JPH0460488B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a new and useful method for producing a paper coating resin. (Prior art) In recent years, printing has become faster, more precise, and more colorful, and coated paper and art paper are required to have even higher surface strength and improved receptivity to printing ink. . Melamine-formaldehyde resins have traditionally been used to impart water resistance to various paper coating compositions consisting of pigments, adhesives, dispersants, and other auxiliary agents, or to improve ink receptivity. It is known to use formaldehyde-based resins such as urea-formaldehyde resins or polyamide-urea-formaldehyde resins, or cationic epoxy-modified polyamide resins such as polyamide-epihalohydrin resins. (Problems to be Solved by the Present Invention) However, as the demand for particularly improving ink receptivity has recently increased, the above-mentioned resins are no longer sufficient, and there is an urgent need to develop new resins. (Means for Solving the Problems) As a result of extensive research, the present inventors have developed a paper coating resin that is not only water resistant but also has particularly excellent ink receptivity. The configuration of the present invention will be explained below. That is, in the present invention, for 1 mole of dibasic carboxylic acid or dibasic carboxylic acid derivative,
At least a primary compound having 2.0 mol or less of an amino compound having one primary amino group and/or a monobasic carboxylic acid or a monobasic carboxylic acid derivative, and a polyalkylene polyamine and/or a polyalkylene polyurea as components. A polyamide polyamine and/or polyurea polyamide resin was obtained by reacting with 0.5 to 5.0 moles of an amino compound having two amino groups, and the resin and the primary amino groups and secondary amino groups in the resin were totaled. 1
Deammonification is carried out by reacting with 0.1 to 3.0 moles of urea per mole, and in the aqueous solution of the obtained reaction product, at least one crosslinking agent selected from epihalohydrin, formaldehyde and dialdehyde, and a primary, Secondary, tertiary amine group or 4
A cationizing agent, which is a compound having a class ammonium base, may be reacted with the cationizing agent simultaneously or with one of them first and the other afterwards, or with the crosslinking agent in an aqueous solution of the reaction product. The present invention provides a method for producing a paper coating resin, which comprises reacting with a reagent and then mixing the cationizing agent. The cationizing agent has the following general formula (),
Examples include compounds represented by () and ().

[expression] or

[expression] or

[expression] or (However, R ¹ , R ² , and R ³ each have 1 to 6 carbon atoms.
R ⁴ and R ⁵ each represent a monovalent aliphatic group having 1 to 6 carbon atoms or a hydrogen atom, and R ⁶ represents a divalent aliphatic group or an aromatic group. , X represents a halogen atom, and Y represents a halogen atom or 1/2SO ₄ or CH ₃ SO ₄ . ) The above cationizing agent is a compound having a primary, secondary, or tertiary amine group or a quaternary ammonium base. In carrying out the method of the present invention, first, a polyalkylene polyamine and/or a polyalkylene polyurea, a dibasic carboxylic acid or a derivative thereof, and further an amino compound containing one primary amino group and/or a monobasic carboxylic acid are used. The polyalkylene polyamine or polyalkylene polyurea used in the reaction with a basic carboxylic acid or its derivative has at least two
Refers to a compound having at least one primary amino group and at least one secondary amino group (imino group), each having the general formula H ₂ N-R ⁷ -NH ₂ [] or the general formula H ₂ N−R ⁸ −NHCONH−R ⁹ −NH ₂ [] [However, R ⁷ , R ⁸ and R ⁹ in the formula are each,
It represents a divalent aliphatic group and/or an aromatic group having at least one secondary amino group in the main chain. ] is displayed. In the following, these polyalkylene polyamines and polyalkylene polyureas are collectively represented by the general formula H ₂ N-A-NH ₂ [] [However, A in the formula is the above-mentioned R ⁷ or R ⁸ -
NHCONH-R ⁹ is represented, and R ⁷ , R ⁸ and R ⁹ are each as described above. ] May also be displayed. Here, typical examples of the polyalkylene polyamine include polyethylene polyamine, polypropylene polyamine, and polybutylene polyamine, among which polyethylene polyamine is preferred, and diethylene triamine, triethylene tetramine, and tetraethylene pentamine are particularly preferred. Most preferred. On the other hand, typical examples of the polyalkylene polyurea include deammonization reaction products from polyalkylene polyamines and urea as described above. Of course, these polyalkylene polyamines or polyalkylene polyureas may be used alone or in combination of two or more types, and they may also be used in combination with each other.
Furthermore, there is nothing to prevent the use of aliphatic diamines such as ethylene diamine, propylene diamine, hexamethylene diamine, etc. in an amount of 50 mol % or less in combination with these polyalkylene polyamines and/or polyalkylene polyureas. The above-mentioned dibasic carboxylic acid or its derivative is a general term that includes compounds having two carboxyl groups in the molecule, their esters, and even their acid anhydrides. Typical such carboxylic acids include aliphatic dibasic carboxylic acids and their esters such as succinic acid, glutaric acid, adipic acid or sebacic acid or maleic acid or fumaric acid, or isophthalic acid or terephthalic acid. There are aromatic dibasic carboxylic acids and their esters, as well as acid anhydrides such as succinic anhydride and maleic anhydride, but it goes without saying that these may be used alone or in combination of two or more. . In addition, the above-mentioned amino compound containing one primary amino group refers to a compound having one primary amino group in the molecule, and in this case, a secondary amino group (imino group) or It may contain one or more tertiary amino groups. Typical amino compounds include aliphatic amines such as laurylamine, stearylamine, monoethanolamine, diethylaminoethylamine, methylaminopropylamine, or N-aminoethylpiperazine, or aromatic compounds such as benzylamine or phenethylamine. These include group amines. Furthermore, the above-mentioned monobasic carboxylic acid or its derivative is a general term for compounds having one carboxyl group in the molecule and their esters, among which representative examples include formic acid, acetic acid, and These include aliphatic carboxylic acids and their esters, such as lauric acid, and aromatic carboxylic acids and their esters, such as benzoic acid or phenyl acetic acid. The step of preparing the polyamide polyamine or polyurea polyamide, which can also be referred to as the first reaction in the method of the present invention, is a process in which the polyalkylene polyamine and/or polyalkylene polyurea (hereinafter, these are combined with the compound ( a)) and a dibasic carboxylic acid or its derivative (hereinafter referred to as compound (b)).
It may also be displayed as . ), an amino compound containing one primary amino group (hereinafter, this may be referred to as compound (c)) and/
or a reaction of dehydration condensation in the presence or absence of a monobasic carboxylic acid or a derivative thereof (hereinafter sometimes referred to as compound (d)), which has the following reaction formula [],
It progresses according to [] or []. H ₂ N− A (a)−NH ₂ +HOOC− R (b) ¹⁰ −COOH ――→(−HN−A− NHCO (e)−R ¹⁰ −CO)−l [] H ₂ N− A (a )−NH ₂ +HOOC− R (b) ¹⁰ −COOH+R ¹¹ (c)−NH ₂ --→(—HN−A−NHCO− R (f) ¹⁰ −CO) _n --NH−R ¹¹ [] H ₂ N− A (a)−NH ₂ +HOOC−R ¹⁰ (b)−COOH+R ¹² − COOH (d) --→R ¹² −CO(−HN−A− NHCO (g)−R ¹⁰ −CO) _o -- [] [However, R ¹⁰ and R ¹¹ in the formula each represent a divalent or monovalent aliphatic group and/or an aromatic group, and R ¹² represents a hydrogen atom, a monovalent aliphatic group, and/or an aromatic group. represents a group, l, m and n
are all natural numbers. Also, A is as described above. ] In carrying out such a reaction, the amount of the polyalkylene polyamine and/or polyalkylene polyurea [compound (a)] used is equal to 1 of the amount of the dibasic carboxylic acid or its derivative [compound (b)].
0.5 to 5.0 mole to mole, preferably 1.0 to 3.0
The molar range is appropriate, and the amount of the amino compound containing one primary amino group [compound (c)] and/or the monobasic carboxylic acid or its derivative [compound (d)] is the same as that of the compound. A suitable range is 0 to 2.0 mol, preferably 0 to 1.0 mol, per 1 mol of (b). In addition, the reaction temperature at this time is suitably in the range of 100 to 300°C, preferably 140 to 220°C, and the reaction is carried out for 1 to 10 hours while removing the water produced from the system. A polyamide polyamine or polyurea polyamide represented by the reaction formula [], [] or [] is obtained. Next, in the second stage reaction, the polyamide polyamine or polyurea polyamide (e), (f), (g) obtained in the so-called first stage reaction (dehydration condensation reaction) as described above is used. A deammonification reaction is carried out with urea according to reaction formula [X] as described later. The amount of urea in this reaction is based on the polyamide polyamine or polyurea polyamide (e), (f), (g) obtained in the first stage reaction.
The range is from 0.1 to 3.0 mol, preferably from 0.2 to 1.5 mol, per mol of the primary and secondary amino groups in total. The reaction temperature is 90 to 160°C, preferably 110 to 140°C, and the reaction is carried out at this temperature for 0.5 to 10 hours while removing generated ammonia from the system. Of the deammoniation reactions (e), (f), and (g) above, (e)
If you display it as an example, it will look like the following. (-HN-A-NHCO-R ¹⁰ -CO) _l -- in (e) represents A as, for example, (-CH ₂ ) _p -- N H-B- NH-(CH ₂ ) _q -- and [-NH(-CH ₂ ) _p -- N H-B- NH(-CH ₂ ) _q --NHCO-R ¹⁰ -CO] _l --, so becomes. [However, B in the formula represents a divalent aliphatic group and/or aromatic group containing or not containing -NHC(=O)NH-, p and q are each natural numbers, and R ¹⁰ , l are as described above. In the third stage reaction in the method of the present invention, the deammoniated product (h) obtained by the so-called second stage reaction is dissolved in water, and then epirohydrin, formaldehyde and dialdehyde are added to it. At least one of the crosslinking reagents is reacted with at least one of the cationizing agents described in the general formulas [], [], and [], or the crosslinking reagent is reacted with the above-mentioned crosslinking reagent. After that, the cationizing agent is mixed. Epichlorohydrin or epibromohydrin is a typical epihalohydrin, and when combined with a cationizing agent, the amino acids in compound (a) and compound (c) used to synthesize compound (h) are It is preferable to add in an amount of 4 equivalents or less per 1 equivalent of the total number of groups. In addition, the combined amount of formaldehyde and dialdehyde is suitably 2 equivalents or less based on 1 equivalent of the total urea used to synthesize compound (h). Examples of the dialdehyde include glyoxal and glutaraldehyde. The order of addition of these epihalohydrin, formaldehyde, dialdehyde and cationizing agent is not particularly limited, and they may be added sequentially in any order or may be added at the same time. It is essential to add one or more reagents selected from among them and one or more reagents selected from among cationizing agents. Further, this reaction is carried out in an aqueous solution having a concentration of 20 to 80% by weight, preferably 30 to 60% by weight, at a pH in the range of 3 to 12, and at a reaction temperature of 40 to 90°C for 0.5 to 10 hours. Here, epichlorohydrin and formalin are used as crosslinking reagents, and 3-chloro-2-hydroxypropyltrimethylammonium chloride (trade name: Epinox SC-
For example, in the case where the reaction is carried out using 60 (manufactured by Derik Hercules), the cationic resin [i] is obtained as shown in the following general formula [XI]. [However, R ¹⁰ , B, p, q, and l in the formula are as described above. l αs are -C(=0)NH ₂ and/or -C(=O)NHCH ₂ OH, and l βs are hydrogen atoms and/or -CH ₂ CH(OH)
_CH2Cl and/or _-CH2CH (OH) _CH2N
(CH ₃ ) ₃ Cl. (Effects of the Invention) The resin thus obtained by the method of the present invention has not only excellent water resistance but also excellent ink receptivity, and is extremely important as an additive for paper coating compositions. (Example) Next, the present invention will be specifically explained using Examples, Comparative Examples, and Application Examples.
Unless otherwise specified, all values are based on weight. <Examples 1 to 6, Comparative Examples 1 to 6> Example 1 206 g of diethylenetriamine (2
mol) and monoethanolamine 12.2g (0.2 mol)
and 146g (1 mol) of adipic acid.
and conduct a condensation reaction at 160-170℃ for 3 hours,
The generated water was removed from the system. Then this
After cooling to 120°C, 176 g (2.94 mol) of urea was added and ammonia removal reaction was carried out at 120-130°C for 3 hours. Thereafter, water was added to this to obtain a 50% aqueous solution of polyamide polyurea. Next, a 60% aqueous solution of 3-chloro-2-hydroxypropylmethylammonium chloride (trade name: Epinox)
SC-60 (manufactured by Deitzk Hercules) 263g
(0.84 mol) and 67 g of 50% sodium hydroxide aqueous solution
After adding (0.84 mol) and reacting at 80°C for 2 hours, 78 g (0.84 mol) of epichlorohydrin was further added and the reaction was continued at 70-80°C for another 1 hour. After that, cool to 30℃ and add 51g of 37% formalin.
(0.63 mol) was added, the pH was adjusted to 5 with a 50% aqueous sulfuric acid solution, and the mixture was stirred while being maintained at 60 to 70°C for 3 hours. Further water was added to obtain a water-soluble resin with a solid content of 50%. Hereinafter, this resin aqueous solution will be abbreviated as "i-1". Example 2 In a reaction vessel similar to Example 1, 103 g (1 mol) of diethylenetriamine and triethylenetetramine were added.
146 g (1 mole) and 60 g (1 mole) of urea were charged, and the deammonia reaction was carried out at 140 to 150° C. for 3 hours with stirring. Next, this was cooled to 100°C, and 102 g (0.7 mol) of adipic acid and 37 g (0.3 mol) of benzoic acid were added to carry out a condensation reaction at 160 to 170°C for 3 hours, and the generated water was removed from the system. did. Next, after cooling this to 120°C, 238 g (3.96 mol) of urea was added and a deammonification reaction was carried out at 120 to 130°C for 3 hours. Thereafter, water was added to this to obtain a 50% aqueous solution of polyamide polyurea. Next, 100 g (0.66 mol) of glycidyltrimethylammonium chloride was added and reacted at 80°C for 2 hours, then cooled to 30°C and 37% formalin 268
g (3.3 mol) was added thereto, the pH was adjusted to 11 with a 30% aqueous sodium hydroxide solution, and the mixture was kept under stirring at 60 to 80°C for 3 hours. Further water was added to obtain a water-soluble resin with a solid content of 30%. Hereinafter, this resin aqueous solution will be referred to as "i-2".
It is abbreviated as Example 3 In a reaction vessel similar to Example 1, 219 g (1.5 mol) of triethylenetetramine and 73 g of adipic acid were added.
(0.5 mol) and 49 g (0.5 mol) of maleic anhydride were added and a condensation reaction was carried out at 160 to 170°C for 3 hours.
The generated water was removed from the system. Then set this to 120
After cooling to 0.degree. C., 216 g (3.6 mol) of urea was added and deammonization reaction was carried out at 120 to 130.degree. C. for 3 hours. Thereafter, water was added to this to obtain a 60% aqueous solution of polyamide polyurea. Next, 37 g (0.4 mol) of epichlorohydrin was added and reacted at 60 to 80°C for 2 hours, and then 58 g (0.4 mol) of 40% glyoxal aqueous solution
% diethylamine aqueous solution (0.4 mol), 37 g (0.4 mol) of epichlorohydrin, and 16 g (0.4 mol) of sodium hydroxide.
It was kept under stirring at ~80°C for 4 hours. Next, add 50% sulfuric acid aqueous solution to adjust the pH to 4 and further increase the pH to 60.
The mixture was stirred while being maintained at ~80°C for 4 hours, and water was added to obtain a water-soluble resin with a solid content of 40%. Hereinafter, this resin aqueous solution will be abbreviated as "i-3". Example 4 292 g (2 mol) of triethylenetetramine and 146 g (1 mol) of adipic acid were added to the same reaction vessel as in Example 1, and a condensation reaction was carried out at 160 to 170°C for 3 hours, and the generated water was removed from the system. It was removed. Then, after cooling this to 120°C, 216 g (3.6 mol) of urea
was added to carry out a deammoniation reaction at 120 to 130°C for 3 hours. Thereafter, water was added to this to obtain a 50% polyamide polyurea aqueous solution. Next, 192 g (2.4 mol) of 50% aqueous sodium hydroxide solution, 70 g (0.6 mol) of 2-chloroethylamine hydrochloride, and 103 g (0.6 mol) of N-(2-chloroethyl)diethylamine hydrochloride were added, and the mixture was heated at 60 to 80°C. After reacting for an hour, 56 g (0.6 mol) of epichlorohydrin was further added and the reaction was further continued at 60 to 80°C for 3 hours. Water was added to obtain a water-soluble resin with a solid content of 30%. Hereinafter, this resin aqueous solution will be abbreviated as "i-4". Example 5 In a reaction vessel similar to Example 1, 103 g (1 mol) of diethylenetriamine and triethylenetetramine were added.
Add 146g (1 mol) and add succinic anhydride.
120 g (1.2 mol) was added and a condensation reaction was carried out at 160 to 170°C for 3 hours, and the generated water was removed from the system.
Then, after cooling this to 120℃, 221g of urea
(3.68 mol) was added to carry out deammoniation reaction at 120-130°C for 3 hours. Thereafter, water was added to this to obtain a 60% polyamide urea aqueous solution. then 40%
After adding 133 g (0.92 mol) of glyoxal aqueous solution and adjusting the pH to 9 with a 30% aqueous sodium hydroxide solution, the mixture was stirred at 80°C for 2 hours. After cooling to 30°C, 577 g (1.84 mol) of Epinox SC-60 was mixed,
Further water was added to obtain an aqueous resin solution with a solid content of 50%. Hereinafter, this resin aqueous solution will be abbreviated as "i-5". Example 6 310 g (3 moles) of diethylenetriamine and 60 g (1 mole) of urea were placed in the same reaction vessel as in Example 1, and ammonia removal reaction was carried out at 140 to 150° C. for 3 hours with stirring. Next, heat this to 100℃
Then, 94 g (0.8 mol) of succinic acid and 39 g (0.2 mol) of dimethyl isophthalate were added to carry out a condensation reaction at 170 to 190°C for 4 hours, and the generated water and methanol were removed from the system. Next, after cooling this to 120℃, 360g of urea
(6 mol) was added thereto, and deammonization reaction was carried out at 120 to 140°C for 3 hours. Thereafter, water was added to this to obtain a 50% polyamide polyurea aqueous solution. Next, 46 g (0.5 mol) of epichlorohydrin, 122 g (1.5 mol) of 37% formalin, 145 g (1 mol) of 40% aqueous glyoxal solution, 58 g (0.5 mol) of 2-chloroethyleneamine hydrochloride, and 76 g of glycidyltrimethylammonium chloride ( 0.5 mol) was added at the same time and kept under stirring at 60-8°C for 5 hours. Further water was added to obtain a water-soluble resin with a solid content of 40%. Hereinafter, this resin aqueous solution will be abbreviated as "i-6". Comparative Example 1 Example 1 except that there was no reaction with Epinox SC-60 and 50% aqueous sodium hydroxide solution.
A similar reaction was carried out to obtain a water-soluble resin with a solid content of 50%. Hereinafter, this resin aqueous solution will be abbreviated as "r-1". Comparative Example 2 A water-soluble resin with a solid content of 30% was obtained by carrying out the same reaction as in Example 2, except that the reaction with glycidyltrimethylammonium chloride was omitted. Hereinafter, this resin aqueous solution will be abbreviated as "r-2". Comparative Example 3 The same reaction as in Example 3 was carried out except that glycidylethylamine was omitted to obtain a water-soluble resin with a solid content of 40%. Hereinafter, this resin aqueous solution will be referred to as "r-3".
It is abbreviated as Comparative Example 4 50% aqueous sodium hydroxide solution, 2-chloroethylamine hydrochloride, and N-(2-chloroethyl)
The same reaction as in Example 4 was carried out except that the reaction with diethylamine hydrochloride was omitted to obtain an aqueous resin solution with a solid content of 30%. Below, this resin aqueous solution was
It is abbreviated as ``4''. Comparative Example 5 The same reaction as in Example 5 was carried out except that the mixing of Epinox SC-60 was omitted to obtain an aqueous resin solution with a solid content of 50%. Below, this resin aqueous solution was
It is abbreviated as ``5''. Comparative Example 6 The same reaction as in Example 6 was carried out except that 2-chloroethylamine hydrochloride and glycidyltrimethylammonium chloride were omitted to obtain an aqueous resin solution with a solid content of 40%. Below, this resin aqueous solution was
It is abbreviated as ``6''. Application Examples 1 to 6 and Comparative Application Examples 1 to 7 Each resin aqueous solution obtained in Examples 1 to 6 and Comparative Examples 1 to 6 was used as a printability improver according to the coating liquid blending ratio as shown below. After blending,
Water was added to give a concentration of 55%, and the pH was adjusted to 11 with a 30% aqueous sodium hydroxide solution to prepare various paper coating compositions. A paper coating composition containing no printability improver was also prepared in the same manner. "Ultra White 90" (clay manufactured by Engelhard Minerals, USA) 85 parts "Carbital 90" (calcium carbonate manufactured by Fuji Kaolin Co., Ltd.) 10〃 "Sachin White" (adjusted from aluminum sulfate and calcium hydroxide) 5 〃 "JSR-0692" (latex manufactured by Japan Synthetic Rubber Co., Ltd.)
10〃 “Oji Ace C” (starch manufactured by Oji Cornstarch Co., Ltd.)
4. “Aron T-40” (dispersant manufactured by Toagosei Kagaku Kogyo Co., Ltd.)
0.4〃 Printability improver 0.5〃 Note) The above “parts” are all solid weights. The above coating composition was coated on one side of a base paper with a basis weight of 75 g/m ² using an applicator so that the coating amount was about 12 g/m ² . Immediately then 100℃
Dry in a hot air dryer for 1 minute at a temperature of 50℃.
It was calendered twice under the following conditions: °C and a linear pressure of 80 kg/cm. The resulting single-sided coated paper was kept at 20℃ and 65%RH.
After conditioning the coated paper for 24 hours under the following conditions, the water resistance and ink receptivity of the coated paper were measured. The results of these measurements are shown in Table 1. In addition, each test method is as follows. (1) Ink receptivity Using an RI tester, moisten the coated surface with a water supply roll, then print, observe ink receptivity with the naked eye, and grade it in stages from Excellent 5 to Poor 1. did. (2) Water resistance (i) Wet pick method Using an RI tester, moisten the coated surface with a water supply roll, print, observe the peeling condition with the naked eye, and check the water resistance. Judgments were made from "Excellent 5 to Poor 1". (ii) Wet rub method Drop about 0.1ml of ion exchange water onto the coated surface and rub it with your fingertips 3, 5, 10, 15 and 20 times.
After being abraded several times, the eluted portion corresponding to each number of times was transferred to black paper, and the amount of eluted water was observed with the naked eye, and the water resistance was judged as "water resistance excellent 5 to poor 1". 3. Dry pick The paper was printed using an RI tester, the paper peeling condition was observed with the naked eye, and the result was determined as "dry pick resistance excellent 5 to poor 1". 4 Viscosity of the coating liquid Using a BM type viscometer, the viscosity of the coating liquid was measured at 60 rpm using a No. 3 rotor immediately after preparation of the coating liquid and after standing still at room temperature for 24 hours at 25℃. did.

【table】

Claims (1)

[Claims] 1. An amino compound having one primary amino group and/or a monobasic carboxylic acid or a monobasic carboxylic acid per mol of the dibasic carboxylic acid or dibasic carboxylic acid derivative. derivative
2.0 mol or less and 0.5 to 5.0 mol of an amino compound having at least two primary amino groups having polyalkylene polyamine and/or polyalkylene polyurea as a component are reacted to form a polyamide polyamine and/or polyurea polyamide. 0.1 to 1 mole of the total of the resin and the primary and secondary amino groups in the resin.
Deammonification is carried out by reacting with 3.0 mol of urea, and in the aqueous solution of the reaction product obtained, at least one crosslinking agent selected from epihalohydrin, formaldehyde and dialdehyde, and 1
with a cationizing agent that is a compound having a primary, secondary, or tertiary amine group or a quaternary ammonium base at the same time, or reacting one of them first and the other after, or reacting one of them first and both afterwards; Alternatively, a method for producing a paper coating resin, which comprises reacting the reaction product with the crosslinking agent in an aqueous solution and then mixing the cationizing agent. 2. The paper according to claim 1, wherein 2.0 moles or less of the amino compound having one primary amino group and/or monobasic carboxylic acid or monobasic carboxylic acid derivative is 0. Method for producing coating resin. 3 The cationizing agent has the following general formula [ ] [formula] or (However, R ¹ , R ² , and R ³ each have 1 to 6 carbon atoms.
X represents a halogen atom, and Y represents a halogen atom or 1/2SO ₄ or CH ₃ SO ₄ . ) The method for producing a paper coating resin according to claim 1 or 2, which is a quaternary ammonium salt having a glycidyl group or a halohydrin moiety represented by: 4 The cationizing agent has the following general formula [ ] [formula] or (However, R ⁴ and R ⁵ each represent a monovalent aliphatic group having 1 to 6 carbon atoms or a hydrogen atom, and X represents a halogen atom.) The method for producing a paper coating resin according to claim 1 or 2, wherein the resin is a grade or tertiary amine. 5 The cationizing agent has the following general formula [ ] [formula] or (However, R ¹ , R ² , and R ³ each have 1 to 6 carbon atoms.
R ⁴ and R ⁵ are each a monovalent aliphatic group having 1 to 6 carbon atoms or a hydrogen atom,
R ⁶ represents a divalent aliphatic group or an aromatic group,
X represents a halogen atom, and Y represents a halogen atom or 1/2SO ₄ or CH ₃ SO ₄ . ) The method for producing a paper coating resin according to claim 1 or 2, which is a quaternary ammonium salt or a primary, secondary or tertiary amine having a halogen atom represented by the following. 6. The method for producing a paper coating resin according to claim 1 or 2, wherein the dialdehyde is glyoxal or glutaraldehyde. 7. The combined amount of the cationizing agent and the epihalohydrin among the crosslinking agents is 1 equivalent of the amino group containing one primary amino group and the amino groups in the polyalkylene polyamine and/or polyalkylene polyurea. The method for producing a paper coating resin according to claim 1 or 2, wherein the amount is 4 equivalents or less. 8. The paper coating according to claim 1 or 2, wherein formaldehyde or dialdehyde is used as a crosslinking agent, and the total amount used is 2 equivalents or less per equivalent of the total amount of urea used in the reaction. Method of manufacturing resin for use.