the amount of treatment agent "B" as shown in Table 2 based on the fiber weight (in terms of resin content) was added, and Example 6t was added.
Paper was made in the same manner as in the paper mill. The kaolin retention rate of the paper thus obtained was measured based on the method described in TAPPI-T-4B-M-58.

The results were as shown in Table 2. Example
10 The flushing performance of the treatment agent "E" on cardboard waste paper with a freeness of 550 d (C.S.F.) was tested based on the method described in JIS-P-8121.

The results were as shown in Table 3.

[Brief explanation of the drawing]

Figure 1 shows the diluting agent "Gl (resin content: 1") obtained in Example 7.
%) is a drawing showing the change in transmittance of light at a wavelength of 560 mμ with respect to the pH change, and shows the clear difference between the paper processing agent of the present invention based on an aminoesterification reaction and simple polyion flux. . Symbol 4: This is a plot of the light transmittance change with respect to the PH change of the diluting agent "G". 5: This is a plot of the light transmittance change with respect to the PH change of a simple mixture of anionic polymer-polyethyleneimine-epihalohydrin before being subjected to the reaction in Example 7.

Claims (1)

[Claims] 1 acrylamide and/or methacrylamide 6
0.0 to 98.0% by weight of a copolymerizable unsaturated monomer containing a carboxyl group and/or a carboxylate group.
．． An anionic polymer consisting of 0 to 20.0% by weight and 0 to 38.0% by weight of other copolymerizable unsaturated monomers (however, the total amount is 100%) and a polyamine with a molecular weight of about 500 or more and epihalohydrin in an aqueous medium at a temperature of 75°C or lower in an amount corresponding to 0.5 to 5.0 amino groups in the polyamine per carboxyl group and/or carboxylate group, and 1 amino group in the polyamine. Paper processing characterized by being made of a water-soluble or water-dispersible resin containing a polyaminohydroxyalkyl ester obtained by an amino ester chemical reaction in an amount equivalent to 0.2 to 3.0 moles of epihalohydrin per piece. Processing agent. 2 Acrylamide and/or methacrylamide 6
2.0 to 100.0% by weight and 0 to 38.0% by weight of other copolymerizable unsaturated monomers (however, the total amount is 100%)
The carboxyl group and/or carboxylate group is derived by hydrolyzing a homopolymer or copolymer consisting of 2.8 x 10^-4 molar equivalents to 2.7 x 10 per gram of polymer. ^-^ An anionic polymer containing a proportion of 3 molar equivalents, a polyamine having a molecular weight of about 500 or more, and an epihalohydrin are mixed in an aqueous medium at a temperature of 75°C or less to form carboxyl groups and/or carboxylate groups 1
By carrying out an amino ester chemical reaction in an amount corresponding to 0.5 to 5.0 mol of epihalohydrin per amino group in the polyamine, and in an amount corresponding to 0.2 to 3.0 mol of epihalohydrin per amino group in the polyamine. A paper processing agent comprising a water-soluble or water-dispersible resin containing the resulting polyaminohydroxyalkyl ester.