JP2002121280A - Method for producing aqueous solution of cationic thermosetting resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyamide-epihalohydrin resin aqueous solution with the low content of low-molecular organohalogen substance(s) and negative judgment of a mutagenicity test using microorganisms. SOLUTION: This method for producing a polyamide-epihalohydrin resin aqueous solution comprises the following process: a polyamide-polyamine is first prepared by condensation reaction under heating between an aliphatic dibasic carboxylic acid and/or a derivative thereof and a polyalkylene polyamine in the molar ratio of 1:(0.8-0.89), in the presence of a basic compound, and is incorporated with an epihalohydrin, which is then reacted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is useful as a wet paper strength enhancer for paper, has a low content of low molecular weight organic halogen substances, and is one of the powerful carcinogenic evaluation methods (Ames test). Ames Test) is a method for producing an aqueous solution of a cationic thermosetting resin having a negative judgment.

[0002]

2. Description of the Related Art The usefulness of an aqueous solution of a polyamide polyamine-epihalohydrin resin as a wet paper strength enhancer for paper is described, for example, in Japanese Patent Publication No. 35-3547 and is well known. Further, with respect to a method for producing an aqueous solution of a polyamide polyamine-epihalohydrin resin having a low content of a low-molecular-weight organic halogen compound, in the reaction between the polyamide polyamine and epihalohydrin,
(I) Production method via a two-step reaction (JP-A-6-2070)
No. 13, JP-A-9-278880),
(Ii) a method of adding a mineral acid containing no halogen during the two-step reaction to suppress the formation of low-molecular-weight organic halogen compounds (JP-A-6-256508); (iii) a sulfur atom during the two-step reaction (Japanese Unexamined Patent Publication (Kokai) No. 6-220189), in which a nucleophilic substance containing a compound is added to replace the halogen group of a low-molecular-weight organic halogen compound, and (iv) an unreacted epihalohydrin is added by adding a basic substance during the two-step reaction. (V) Japanese Patent Application Laid-Open (JP-A) No. 6-1842, (v) a method for dehalogenating a low-molecular-weight organic halogen compound by further adding an amine compound through a two-step reaction (Japanese Patent Laid-Open No. 6-1842). 11-166034).

[0003]

However, in recent years, due to the growing tendency to protect the environment, not only is the content of low-molecular-weight organic halogen compounds low, but also an aqueous solution of a polyamide polyamine-epihalohydrin resin having low carcinogenicity of the resin itself. There is a need for a technology for manufacturing a semiconductor. An object of the present invention is to industrially produce a cationic thermosetting resin aqueous solution having a low content of a low-molecular-weight organic halogen compound and having a negative Ames test, which is one of the powerful evaluation methods for carcinogenicity. It is to provide a manufacturing method that can be provided.

[0004]

The present inventors have conducted intensive studies on the drawbacks of the resin produced by the above-mentioned known method, and as a result, have found that aliphatic dibasic carboxylic acids having 3 to 12 carbon atoms and / or By synthesizing a polyamide polyamine with a specific ratio of the reaction between the derivative and the polyalkylene polyamine and performing the reaction between the polyamide polyamine and epihalohydrin under specific conditions, (i) excellent wet paper strength enhancing effect; ii) a method for producing an aqueous solution of a cationic thermosetting resin having a low content of low-molecular-weight organic halogen compounds and (iii) a negative judgment of the Ames test, which is one of the powerful evaluation methods for carcinogenicity, The present invention has been completed.

That is, the present invention relates to (1) a method for producing an aqueous solution of a cationic thermosetting resin, which comprises reacting a polyamide polyamine with epihalohydrin;
(I) Polyamide obtained by heat-condensing an aliphatic dibasic carboxylic acid having 3 to 12 carbon atoms and / or a derivative thereof and a polyalkylene polyamine so that the molar ratio thereof becomes 1: 0.8 to 1. Obtaining a polyamine-containing liquid; (ii) adding a basic substance to the polyamide polyamine-containing liquid to obtain a basic substance-containing liquid; and (iii) a polyamide polyamine in the basic substance-containing liquid and a secondary in the polyamide polyamine. After the step of reacting 0.5 to 1.6 equivalents of epihalohydrin with respect to the amino group at a temperature of 5 to 50 ° C., (iv) diluting the reaction mixture obtained in the step (iii) without diluting the reaction mixture. Or a method of producing an aqueous solution of a cationic thermosetting resin, which comprises a step of reacting at a temperature of 30 to 80 ° C. by diluting or diluting the polyamide polyamine and epihalohydrid. The method of manufacturing a cationic thermosetting resin solution which comprises reacting a
(I) heat-condensing an aliphatic dibasic carboxylic acid having 3 to 12 carbon atoms and / or a derivative thereof with a polyalkylene polyamine so that the molar ratio thereof is 1: 0.8 to 0.89; A polyamide polyamine-containing liquid is obtained, and (ii) a polyamide polyamine in the polyamide polyamine-containing liquid and 0.5 to 1.6 equivalents of epihalohydrin with respect to the secondary amino group in the polyamide polyamine are mixed at 5 to 50 ° C.
After the step of reacting at a temperature of (iii), a step of reacting at a temperature of 30 to 80 ° C. without or by diluting the reaction mixture obtained in the step (ii). (3) The method according to the above (1) or (2), wherein 0.5 to 1 of the secondary amino group in the polyamide polyamine is used. A method for producing an aqueous solution of a cationic thermosetting resin in which a nucleophilic substance containing a sulfur atom is added during the step of reacting .6 equivalents of epihalohydrin with the polyamide polyamine at a temperature of 5 to 50 ° C. It is.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The number of carbon atoms used in the present invention is 3 to 1
Examples of the aliphatic dibasic carboxylic acid 2 include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, dodecane diacid, and the like. Is preferably an aliphatic dibasic carboxylic acid having 5 to 10 carbon atoms, particularly 5 to 8 carbon atoms.
Are preferred. Further, as the aliphatic dibasic carboxylic acid derivative having 3 to 12 carbon atoms, an acid anhydride of each of the above acids, or a C1 to C12 of each of the above acids.
5, in particular, lower alcohol (methyl, ethyl, propyl) esters having 1 to 3 carbon atoms, and industrially, glutaric acid methyl ester and adipic acid methyl ester are preferred.

Examples of the polyalkylene polyamine include diethylene triamine, triethylene tetramine, tetraethylene pentamine, iminobispropylamine and the like, and industrially, diethylene triamine is preferable.

In the case where a basic substance is added to a polyamide polyamine and then reacted with epihalohydrin, the polyamide polyamine has 3 to 3 carbon atoms.
The reaction molar ratio of the aliphatic dibasic carboxylic acid and / or a derivative thereof to the polyalkylene polyamine is 1: 0.
The heat condensation is carried out so as to be 8 to 1, preferably 1: 0.8 to 0.98. The ratio of polyalkylene polyamine is 1
If it is larger than the above, the obtained aqueous solution of the cationic thermosetting resin becomes positive in the judgment of the Ames test. When the ratio of the polyalkylene polyamine is smaller than 0.8, the obtained cationic thermosetting resin aqueous solution becomes negative in the judgment of the Ames test, but the storage stability is deteriorated, and the wet paper strength enhancing effect is reduced. Not enough.

On the other hand, when the polyamide polyamine is reacted with epihalohydrin without adding a basic substance, the reaction molar ratio of the polyamide polyamine is 1: 0.8 to 0.8.
9, heat condensation is carried out so as to be preferably 1: 0.8 to 0.875. When the ratio of the polyalkylene polyamine is 0.
When it is larger than 89, a low-molecular-weight organic halogen compound, for example, 1,3-
The content of dichloro-2-propanol, 3-chloro-1,2-propanediol, etc. increases and becomes positive in the Ames test. When the ratio of the polyalkylene polyamine is smaller than 0.8, the obtained cationic thermosetting resin aqueous solution becomes negative in the judgment of the Ames test,
Storage stability is deteriorated, and the effect of enhancing wet paper strength is insufficient.

By adding a basic substance as described above,
The addition reaction between the polyamide polyamine and the epihalohydrin proceeds efficiently, and the low-molecular-weight organic halogen compound, for example, 1,3-, contained in the aqueous solution of the cationic thermosetting resin.
The content of dichloro-2-propanol, 3-chloro-1,2-propanediol and the like can be significantly reduced, and even when the ratio of polyalkylenepolyamine is higher than when no basic substance is added, Ames It is considered negative in the test.

In the reaction of an aliphatic dibasic carboxylic acid having 3 to 12 carbon atoms and / or a derivative thereof with a polyalkylene polyamine, the aliphatic dibasic carboxylic acid and / or a derivative thereof or the polyalkylene polyamine is added. When the basic substance is added as described above with or without fixing the reaction molar ratio of the aliphatic dibasic carboxylic acid and / or derivative thereof and the polyalkylene polyamine in the reaction mixture by the addition, Finally 1: 0.
In the range of 8 to 1, even when the basic substance is not added as described above, the heat condensation can be finally performed in the range of 1: 0.8 to 0.89.

Polyalkylene polyamine and C3 to C1
The reaction with the aliphatic dibasic carboxylic acid (2) and / or a derivative thereof may be carried out by utilizing the heat of reaction generated at the time of charging the raw materials, or by heating from the outside while performing dehydration and / or dealcoholization reaction. I do. The reaction temperature is 110-
The temperature is 250 ° C., preferably 130 to 170 ° C., and the temperature condition depends on whether the starting material is an aliphatic dibasic carboxylic acid having 3 to 12 carbon atoms or a derivative thereof. In this case, as a catalyst for the polycondensation reaction, sulfuric acid, benzenesulfonic acid, sulfonic acids such as paratoluenesulfonic acid and phosphoric acid, phosphonic acid, phosphoric acids such as hypophosphorous acid, and other known catalysts alone or in combination. Can be used. The amount used is 0.005 to 0.1 mol, preferably 0.01 mol to 1 mol of the polyalkylene polyamine.
０．０５0.05 mol.

In this condensation reaction, the viscosity of a 50% by weight aqueous solution of the resulting polyamide polyamine at 25 ° C. is 50%.
It is continued until it becomes と 1,000 mPa · s. If the viscosity of the produced polyamide polyamine in a 50% aqueous solution is less than 50 mPa · s, the resulting cationic thermosetting resin aqueous solution may not have sufficient wet paper strength enhancing effect, which is not preferable. In addition, the viscosity is 1,000
When it exceeds 0 mPa · s, the obtained cationic thermosetting resin aqueous solution has an excellent wet paper strength effect, and although its usefulness as a drainage improver or a retention improver is great,
The storage stability of the resulting aqueous solution of the cationic thermosetting resin is remarkably deteriorated, which may lead to gelation, which is not preferable.

The condensation reaction of an aliphatic dibasic carboxylic acid having 3 to 12 carbon atoms and / or a derivative thereof with a polyalkylene polyamine preferentially reacts at a primary amino group of the polyalkylene polyamine, and then reacts with a secondary amino acid. Assuming that it reacts with the groups, the amount of secondary amino groups of the polyamide polyamine obtained in the above step is calculated by the following equation.

Amount of secondary amino group (equivalent / g) = (D1
× n-A1 × 2) / (D2 + A2 + CH) Here, D1 is a molar amount (mol) of the polyalkylene polyamine in the system, A1 is an aliphatic dibasic carboxylic acid having 3 to 12 carbon atoms in the reaction system and And / or the molar amount of its derivative (m
ol), D2 is the weight (g) of the polyalkylene polyamine in the system, A2 is the weight (g) of the aliphatic dibasic carboxylic acid having 3 to 12 carbon atoms and / or its derivative in the reaction system, C
Is the weight (g) of the catalyst in the system, H is the weight (g) of water and / or alcohol produced by the condensation reaction, and n is the number of primary and secondary amino groups in one molecule.

In the method for producing an aqueous solution of a cationic thermosetting resin according to the present invention, 0.01 to 0.5 equivalent, preferably 0.1 to 0.5 equivalent to the secondary amino group of the polyamide polyamine.
A low molecular organic compound contained in an aqueous solution of a cationic thermosetting resin obtained by reacting a polyamide polyamine with an added basic substance of 0.5 to 0.3 with epihalohydrin compared with the same one under other reaction conditions Halogen compounds,
For example, the content of 1,3-dichloro-2-propanol, 3-chloro-1,2-propanediol and the like can be further reduced, which is preferable because the result of the Ames test is negative.

When the amount of the basic substance is less than 0.01 equivalent relative to the secondary amino group of the polyamide polyamine,
The effect of adding a basic substance, that is, the effect of reducing the content of a low-molecular organic halogen compound in an aqueous solution of a cationic thermosetting resin may not be recognized. Also,
When the amount of the basic substance is more than 0.5 equivalent to the secondary amino group of the polyamide polyamine, the reaction between the polyamide polyamine and the epihalohydrin proceeds rapidly, the rate of increase in the viscosity of the reaction solution is remarkably fast, It is not preferable because the solution may be converted or the storage stability of the aqueous solution of the cationic thermosetting resin may be poor.

Examples of the basic substance of the present invention include inorganic alkaline substances such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, calcium hydroxide, and the like.
Alternatively, organic compounds such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and iminobispropylamine Amines, or ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and trimethylbenzylammonium hydroxide, etc., are industrially preferred, and inorganic alkaline substances are preferred, and sodium hydroxide and potassium hydroxide are preferred. Is particularly preferred.

Next, the polyamide-polyamine-containing liquid thus obtained is reacted with epihalohydrin. As epihalohydrin, epichlorohydrin,
Epibromohydrin and the like can be mentioned, but epichlorohydrin is industrially preferable. The molar ratio of epihalohydrin to secondary amino groups in the polyamide polyamine is from 0.5 to 1.6, preferably from 0.8 to 1.3. When the molar ratio of epihalohydrin is greater than 1.6,
The content of low molecular organic halogen compounds, for example, 1,3-dichloro-2-propanol, 3-chloro-1,2-propanediol, etc. in the obtained aqueous solution of the cationic thermosetting resin increases, and the Ames test is performed. Is liable to be positive, and the object of the present invention cannot be achieved. On the other hand, if the molar ratio of epihalohydrin is less than 0.5, the resulting cationic thermosetting resin aqueous solution will be negative in the determination of the Ames test, but the wet paper strength enhancing effect will be reduced, and the storage stability will be reduced. It is not preferable because the object of the present invention cannot be achieved due to deterioration.

The reaction between the polyamide polyamine and the epihalohydrin is usually carried out at a polyamide polyamine concentration of 30-8.
It is preferably carried out at 0% by weight. If the concentration of the polyamide polyamine is lower than 30% by weight, the progress of the reaction is remarkably slow, and the wet paper strength effect of the resulting aqueous solution of the cationic thermosetting resin is sometimes undesirably reduced. On the other hand, when the concentration of polyalkylene polyamine is 8
If it is higher than 0% by weight, the progress of the reaction is remarkably rapid, that is, the rate of increase in viscosity is remarkably high, which often leads to gelation, not only difficult to control the reaction, but also preservation of the product. It is not preferable because the stability may be extremely poor. Regarding the reaction temperature, relatively low temperature, ie, 5
The reaction is maintained at a temperature of ５０50 ° C., preferably 10-45 ° C., more preferably 25-35 ° C. (first step).

After the first step, the reaction temperature is set to 30 to 80.
C., preferably to 40-75.degree. C., and continue the reaction (second step).

In general, when the heating temperature is increased in the secondary step, the reaction mixture may become so thick that the control of the reaction becomes difficult. It is preferred to dilute to% by weight. Furthermore, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or
Formic acid, an organic acid such as acetic acid, preferably an inorganic acid containing no halogen, or at least one acid such as an organic acid, in order to facilitate the reaction control of the reaction product of the polyamide polyamine and epihalohydrin, 0.01 to 0.7 equivalents to secondary amino groups,
Particularly, it is preferable to add 0.02 to 0.35 equivalent.

In the reaction of the second step, the solid content of the product is 15
The viscosity of the aqueous solution at 25 ° C. is 6 to 300 mPa.
Preferably, the reaction is continued until s is reached. If the viscosity of the 15% by weight aqueous solution is less than 6 mPa · s, the resulting cationic thermosetting resin aqueous solution may not have sufficient performance as a wet paper strength enhancer, which is not preferable.
Further, when it exceeds 300 mPa · s, not only does the storage stability of the obtained cationic thermosetting resin aqueous solution deteriorate, but also when it is added to the pulp slurry in the papermaking process,
With remarkable foaming, not only makes papermaking work difficult,
It is not preferable because the texture of the paper to be made may be damaged.

Preferably, the reaction is stopped by adding water, and the solid content is adjusted to 15 to 40% while cooling.
Further, the pH is adjusted to 2 by adding an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, or an organic acid such as formic acid or acetic acid, preferably an inorganic acid containing no halogen or an organic acid. The viscosity is adjusted to 5 to improve the viscosity stability of the polyamide polyamine-epihalohydrin resin to obtain an aqueous solution of a cationic thermosetting resin.

In the method for producing an aqueous solution of a cationic thermosetting resin according to the present invention, a nucleophilic substance containing a sulfur atom is added in an amount of 0.01 to 0 to the secondary amino group of the polyamide polyamine during the first step. .1 equivalent, preferably 0.015-
By adding 0.08 equivalents and continuing the reaction while maintaining the reaction temperature at 10 to 40 ° C., a low molecular weight organic halogen compound contained in the obtained cationic thermosetting resin aqueous solution,
For example, the content of 1,3-dichloro-2-propanol, 3-chloro-1,2-propanediol, and the like can be further reduced, and a negative result is likely to be obtained in the Ames test, which is preferable.

Examples of the nucleophilic substance containing a sulfur atom include sodium sulfite, potassium sulfite, sodium acid sulfite, sodium metabisulfite, potassium metabisulfite,
Inorganic compounds such as potassium acid sulfite, sodium thiosulfate, potassium thiosulfate, sodium sulfide, potassium sulfide, sodium hydrosulfide, potassium hydrosulfide, ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, and 2-mercaptobenzothiazole; Organic compounds such as sodium salts, 2-mercaptobenzimidazole and sodium salts thereof, 2-mercaptothiazole and sodium salts thereof, 2-mercaptoimidazole and sodium salts thereof, alkylthiols and sodium salts thereof, and thioureas and organic compounds thereof and alkalis thereof Examples thereof include metal salts, and one or more of these can be used.

If the amount of the nucleophilic substance containing a sulfur atom is less than 0.01 equivalent relative to the secondary amino group of the polyamide polyamine, the rate at which the nucleophilic substitution reaction caused by the nucleophilic substance occurs is also reduced. It is not preferable because the ratio of reducing the content of the low-molecular-weight organic halogen compound may decrease. On the other hand, when the amount of the nucleophilic substance is more than 0.1 equivalent to the secondary amino group of the polyamide polyamine, the effect of increasing the wet paper strength of the resulting aqueous solution of the cationic thermosetting resin is reduced. There is. that is,
In polyamide-polyamine-epihalohydrin resins, the rate at which functional groups, such as azetidinium groups, epoxy groups, etc., which have a wet paper strength enhancing effect, react with the nucleophile and no longer lose the ability to thermoset is increased. As a result, it is considered that the amount of the functional group acting on the wet paper strength enhancing effect is reduced.

It is preferable to add a basic substance in the course of the primary step of forming the polyamide polyamine and epihalohydrin, since the amount of the low-molecular organic compound may be further reduced.
At this time, when the amount of the epihalohydrin remaining in the reaction solution becomes 1% by weight, preferably 0.5% by weight or less based on the solid content of the reaction solution, the basic substance is added to the polyamide polyamine in an amount of 0.01% by weight. The reaction may be continued at a reaction temperature of 5 to 50 ° C., preferably 10 to 40 ° C., more preferably 25 to 35 ° C. by adding 0.5 to 0.5 equivalent, preferably 0.05 to 0.2 equivalent. preferable.

In the Ames test of the present invention, an auxotrophic strain of Salmonella typhimurium (Histidine auxotroph His-), which cannot grow without histidine because histidine, which is a kind of amino acid, cannot be biosynthesized. When a chemical induces a mutation, reversion occurs and histidine can be synthesized (histidine-non-requiring strain His +), and grows in a medium containing only histidine and glucose to form white colonies. The Ames test is a method for examining a reversion from histidine auxotrophy to non-auxotrophy. The Ames test is a short-term search method for carcinogenicity evaluation that is currently widely used worldwide.

In the Ames test of the present invention,
A strain of Salmonella typhimurium TA1535 (hereinafter referred to as TA153), which is a strain that is highly sensitive to polyamide polyamine-epihalohydrin and is likely to be positive in the Ames test.
5).

In addition, many carcinogenic substances exhibit carcinogenicity by entering the body of mammals and undergoing metabolic activation. However, microorganisms lack the metabolic activating enzyme system of many carcinogenic substances, so in the Ames test, metabolic activating enzymes obtained by adding coenzymes to metabolic activating enzymes obtained from livers of rats etc. Two types of tests are performed: a metabolic activation test performed with the addition of the system (S9mix), and a non-metabolic activation test performed without the addition of the metabolic activating enzyme system (S9mix). In the present invention, only the metabolic activation test is carried out since the metabolic activation test shows a stronger mutagenicity of the polyamide polyamine-epihalohydrin. The operation procedure of the Ames test is described in detail in, for example, "Anti-mutagens and anti-carcinogens and their search methods", edited by Yukiaki Kuroda (Kodansha), and will be briefly described here.

The pre-culture solution of the test strain was obtained by inoculating TA1535 into a medium obtained by adding 100 g of distilled water to 2.5 g of nutrient broth manufactured by Oxoid, and then inoculating TA1535 and shaking reciprocally at 37 ° C. for 11 hours. The culture was used.

A test substance solution (polyamide polyamine-epihalohydrin resin aqueous solution) 0.1 m was put into a sterilized test tube.
1, S9mix 0.5 ml, test strain preculture 0.1
Add ml and stir with a mixer. Then pre-incubate for 20 minutes with shaking at 37 ° C. After preincubation, add 0.05 mM L-
Histidine-0.05 mM D-biotin and 0.6%
NaCl, 0.6% agar (Bacto manufactured by Difco)
agar containing 2 ml of soft agar, poured onto a minimal glucose agar plate, spread evenly, and shield from light. After culturing at 37 ° C. for 48 hours or more, the number of colonies generated by reversion is counted. It is determined to be positive if the number of revertant colonies is twice or more the number of colonies in a solvent control test performed using sterile distilled water instead of the test substance solution.

Composition of minimum glucose agar plate medium: distilled water 900 ml Vogel-Bonner minimum medium E stock solution 100 ml glucose 20 g agar (Bacto agar, manufactured by Difco) 15 g A 30 ml portion was dispensed into a petri dish and left on a horizontal surface to be cooled and solidified. In addition, Vo
The composition of the gel-Bonner minimal medium E stock solution was magnesium sulfate heptahydrate 2 g, citric acid monohydrate 20 g
g, dipotassium phosphate / anhydrous salt 100 g, monoammonium phosphate 19.2 g, and sodium hydroxide 6.6 g were dissolved in distilled water to make 1000 ml.

[0035]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, in each example, all percentages are by weight unless otherwise specified.

Example 1 702 g (6.8 mol) of diethylenetriamine and 11.9 g (88% phosphoric acid) were placed in a 5-liter four-necked round bottom flask equipped with a thermometer, a cooler, a stirrer, and a nitrogen inlet tube. .11 mol), 1169 g (8 mol) of adipic acid was added with stirring, the temperature was raised while removing generated water outside the system, and the mixture was reacted at 135 ° C. for 7 hours. Then, 1583 g of water was gradually added. Thus, a polyamide polyamine-containing liquid was obtained. This polyamide polyamine-containing liquid had a solid content of 51.8%, and had a viscosity of 405 mPa · s (25 ° C.) when the solid content was 50%.

In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 125.5 g of the polyamidepolyamine-containing liquid obtained above (0.18 equivalent as a secondary amino group) was placed. Water (18.9 g) was charged (solid content: 45%), and epichlorohydrin was added at 20 ° C.
3 g (0.2 mol) was added dropwise over 30 minutes.
And kept at the same temperature for 3 hours. Then, water 75.
After adding 3 g to a solid content of 35%, 30% sulfuric acid was added.
Add 94 g, heat to 65 ° C. and hold at this temperature,
When the viscosity of the reaction solution reached 360 mPa · s (25 ° C.), the reaction solution was further diluted with 82.5 g of water, and the pH was adjusted to 3 with sulfuric acid.
After adjusting to 6, 1.88 g of 88% formic acid was added.

Example 2 744 g (7.2 mol) of diethylenetriamine was charged into a 5-liter four-necked round-bottomed flask equipped with a thermometer, a cooler, a stirrer, and a nitrogen inlet tube, and 1169 g of adipic acid was stirred ( 8 mol) was added thereto, the temperature was raised while removing generated water outside the system, and the mixture was reacted at 170 ° C. for 4 hours. Then, 1560 g of water was gradually added to obtain a polyamide polyamine-containing liquid. This polyamide-polyamine-containing liquid had a solid content of 51.2% and a viscosity of 327 mPa · s (25 ° C.) when the solid content was 50%.

In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 127 g of the polyamidepolyamine-containing liquid obtained above (0.22 equivalent as a secondary amino group) and water 17 , And a 30% aqueous sodium hydroxide solution.
98 g (0.022 mol) were added. After adding 22.8 g (0.25 mol) of epichlorohydrin dropwise at 20 ° C. over 30 minutes, the mixture was heated to 30 ° C. and kept at the same temperature for 3 hours.
Next, 88.9 g of water was added to bring the solid content to 35%, then 7.32 g of 30% sulfuric acid was added, the mixture was heated to 65 ° C. and maintained at this temperature, and the viscosity of the reaction solution was 360 mPa · s.
When the temperature reached (25 ° C.), the mixture was further diluted with 87.8 g of water, adjusted to pH 3.6 with sulfuric acid, and cooled by adding 2.34 g of 88% formic acid.

Example 3 A 500 ml four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel was prepared.
125.5 g (0.18 equivalent as a secondary amino group) of a polyamide polyamine-containing liquid prepared in the first half of Example 1 and 19 g of water were charged (solid content: 45%), and epichlorohydrin was added at 20 ° C. After dropping 3 g (0.2 mol) over 30 minutes, the mixture was heated to 35 ° C. and kept at the same temperature for 2 hours. Then, 0.86 g of sodium metabisulfite
(0.0045 mol) was added and the mixture was kept at 30 ° C. for 1 hour. Next, 76.9 g of water was added to bring the solid content to 35%, then 2.94 g of 30% sulfuric acid was added, the mixture was heated to 65 ° C. and maintained at this temperature, and the viscosity of the reaction solution was 360 mPa · s.
When the temperature reached (25 ° C.), the mixture was further diluted with 82.5 g of water, adjusted to pH 3.6 with sulfuric acid, and cooled by adding 1.88 g of 88% formic acid.

Example 4 In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel,
127 g (0.22 equivalent as a secondary amino group) of the polyamide polyamine-containing liquid prepared in the first half of Example 2 and 19 g of water were charged (solid content: 45%), and 2.98 g of a 30% aqueous sodium hydroxide solution was further charged. (0.022 mol). At 20 ° C., 22.8 g of epichlorohydrin (0.2
(5 mol) was added dropwise over 30 minutes, then heated to 30 ° C. and kept at the same temperature for 2 hours. Next, 1.07 g (0.0056 mol) of sodium metabisulfite was added, and the mixture was further kept at 30 ° C. for 1 hour. Next, 85.2 g of water was added to bring the solid content to 35%, and then 7.32 g of 30% sulfuric acid was added to give 6%.
Heat to 5 ° C. and hold at this temperature to make the viscosity of the reaction solution 3
When the temperature reaches 60 mPa · s (25 ° C.), water 8
After diluting with 7.8 g and adjusting the pH to 3.6 with sulfuric acid,
2.34 g of 88% formic acid was added.

Comparative Example 1 The same procedure as in Example 2 was repeated except that sodium hydroxide was not added, and water was further added to reduce the solid content to 35%.
Except that after adding 3.66 g of 30% sulfuric acid,
The reaction was carried out in the same manner as in Example 2.

Comparative Example 2 908 g (8.8 mol) of diethylenetriamine was charged into a 5 liter four-necked round-bottomed flask equipped with a thermometer, a cooler, a stirrer, and a nitrogen inlet tube, and 1169 g of adipic acid was added with stirring. (8 mol) was added thereto, the temperature was raised while removing generated water out of the system, and the mixture was reacted at 170 ° C. for 8 hours. Then, 1,720 g of water was gradually added to obtain a polyamide polyamine-containing liquid. This polyamide polyamine-containing liquid had a solid content of 50.2% and a viscosity of 342 mPa · s (25 ° C.) when the solid content was 50%.

In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 129.5 g of the polyamidepolyamine-containing liquid obtained above (0.38 equivalent as a secondary amino group) was placed. 15 g of water was added (solid content: 45%), and a 30% aqueous sodium hydroxide solution was further added.
04 g (0.038 mol) were added. After adding 38.4 g (0.42 mol) of epichlorohydrin dropwise at 30 ° C. over 30 minutes, the mixture was heated to 30 ° C. and maintained at the same temperature for 3 hours.
Then, after adding 111.9 g of water to a solid content of 35%, 9.26 g of 30% sulfuric acid was added, heated to 65 ° C. and maintained at this temperature, and the viscosity of the reaction solution was 360 mPa · s.
When the temperature reached (25 ° C.), the mixture was further diluted with 104 g of water, the pH was adjusted to 3.6 with sulfuric acid, and 3.95 g of 88% formic acid was added.

Comparative Example 3 The same procedure as in Example 4 was repeated except that sodium hydroxide was not added, and water was further added to reduce the solid content to 35%.
Except that after adding 3.66 g of 30% sulfuric acid,
The reaction was carried out in the same manner as in Example 4.

Comparative Example 4 619 g (6 mol) of diethylenetriamine was charged into a 5 liter four-necked round-bottomed flask equipped with a thermometer, a cooler, a stirrer, and a nitrogen inlet tube, and 1169 g (8 mol) of adipic acid was stirred. ) Was added thereto, the temperature was raised while removing generated water out of the system, and the mixture was reacted at 140 ° C. for 3 hours. Then, 1450 g of water was gradually added to obtain a polyamide polyamine-containing liquid. This polyamide-polyamine-containing liquid had a solid content of 50.6%, and the viscosity when the solid content was 50% was 450 mPa · s (25 ° C.).

In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 128.5 g (0.087 equivalent as a secondary amino group) of the polyamidepolyamine-containing liquid obtained above was added. 19 g of water was charged (solid content: 45%), and 8.82 g of epichlorohydrin was added at 20 ° C.
(0.095 mol) was added dropwise over 30 minutes.
And kept at the same temperature for 3 hours. Then water 57.
After adding 7 g to a solid content of 35%, 30% sulfuric acid was added.
Add 25 g, heat to 65 ° C. and hold at this temperature,
When the viscosity of the reaction solution reached 360 mPa · s (25 ° C.), the reaction solution was further diluted with 75.9 g of water, and the pH was adjusted to 3.0 with sulfuric acid.
After adjusting to 6, 0.91 g of 88% formic acid was added.

Properties of each of the aqueous solutions of the cationic thermosetting resin obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and 1,3-dichloro-2-propanol (hereinafter abbreviated as DCP) in the products. Table 1 shows the content of 3-chloro-1,2-propanediol (hereinafter abbreviated as CPD) and the results of the Ames test of the aqueous solution of the cationic thermosetting resin.

[0049]

[Table 1]

(Reference Example) Examples 1-4 and Comparative Examples 1-4
Each of the aqueous solutions of the cationic thermosetting resin obtained in the above was subjected to a papermaking test using a Noble and Wood type handmade paper machine. The paper strength of the obtained paper when wet was measured. The results are shown in Table 2.

Papermaking conditions Pulp used: bleached kraft pulp (conifer / hardwood = 1 /
1) Beating degree (CSF) 410 Resin addition rate: 0.3% (based on pulp solids) Papermaking basis weight: 65 g / m ² Drying conditions: 100 ° C × 120 sec (using a drum dryer)

[Table 2]

[0052]

Thus, the aqueous solution of the cationic thermosetting resin obtained according to the method of the present invention has an excellent wetness equivalent to or higher than that of the polyamide polyamine-epichlorohydrin resin produced by a known method. Gives paper-strengthening effect, and has excellent storage stability despite high solids content, extremely low content of low-molecular-weight organic halogen compounds contained in resin, and resin solution is carcinogenic It has an extremely excellent performance in which the judgment of the Ames test as an index is negative.

The aqueous resin solution obtained by the method of the present invention is useful only as a wet paper strength improver for paper, a drainage improver used in the papermaking process, or a retention improver such as a filler or a sizing agent. Instead, it can be used as a flocculant in plant wastewater treatment, or as a water-proofing agent for cellulose materials, a water-proofing agent such as polyvinyl alcohol, a natural fiber treating agent for wool, or a synthetic fiber treating agent.

Continuing on the front page (72) Inventor Liu Iwai 17-2 Yawata Kaigandori, Ichihara-shi, Chiba Prefecture Inside PMMC Corporation (72) Inventor Koji Kawaguchi 17-2 Yawatakaigan-dori, Ichihara-shi, Chiba Within MC Corporation (72) Inventor Hideomi Matsuoka 17-2 Yawata Kaigandori, Ichihara-shi, Chiba F-term within PCMC Corporation (reference) 4J001 DA01 DB01 DC06 DD12 EB05 EB06 EB07 EB08 EB09 EC86 EC87 EE04E EE12E EE14D EE16D EE38C EE43E EE44E EE45E EE64E EE72D EE72E EE78D FB03 FB05 FC03 FC05 FD01 FD03 GB02 GB04 GE02 JA17 JB02 JC08 4L055 AG37 AG32 FA93 EA30 EA20

Claims (3)

[Claims] 1. A method for producing an aqueous solution of a cationic thermosetting resin, comprising reacting a polyamide polyamine with epihalohydrin, wherein (i) an aliphatic dibasic carboxylic acid having 3 to 12 carbon atoms and / or a derivative thereof. And a polyalkylene polyamine in a molar ratio of 1: 0.8
To 1 to obtain a polyamide polyamine-containing liquid, and (ii) a basic substance is added to the polyamide polyamine-containing liquid to obtain a basic substance-containing liquid. And 0.5 to 1.6 with respect to the secondary amino group in the polyamide polyamine.
After the step of reacting an equivalent amount of epihalohydrin at a temperature of 5 to 50 ° C, (iv) the reaction mixture obtained in the step (iii) can be diluted without dilution or by dilution.
A method for producing a cationic thermosetting resin aqueous solution, comprising a step of reacting at a temperature of 0 to 80 ° C. 2. A method for producing an aqueous solution of a cationic thermosetting resin, comprising reacting a polyamide polyamine with epihalohydrin, wherein (i) an aliphatic dibasic carboxylic acid having 3 to 12 carbon atoms and / or a derivative thereof. And a polyalkylene polyamine in a molar ratio of 1: 0.8
To 0.89 to obtain a polyamide polyamine-containing liquid, and (ii) a polyamide polyamine in the polyamide polyamine-containing liquid and a secondary amino group in the polyamide polyamine of 0.5 to 1. After the step of reacting 6 equivalents of epihalohydrin at a temperature of 5 to 50 ° C, (iii) the reaction mixture obtained in the step (ii) is diluted without dilution or at a temperature of 30 to 80 ° C.
A method for producing an aqueous solution of a cationic thermosetting resin, comprising the step of reacting at a temperature of: 3. A process comprising the step of reacting 0.5 to 1.6 equivalents of epihalohydrin with respect to the secondary amino group in the polyamide polyamine and the polyamide polyamine at a temperature of 5 to 50 ° C., including a sulfur atom. The method for producing a cationic thermosetting resin aqueous solution according to claim 1 or 2, wherein the reaction is continued by adding a nucleophilic substance.