PREPARATION OF THERMOSETTING RESINS AND OF PIGMENTED COMPOSITIONS THEREOF FOR COATING ON PAPER

Abstract: A thermosetting resin is prepared by mixing or reacting (a) an alkylene diamine or polyalkylenepolyamine with (b) an epihalohydrin (preferably chlorohydrin), and (Y) a watersoluble resin obtained by reacting (i) urea, (ii) a polyalkylenepolyamine, and (iii) a dibasic carboxylic acid (e.g. adipic) and reacting the resultant polyamidopolyurea (PAPU) formaldehyde. The PAPU can be made by reacting (i) + (ii) and the product with (iii), or (ii) + (iii) and the product with (i), at specified reaction conditions. (Y), (a) and (b) may all be reacted or mixed together, or first (Y) and (b) and then (a), or (a) and (b) then (Y). The thermosetting resin is mixed into a paper coating composition including a conventional pigment, binder and water, and the composition is coated onto paper and dried to make a coated paper which has good waterresistance (due to the resin (Y)) whilst being receptive to rotary offset printing ink.

Description: Preparation of thermosetting resins and of pigmented compositions thereof for coating on paper The present invention relates to the preparation of a paper coating composition which provides coated paper having excellent water resistance, ink receptivity and excellent blister resistance, the coated paper being free from coloring and releasing only an extremely slight quantity of formaldehyde; and to a process for producing a novel thermosetting resin aqueous solution to be used as one component of the paper coating composition. It has hitherto been known to produce coated paper having excellent printability by coating on paper a paper coating composition containing a pigment and an aqueous binder as major components, and further containing auxiliary agents such as water resistance-imparting agents. Recent years have seen remarkable progress in techniques for producing coated paper. For example, concentrating the solids of a coating composition has been proposed to allow high-speed coating using a blade coater for the purpose of increasing productivity. Thus, it has been required to increase the solids concentration without an increase in viscosity in order to obtain good coating properties. In addition, with up-grading and speed-up of printing and with rotary offset printing, a coated layer is required to possess higher water resistance, higher ink receptivity and higher blister resistance. In order to improve these properties many proposals have been made, such as improvement of the aqueous binder component and improvement of auxiliary agents. For example, in order to improve water resistance, a water resistance imparting agent is ordinarily introduced as an auxiliary agent because, although water resistance may be improved to some extent by increasing the weight ratio of aqueous binder to pigment, it in turn reduces ink receptivity when printing on the coated paper. Typical examples of the water resistance-imparting agents are the same as those of aqueous binders. However, although conventionally used or proposed water resistance-imparting agents have some merits, they also possess serious defects, and are thus unsatisfactory in practice. For example, some problems with a melamine-formaldehyde precondensate are that it gives insufficient ink receptivity; that when the pH of the coating composition containing the precondensate is high, it imparts insufficient water resistance; and that free formaldehyde is released from coated paper in a significant amount. No reaction product between polyamidopolyurea and formaldehyde has yet provided sufficient water-resisting and ink receptivity-improving effects, although such products do show some ink receptivity-improving effect, impart some water resistance, and release only small amounts of free formaldehyde from coated paper. Dialdehydes such as glyoxal are not preferred, because they color coated paper and have poor ink receptivityimproving effect. Mhltivalent metal salts such-as zirconium salts are not preferred either, because they seriously thicken the coating composition We have now found that a paper coating composition containing a specific thermosetting resin as a water resistanceimparting agent gives excellent effects. According to the present invention there is provided a paper coating composition which contains a pigment and an aqueous binder as maJor components, and further contains a thermosetting resin aqueous solution obtained by reacting or mixing (a) at least one alkylenediamine or polyalkylenepolyamine, (b) epihalohydrin, and (Y) water-soluble resin obtained by reacting urea, polyalkylenepolyamine, and dibasic carboxylic acid to form a polyamidopolyurea and reacting the resulting polyamidopolyurea with formaldehyde; and a process for producing a thermosetting resin aqueous solution which comprises reacting or mixing components (a), (b) and (Y) with each other. Alkylenediamines that can be used in the present invention include ethylenediamine, trimethylenediamine, 1,2-propylenediamine, tetramethylenediamine and hexamethylenediamine. These alkylenediamines may be used alone or in combinations of two or more. The polyalkylenepolyamines to be used in the present invention are preferably polyaIkylenepolyamines having two primary amino groups and at least one secondary amino group per molecule and include, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, 3-azáhexane-1,6-diamine and 4, 7-diazadecane-1 , 10- diamine. These polyalkylenepolyamines may be used alone or in combination of two or more. Examples of dibasic carboxylic acids that can be used in the present invention include aliphatic carboxylic acids such as, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid and fumaric acid; aromatic carboxylic acid such as isophthalic acid and terephthalic acid; and mixtures thereof. Examples of epihalohydrins that can be used in the present invention include epichlorohydrin and epibromohydrin, with epichlorohydrin being particularly preferred. The-polyamidopolyureas to be used in the present invention include polyamidopolyureas obtained by a deammoniation reaction: between urea and polyalkylenepolyamine, a dehydration condensation between the resulting product and dibasic carboxylic acid, and a deammoniation reaction between the resulting product and urea (hereinafter referred to as polyamidepolyurea (I)); and polyamidopolyureas obtained by a dehydration condensation between polyalkylenepolyamine and dibasic carboxylic acid, then a deammoniation reaction between the resulting product and urea (hereinafter referred to as polyamidopolyurea (it)). In obtaining the polyamidopolyurea (I), the molar ratio of urea to polyalkylenepolyamine is from 1:1.5 to 2,5f and preferably about 1:2 The reaction temperature is suitably from 100 to 2000C, and preferably from 120 to 1700C. This reaction is conducted for from 2 to 8 hours while removing ammonia produced from the reaction system. Then, the reaction product is subjected to a dehydration condensation with 0.3 to 0.7 mol, per mol of polyalkylanepolyam'ine used, of a dibasic carboxylic acid. This reaction is conducted at a reaction temperature of from 120 to 2500C, and preferably of from 140 to 200O, for from 2 to 10 hours while removing water produced from the reaction system. The thus obtained condensation reaction product is further reacted with urea. The amount of urea reacted is from 0.2 to 1,5 moles, and preferably from 0.5 to 1.1 moles, per mole of secondary amino group in the starting polyalkylenepolyamine. The reaction temperature is from 100 to 1800C, and preferably from 120 to 1500C, and the reaction is carried out for from 1 to 5 hours while removing ammonia produced from the reaction system. Thus, a polyamidopolyurea'(I) is obtained. In obtained the polyamidopolyurea (it), the reaction between polyalkylenepolyamine and dibasic carboxylic acid is carried out at a temperature of from 120 to 2500C, and preferably of from 140 to 200 C, for from 2 to 10 hours while removing water produced from the reaction system. From 1.4 to 3.0 moles, and preferably from 1.8 to 2.5 moles, of the polyalkylenepolyamine is used per mole of the dibasic carboxylic acid. The thus obtained dehydration condensation reaction product is then reacted with urea. The urea is used in an amount of from 0.2 to 1.0 mole, and preferably from 0.4 to 0.8 mole, per mole of amino group in the starting polyalkylenepolyamine. The reaction temperature is from 100 to 1800C, and preferably from 120 to 1500C. The reaction is carried out for from 1 to 5 hours while removing ammonia produced from the reaction system. The desired amount of urea may be charged at one time to react, or a part of the desired amount of urea may first be charged, and, after completion of the deammoniation reaction, the remaining amount of urea may be charged, followed by again conducting deammoniation reaction. Thus, polyaminopolyurea (II) is obtained. The thus obtained polyaminopolyurea is dissolved in water to react it with formaldehyde. This reaction is conducted in an aqueous solution containing from 20 to 70 weight%, and preferably 30 to 60 weight%, of the polyamidopolyurea and having a pH adjusted to 7 or less, preferably 3.5 to 6.5, with an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid or acetic acid, at a reaction temperature of 40 to 800C for 1 to 10 hours. This reaction is preferably conducted under acidic conditions as described above. However, the end product of the present invention can also be obtained by initially conducting the reaction under alkaline conditions of, for example, pH 8 to 12, adjusting the pH to 7 or less, and preferably 3.5 to 6.5, and continuing the reaction. In this case, the reaction under alkaline conditions is conducted at from 40 to 80 0C for from -0.5- to 3 hours, and the subsequent reaction under acidic conditions is carried out at from 40 to 800C for from 1 to 10 hours. The amount of formaldehyde is suitably from 0.2 to 1 mole, and preferably from 0.3 to 0.7 mole, per mole of the total urea used for synthesizing the polyamidopolyurea. After completion of the reaction, the pH of the resulting reaction product may, if desired, be adjusted to from 6 to 9. The water-soluble resin thus obtained is hereinafter referred to as (Y). The water-soluble resin (Y) obtained as described above by reacting polyamidopolyurea with formaldehyde is further reacted or mixed with (a) at least one (e.g., one, two or more) polyalkylenepolyamine or alkylenediamine and (b) epihalohydrin. In this reaction, the components (Y), (a) and (b) may be reacted with each other at the same time, or (Y) and (b) may be first reacted with each other, followed by reacting the resulting reaction product with (a), or a reaction product (X) obtained by the reaction between (a) and (b) may be reacted with (Y). In using these ingredients as a mixture, (Y) may be mixed with (a) and (b), or a reaction product between CY) and (b) may be mixed with (a),(Y) may be mixed with a reaction product (X) between (a) and (b). As to the manner of addition to a paper coating composition, a previously prepared mixture may be added to a paper coating composition,mor individual ingredients may separately be added to a paper coating composition. The reaction temperature in-simultaneously reacting (Y), (a) and (b) with each other is from 30 to 800C, that of the reaction between (Y) and (b) is from 300C to the reflux temperature thereof, and that of the reaction between (a)and the reaction product between (Y) and (b) is from 300C to 1000C. These reactions are conducted for from 0.5 to 10 hours. The amount of polyalkylenepolyamine or alkylenediamine, component (a), to be used in the reaction or mixing is suitably from 0.1 to 3 moles, and preferably from 0.2 to 1.5 moles, per mole of the dibasic carboxylic acid used for synthesizing polyamidopolyurea. The amount of epihalohydrin, (b), is suitably from 0.1 to 4 moles, and preferably 0.5 to 3 moles, per mole of the polyalkylenepolyamine or alkylenediamine, (a), used. After completion of the reaction or mixing, the pH of the resulting reaction product or mixture may, if desired, be adjusted to from 2.5 to 8. On the other hand, in the case of reacting the reaction product (X) between (a) and (b) with (Y), the reaction between (a) and (b) is conducted at from 30 to 800C for from 30 minutes to 10 hours. The molar ratio of amine (a) to epihalohydrin (b) is suitably 1:0.1 to 20., and preferably 1:2 to 10. In mixing component (X) with (Y), (X) and (Y) may separately be mixed with a paper coating composition, or a previously prepared mixture of (X) and (Y) may be added to a paper coating composition. The amount of (X) to be used is from 0.05 to 5 moles, and preferably from 0.1 to 2 moles, of (a) in (X) per mole of the dibasic carboxylic acid used for synthesizing (Y). In reacting (X) with (Y), this reaction is carried out at from 20 to 800C for from 30 minutes to 10 hours. After completion of the reaction, the pH of the product may, if desired, be adjusted to 2 to 6. The paper coating composition of the present invention is prepared in a conventional manner, but, for fully attaining the desired effect, an aqueous binder is compounded in a solid amount of from 3 to 30 weight%, and preferably-from 5 to 20 weight%, based on the weight of pigment, and a reaction product or mixture of (a), (b), and (Y) is compounded in a solid amount of from 0.05 to 5 weight%, and preferably from 0.1 to 2 weight%, based on the weight of pigment. In some cases, it may be useful to add another water resistance-imparting agent. As the aqueous binder and the pigment to be used in preparing the paper coating composition of the present invention, any conventionally known may be used. Examples of the aqueous binder are water-soluble binders such as starch, oxidized starch, modified starch, polyvinyl alcohol, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose and soybean protein; and aqueous emulsion or dispersion system binders such as a styrene-butadiene type resin, vinyl acetate resin, ethylene-vinyl acetate resin or methyl methacrylate resin. Examples of pigment are inorganic pigments such as kaolin clay, titanium dioxide, aluminum hydroxide, calcium carbonate, satin white or barium sulfate; and organic pigments containing styrene or urea as major components. These may be used alone or in combinations of two or more in any desired mixing ratio. The paper coating composition of the present invention may contain, if desired, other ingredients such as a dispersing agent, a thickening agent, a thinning agent, a defoaming agent, a foam inhibitor, an antiseptic, an antifungal agent, a fluidity-adjusting agent, a repellent, a colorant (e.g., a dye or colored pigment) or an agent for imparting special properties (e.g., an electroconductive agent). The coating composition of the present invention can be prepared in a manner analogous to conventional coating compositions. Usually, the solids concentration of the coating composition is adjusted to from 30 to 80 weight%, and preferably from 50 to 65 weight%. The paper coating composition of the present invention is coated on a paper substrate in a conventionally known manner using a blade coater, air-knife coater, roll coated, size-press coater, cast coater or the like, subjected to necessary drying in an ordinary manner, and, if desired, subjected to super calendering, machine calendering or the like to produce coated-paper. The paper coating composition of the presentinvention obtained as described above has numerous merits; it suffers no color shocks (a serious increase in viscosity of the composition or aggregation of pigment), has excellent stability, and, when coated on a paper substrate, it forms thereon an excellent water resisting coating layer, releases only a much decreased amount of formaldehyde, shows improved ink-receptivity undergoes no coloration, and imparts improved blister resistance in rotary offset printing. The present invention will now be illustrated by the following examples and comparative examples, in which percentages are by weight unless otherwise specified. Examples 1 and 2 describe the synthesis of components. used in the subsequent examples of compositions according to the invention. Example 1 (1) Synthesis of Resin (A): 292 g (2:moles) of triethylenetetramine and 60 g (1 mole) of urea were charged into a four-neck flask equipped with a thermometer, a reflux condenser, and a stirring rod, and reaction was carried out at 1450 to 1500C.for 4 hours while removing ammonia produced from the reaction system. Then, 146 g (1 mole) of adipic acid was added thereto, and condensation reaction was conducted at 150 to 1550C for 5 hours. - After cooling the reaction mixture to 1200C, 240 g (4 moles) of urea was added thereto, and a deammoniation reaction was conducted at 1250 to 1300C for 2 hours, followed by gradual addition of 1,350 g of water to obtain an aqueous solution of polyamidopolyurea. Thereafter, 202.5 g (2.-5 moles) of 37% formalin was added thereto, the pH of the resulting mixture was adjusted to 5 with concentrated hydrochloric acid, and the mixture was kept at 650C for 4 hours while stirring, to obtained a water-soluble resin (A) containing 30 weight% solids. (2) Synthesis of Resin (B): Resin (A) was prepared in the same manner as in step (1), and 92.5 g (1 mole) of epichlorohydrin and 217 g of water were added thereto. The resulting mixture was.kept at 600C for 2 hours while stirring, then cooled to 250C to obtain a thermosetting resin (B) containing 30 weight% solids. (3) Synthesis of Resin (C): Resin (A) was prepared in the same manner as in step (1), and 210 g of water, 146 g (1 mole) of triethylenetetramine, and 92.5 g (1 mole) of epichlorohydrin were added thereto. The resulting mixture was kept at 600C for 2 hours while stirring, then cooled to 25 0C to obtain a thermosetting resin (C) containing 3546 solids. (4) Synthesis of Resin (D): Resin (B) was prepared in the same manner as in step (2), and 73 g (0.5 mole) of triethylenetetramine and 170 g of water were added thereto. The resulting mixture was kept at 600C for 3 hours while stirring, then cooled to 250C to obtain a thermosetting resin (D) containing 30 weight,' solids. (5) Synthesis of Resin (E): 206 g (2 moles) of diethylenetriamine and 60 g (1 mole) of urea were charged into the same apparatus as in (1), and deammoniation reaction was-carried out at 140- to 1450C for 5 hours. Then, 146 g (1 mole) of adipic acid was added thereto, and dehydration condensation was conducted at 160 to 1700C for 2 hours. After cooling the reaction mixture to 1200C, 120 g (2 moles) of urea was added thereto, and deammoniation reaction was carried out at 130 to 1400C for 1.5 hours, followed by gradual addition of 900 g of water to obtain an aqueous solution of polyamidopolyurea. Then, 145.8 g (1.8 moles) of 37% formalin was added to the aqueous solution, and the resulting mixture was adjusted to pE 4.5 with 20 N sulfuric acid and kept at 600C for 3 hours while stirring. Subsequently, 185 g (2 moles) of epichlorohydrin and 277 g of water were added thereto, and the resulting mixture was kept at 600C for 3 hours while stirring, then cooled to 25 0C to obtain a thermosetting resin (E) containing 40% solids. (6) Synthesis of Resin (F): Resin (E) was prepared in the same manner as in (5), and 146 g (1 mole) of diethylenetriamine and 219 g of water were added thereto to obtain a thermosetting resin (F) containing 40% solids. (7) Synthesis of Resin (G): 365 g (2.5 moles) of triethylenetetramine, 20 g of water, and 146 g (1 mole) of adipic acid were charged into the same apparatus as in (1), and a dehydration condensation was conducted at 155 to 1600C for 4 hours. Then, 60 g (1 mole) of urea was added thereto, and a deammoniation reaction was conducted at 145 to 1500c for 3 hours. The reaction mixture was cooled to 1300C, and 240 g (4 moles) of urea was added thereto. Then, a deammoniation reaction was conducted at 130 to- 1400C for 3 hours, followed by gradual addition of 595 g of water to obtain an aqueous solution of polyamidopolyurea. Then, 162 g (2 moles) of 37% formalin was added thereto, and the resulting mixture was adjusted to pH 4.5 with 20N sulfuric acid and kept at 606C for 4 hours while stirring. Subsequently, 180 g of water, 51.5 g (0.5 mole) of diethylenetriamine, and 92.5 g (t mole) of epichlorohydrin were added thereto, and the resulting mixture was kept at 650c for 2.5 hours while stirring. The reaction solution was cooled to 250c to obtain a thermosetting resin (G) containing 50% solids. (8) Synthesis of Resin (H): 206 g (2 moles) of diethylenetriamine and 60 g (1 mole) of urea were charged in the same reaction apparatus as in (1), and a deammoniation reaction was conducted at 145 to 1500c for 3 hours. Then, 118 g (1 mole) of succinic acid was added thereto, and a dehydration condensation was conducted at 1500C for 4 hours. After cooling the reaction solution to 130 C, 96 g (1.6 moles) of urea was added thereto, and a deammoniation reaction was conducted at 125 to 1300C for 3 hours, followed by gradual addition of 540 g of water to obtain an aqueous solution of polyamidopolyurea. Then, 105.3 g (1.3 moles) of 37% formalin was added thereto, and the solution was adjusted to pH 10 with 10 N sodium hydroxide, kept at 600C for 2 hours while stirring, adjusted to pH 5.5 with concentrated hydrochloric acid, and kept at 600c for 3 hours while stirring. Thereafter, 250 g of water, 103 g t1 mole) of diethylenetriamine, and 46.3 g (o.s mole) of epichlorohydrin were added thereto. The resulting mixture was kept at 650C for 2 hours while stirring, then cooled to 25 0C to obtain a thermosetting resin (H) containing 40% solids. (9) Synthesis of Resin (I): 185.4 g (1.8 moles) of diethylenetriamine, 10 g of water, and 118 g t1 mole) of succinic acid were charged in the same apparatus as in (1), and dehydration condensation was carried out at 150 to 1550C for 8 hours. After cooling the reaction solution to 1200C., 180 g (3 moles) of urea was added thereto, and, after raising the temperature of the solution to 1300C, a deammoniation reaction was conducted at 130 to 135 0c for 4 hours. Then, 860 g of water was gradually added thereto to obtain an aqueous solution of polyamidopolyurea. 145.8 g (1.8 moles) of 37% formalin solution was added thereto, and the resulting solution was adjusted to pH 10 with ION sodium hydroxide aqueous solution, kept at 600C for 2 hours, adjusted to p-H 5.5 with concentrated hydrochloric acid, and kept at 600C for 3 hours while stirring. Subsequently, 160 g of water, 219 g (1.5 moles) of triethylenetetramine, and 92.5 g (1.0 mole) of epichlorohydrin were added thereto and the resulting solution was kept at 650C for 5 hours while stirring. The reaction solution was cooled to 250C to obtain a thermosetting resin (I) containing 40% solids. (10) Synthesis of Resin (J): 103 g (1 mole) of diethylenetriamine, 146 g (1 mole) of triethylenetetramine, 20 g of water, and 100 g (0.77 mole as dibasic carboxylic acid) of a dibasic carboxylic acid mixture composed of 22% of succinic acid, 64% of glutaric acid and 14% of adipic acid were charged into the same reaction apparatus as in (1), and dehydration condensation was conducted at 160 to 1650C for 4 hours. Then, 60 (1 mole) of urea was added thereto to conduct a deammoniation reaction at 145 to 1500C for 4 hours. The reaction solution was cooled to 300C, and 180 g (3 moles) of urea was added thereto to conduct a deammoniation reaction at 130 to 1400c for 5 hours. Thereafter, 410 g of water was gradually added thereto to obtain a polyamidopolyurea aqueous solution. 97 g (1.2 moles) of a 3796 formalin was added thereto, and the resulting solution was adjusted to pH 4 with concentrated hydrochloric acid, and kept at 500C for 6 hours while stirring. Then, 280 g of water, 146 g CI mole) of triethylenetetramine, and 92.5 g (1 mole) of epichlorohydrin were added thereto. The resulting mixture was kept at 600C for 2 hours while stirring, then cooled to 250C to obtain a thermosetting resin (J) containing 50% solids. (11) Synthesis of Resin (K): 206 g (2 moles) of diethylenetriamine, 10 g of water, and 146 g (1 mole) of adipic acid were charged into the same reaction apparatus as in (1), and the temperature of the mixture was raised to 1500C, then kept at 150 to 1550C for 6 hours while evaporating water produced. Then, after cooling the reaction solution to 1300C, 240 g (4 moles) of urea was added thereto, and a deammoniation reaction was conducted at 125 to 130 0c for 3 hours while removing ammonia produced from the reaction system. Thereafter, 420 g of water was gradually added thereto to obtain an aqueous solution of polyamidopolyurea. Then, 162 g (2 moles) of a 37%-formalin was added thereto and, after adjusting to pH 5 with concentrated hydrochloric acid, kept at 650C for 3 hours while stirring. Subsequently, 225 g of water, 73 g (0.5 mole) of triethylenetetramine, 51.5 g (0.5 mole) of diethylenetriamine, and 92.5 g (1.0 mole) of epichlorohydrin were added thereto, and the resulting mixture was kept at 650C for 2 hours while stirring. This reaction solution was cooled to 25 0c to obtain a thermosetting resin (K) containing 50% solids. (12) Synthesis of Resin CL): 292 g (2 moles) of triethylenetetramine and 60 g (1 mole) of urea were added to the same reaction apparatus as in step (1), and the reaction was conducted at 145 to 1500C for 4 hours while removing ammonia from the system. Then, 146 g (1 mole) of adipic acid was added thereto to conduct condensation reaction at 150 to 155 C for 5 hours. After cooling the mixture to 120 C, 240 g (4 moles) of urea was added thereto to conduct a deammoniation reaction for 2 hours at 125 to 130 C. Then, 1,350 g of water was gradually added thereto to obtain an aqueous solution of polyamidopolyurea. 202.5 g (2.5 moles) of 37% formalin was added thereto, and, after adjusting to pH 5 with concentrated hydrochloric acid, the resulting solution was kept at 650C for 4 hours while stirring. Then, 130 g of water, 120 g (2 moles) of ethylenediamine-, and 278 g (3 moles) of epichlorohydrin were added thereto, and the resulting mixture was kept at 600C for 3 hours while stirring, then cooled to 25 0C to obtain a thermosetting resin (L)- containing 40% solids. Example 2 (i) Synthesis of Compound (X-I): 44 g (0.3 mole) of triethylenetetramine and 189 g of water were charged into a four-neck flask equipped with a thermometer, a reflux condenser, and a stirring rod, and 167 g (1.8 moles) of epichlorohydrin was added thereto while keeping the temperature at 400C. The reaction was continued at 400C for 2 hours, followed by cooling to obtain a 50% aqueous solution of a compound (X-1). (ii) Synthesis of Compound (X-2)-: 60 g (1 mole) of ethylenediamine and 270 g of water were. charged into the same apparatus as used in step (i), and 185 g (2 moles) of epichlorohydrin was added thereto while keeping the inside temperature at 50 C. The reaction was continued for I hour at 500C, then the reaction mixture was cooled to obtain a 50% aqueous solution of a compound (X-2) (iii) Synthesis of Resin (Y-1): 292 g (2 moles) of triethylenetetramine and 60 g (1 mole) of urea were charged in a four-neck flask equipped with a thermometer, a reflux condenser, and a stirring rod, and a deammoniation reaction was conducted at 150 to-1530C for 3 hours. Then, 146 g (1 mole) of adipic acid was added thereto, and a dehydration condensation was conducted at 155 to 1600C for 5 hours. After cooling the reaction mixture to. 1300C, 240 g (4 moles) of urea was added thereto, and a deammoniation reaction was conducted at 130 to 1350C for 2 hours, followed by gradual addition of 550 g of water to obtain a polyamidopolyurea aqueous solution. Then, 121.5 g (1.5 moles) of 37% formalin was added thereto, and the resulting mixture was adjusted to pH 4 with 20 N sulfuric acid, kept at 700C for 4 hours while stirring, cooled to 300C, and adjusted to pH 6.5 with a ION sodium hydroxide aqueous solution to obtain a resin (Y-l) containing 50% solids. (iv) Preparation of Resin (1): The whole amount of compound (it1) obtained in (i) and the whole amount of resin (Y-1) obtained in (iii) were charged into the same apparatus as in (iii), and the pH of the resulting mixture was adjusted to 4 with 20 N sulfuric acid while stirring to obtain an aqueous solution of a thermosetting resin (1) containing 50% solids. (v) Synthesis of Resin (2): As in (iv), the whole amount of compound (X-1) obtained in (i) and the whole amount of (Y-'l) obtained in (iii) were charged and reacted with each other at 35 to 400C for 2 hours, and the pH of the reaction mixture was adjusted to 4 with 20 N sulfuric acid to obtain an aqueous solution of a thermosetting resin (2) containing 50% solids. (vi) Synthesis of Resin (3); 41 g (0.4 mole) of diethylenetriamine and 240 g of water were charged in the same apparatus as in (iii), and 185 g (2 moles) of epichlorohydrin was added thereto while keeping the temperature at 450C. After continuing the reaction at 450C for 1 hour, the resin (Y-1) obtained -in (i) was added thereto in the same amount as in (i), and the reaction was conducted at 40 to 450C for 2 hours. Then, the pH of the reaction solution was adjusted to 3.5 with 20 N sulfuric acid to obtain an aqueous solution of a thermosetting resin (3) containing 50% solids. (vii) Synthesis of Resin (Y-2):- 365 g (2.5 moles) of triethylenetetramine, 20 g of water, and 146 g (1 mole) of adipic acid were charged into the same apparatus as in (iii), and dehydration condensation was conducted at 155 to 1600C for 4 hours. Then, 60 g (1 mole) of urea was added thereto, and a deammoniation reaction was conducted at 145-to 1500C for 3 hours. After cooling the reaction mixture to 1300C, 240 g (4 moles) of urea was further added thereto, and a deammoniation reaction was conducted at 130 to 1400C for 3 hours, followed by gradual addition of 595 g of water to obtain an aqueous solution of polyamidopolyurea. Then, 162 g (2 moles) of 37% formalin was added thereto, and the resulting mixture was adjusted to pH 4.5 with 50% sulfuric acid, and kept at 600C for 4 hours while stirring. After cooling the reaction solution to 250C, its pH was adjusted to 7.5 with a ION sodium hydroxide aqueous solution to obtain a resin (Y-2 > ) containing 50% solids. (viii) Synthesis of Resin (4): The whole amount of compound (X-2) obtained in (ii) and the whole amount of resin (Y-2) obtained in (vii) were charged into the same apparatus as in (iii), and the pH of the mixture was adjusted to 3 with 20 N sulfuric acid while stirring to obtain an aqueous solution of a thermosetting resin (4) containing 50% solids. (ix) Synthesis of Resin (5): The whole amount of compound (X-2) obtained in (ii) and the whole amount of resin (Y-2) obtained in (vii) were charged into the same apparatus as in (iii) and reacted with each other at 45 to 500C for 2 hours. Then, the pH of the reaction solution was adjusted to 3 with 20 N sulfuric acid to obtain an aqueous solution of a thermosetting resin (5) containing 50% solids. (x) Synthesis of Resin (6): 38 g (0.2 mole) of tetraethylenepentamine and 200 g of water were charged into the same apparatus as in (iii), and 130 g (1.4 moles) of epichlorohydrin was added thereto while keeping the temperature at 400C. The reaction was continued at 400C for 3 hours. Then, the whole amount of resin (Y-2) obtained in (vii) was added thereto, and the reaction was conducted at 35 to 400C for 2 hours. After completion of the reaction, the pli of the reaction mixture was adjusted to 4 with 20 N sulfuric acid to obtain an aqueous solution of a thermosetting resin (6) containing 50% solids. (xi) Synthesis of Resin (Y-3): 206 g (2 moles) of diethylenetriamine and 60 g (1 mole) of urea were charged into the same reaction apparatus as in (iii), and a deammoniation reaction was conducted at 145 to 1500C for 3 hours. Then, 118 g (1 mole) of succinic acid was added thereto, and a dehydration condensation was conducted at 150 C for 4 hours. After cooling the reaction mixture to 130 C, 96 g (1.6 moles) of urea was added thereto, and a deammoniation reaction was conducted at 125 to 1300C for 3 hours, followed by adding thereto 355 g of water to obtain a polyamidopolyurea aqueous solution. Then, 105.3 g (1.3 moles) of 37% formalin was added thereto, and the pH of the reaction mixture was adjusted to 10 with ION sodium hydroxide. After keeping the mixture at 600C for 2 hours while stirring, its pH was adjusted to 5.5 with concentrated hydrochloric acid, after which it was kept at 600C for 3 hours while stirring. Thereafter, the mixture was cooled to 250C, and its pH was adjusted to 7.5 with a ION sodium hydroxide aqueous solution to obtain a resin (Y-3) containing 50% solids. (xii) Synthesis of Resin (7): 29 g (0.2 mole) of triethylenetetramine and 130 g of water were charged into the same reaction apparatus as in (iii), and III g (1.2 moles) of epichlorohydrin was added thereto while keeping the temperature at 400C. After continuing the reaction at 400C for 2 hours, the whole amount of water-soluble resin (Y-3) described above was added thereto, and the reaction was conducted at 35 to 400C for 2 hours. Then, the pH of the reaction mixture was adjusted to 5 with 20 N sulfuric acid to obtain an aqueous solution of a thermosetting resin (7) containing 50% solids. (xiii) Synthesis of Resin (8): 29 g (0.2 mole) of tetraethylenepentamine, 21 g (0.2 mole) of diethylenetriamine, and 240 g of water were charged into the same reaction apparatus as in (iii), and 185 g (2.0 moles) of epichlorohydrin was added thereto while keeping the temperature at 400C. After continuing the reaction at 400C for 2 hours, the whole amount of resin (Y-1) obtained in (iii) was added thereto, and reaction was conducted at 40 to 450C for 2 hours. Then, the pH of the reaction mixture was adjusted to 4 with 20 N sulfuric acid to obtain an aqueous solution of a thermosetting resin (8) containing 50% solids. (xiv) Synthesis of Resin (Y-4): 103 g (1 mole) of diethylenetriamine, 146 g (1 mole) of triethylenetetramine, 20g of water, and 100 g of a dibasic carboxylic acid mixture (0.77 mole as dibasic carboxylic acid) (composed of 22% succinic acid, 64% glutaric acid and 14% adipic acid) were charged into the same reaction apparatus as in (iii), and dehydration condensation was conducted at 160 to 165 C for 4 hours. Then, 60 g (1 mole) of urea was added thereto, and a deammoniation reaction was conducted at 145 to 1500C for 4 hours. After cooling the reaction mixture to 1300C, 180 g (3 moles) of urea was further added thereto, and a deammoniation reaction was conducted at 130 to 1400C for 5 hours. Then, 410 g of water was gradually added thereto to obtain a polyamidopolyurea aqueous solution. To this solution was added 97.2 g (1.2 moles) of.3i% formalin, and the resulting mixture was adjusted to pH 4 with concentrated hydrochloric acid and kept at 500C for 6 hours while stirring. After cooling the reaction solution to 300C, its pH was adjusted to 6.5 with a ION sodium hydroxide aqueous solution to obtain a resin (Y-4) containing 50% solids. (xv) Syntheses of Resin -(9): 34 g (0.23 mole) of triethylenetetramine and 190 g of water were charged in the same reaction apparatus as in (iii), and 128 g (1.38 moles) of epichlorohydrin was added thereto while keeping the inside temperature at 500C. After continuing the reaction at 500C for 1 hour, the whole amount of water-soluble resin (Y-4) described above was added thereto, and reaction was conducted at 45 to 500C for 1 hour. Then, the pH of the reaction mixture was adjusted to 5 with 20 N sulfuric acid to obtain an aqueous solution of a thermosetting resin (9) containing 50% solids. Examples 3 to 16 (1) Preparation of Paper Coating Compositions: Kaolin clay, calcium carbonate, and aluminum hydroxide were used as pigments. To a pigment slurry dispersed in water by adding a sodium potyacrylate type dispersing agent were addedan aqueous solution of previously gelatinized oxidized starch and a styrenebutadiene latex. Further, water resistance-imparting agents were added in amounts as indi-¯ cated in Table 1, and the resulting mixtures were stirred well to properly mix the ingredients. The pH of the compositions was finally adjusted to 9.5 with a sodium hydroxide aqueous solution, and the solids concentration thereof was -adjusted to 55 wt% to prepare paper coating compositions. Additionally, the basic compounding ratios of ingredients other than the water resistance-imparting agents in the compositions¯are shown in Table 1. (2) Preparation of Coated Paper: Each of the compositions obtained as described above was coated on both sides of a base paper of 85 g/m2 in basis weight in an amount of 15 g/m2 per one side of the paper using a coating rod, then dried in hot air at 1200C for 30 minutes. Then, the resulting coated papers were subjected to super calendering (roll temperature: 600C; roll linear pressure: 60 kg/cm; passed twice between the rolls), and conditioned at 200C and 65% RH to be used as test samples for various tests. (3) Various Testing Methods: (A) Physical properties of coating solution: (i) pH of coating solution - measured at 200C on a glass electrode pH meter. (ii) Viscosity of coating solution measured at 200C and 60 rpm on a Brookfield viscometer. (3) Physical properties-of coated paper: (i) Water resistance of coated film: (a) Wet Rub method: 0.1 ml of deionized water was dropped onto a coated paper, and rubbed seven times with the tip of a finger. The eluate was transferred to a black paper to judge the amount of the eluate with the naked eye. The judgement was conducted by assigning a value ranging from I (poor water resistance) to 5 (excellent water resistance). (b) Wet Pick method: The coated surface was wetted by a water supply roll using an RI tester (made by Akira Seisakusho) and subjected to printing to observe and judge the state of delamination and damage of coated layer with the naked eye according to the same judging rating as in Wet Rub method. (ii) Determination of formaldehyde released from coated paper - according to the acetylacetone method described in JIS L,1041, liquid phase extraction method (2). Additionally, determination of formaldehyde was conducted, for example, by sealing the sample in a polyethylene bag to protect it from formaldehyde released from other samples or to prevent exhalation of formaldehyde from the sample. (iii) ink receptivity of coated paper: Samples were printed according to either of the following methods using an RI tester, and ink receptivity was observed and judged with the naked eye. The judgement was conducted by assigning a value ranging from 5 (good) to 1 (poor). (a) Method A Water was dropwise added to an ink under milling, then the resulting ink was used for printing. (b) Method B The coated surface of a sample was wetted with a water supply roll, then printed. (c) Method C Printing was conducted by combining the above-described Methods A and B. (iv) Whiteness and heat-resistant whiteness: Whiteness of a coated paper sample before and after heat treatment at 150 C for 30 minutes using a hot-air drying machine was measured according to JIS P-8123 by measuring the B value on a Hunter reflectometer. The higher the value, the better the whiteness. (v) Blister resistance: A double-coated paper sample was printed on both sides with an ink for rotary offset printing using an RI tester and, after conditioning, it was dipped in a heated silicone oil bath to determine the minimum temperature at which blistering took place. (4) Results of Tests: Compositions containing each of the resins obtained in Example 1 were essluated-according to the tests described above. The resins used and compouding formulations are shown in Table 2, together with the results of the tests. Comparative Examples 1 and 2 A coating composition was prepared in the same manner as in the Examples above except for not using resins (B) to (L), polyalkylenepolyamine, alkylenediamine and epihalohydrin as water resistance-imparting agents. The compounding formulations and results of tests are shown in Table 3. Comparative Examples 3 to 6 A coating composition was prepared in the same manner as in the above Examples except for using resin (A) or (B) alone as a water resistance-imparting agent to evaluate its properties. Compounding formulations and results of the tests are shown in Table 3. TABLE 1 Formulation No. Compound Ingredient 1 2 Kaolin clay 85 parts by weight 80 parts by weight Calcium carbonate 15 " Aluminum hydroxide 0 " 20 Dispersing agent -0.4 " 0 0.4 (sodium polyacrylate) Styrene-butadiene 10 " 10 type latex Oxidized starch 6 n 6 TABLE 2 (A) Paper Coating Composition Item Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Compounding Formulation Water resistance Resin Resin Resin Resin Resin Resin Resin Resin Resin Resin Resin Resin Resin Resin imparting agent (A) (B) (C) (D) (E) (F) (B) (D) (G) (H) (I) (J) (K) (L) 0.35 0.45 0.5 0.5 0.4 0.5 0.35 0.5 0.5 0.5 0.5 0.5 0.5 0.5 part part part part part part part part part part part part part part Epihalohydrin Epichloro- No No No No No No No No No No No No No (part) hydrin 0.1 Alkylenediamine Tri- Tri- No No Tetra- No Di- No No No No No No No or polyalkylene- ethylene- ethylene- ethylene ethylene polyamine (part) tetramine tetramine pentamine triamine 0.05 0.05 0.1 Formulation No. 1 1 1 1 1 2 2 2 1 1 1 2 2 2 Physical properties of coating composition Viscosity (cps) Upon prep. 540 560 560 550 580 480 450 470 560 570 570 470 480 480 After 24 hrs. 590 600 600 600 620 530 520 520 600 600 600 610 520 520 pH (upon prep.) 9.5 9.4 9.5 9.5 9.5 9.6 9.4 9.5 9.5 9.5 9.4 9.4 9.5 9.5 (cont'd) TABLE 2 (B) Paper Coating Composition Item Ex.3 Ex.4 Ex.5 Ex.6 Ex.7 Ex.8 Ex.9 Ex.10 Ex.11 Ex.12 Ex.13 Ex.14 Ex.15 Ex.16 Properties of coated paper Coated amount/side (g/mê) 15.0 1.50 14.9 15.2 15.3 14.9 14.9 15.1 14.8 15.0 15.0 15.1 14.9 15.0 Water resistance Wet Pick method 4.7 4.8 4.8 4.7 4.8 4.9 4.8 4.8 4.8 4.7 4.7 4.7 4.8 4.8 Wet Rub method 4.7 4.8 4.9 4.8 4.8 4.8 4.8 4.7 4.8 4.8 4.8 4.8 4.8 4.8 Amount of released 8 9 8 9 9 9 8 9 7 9 8 7 7 7 formaldehyde (ppm) Ink receptivity Method A 4.7 4.8 4.9 4.8 4.9 4.8 4.8 4.8 4.8 4.8 4.8 4.9 4.7 4.7 Method B 4.8 4.9 4.9 4.7 4.8 4.7 4.7 4.7 4.8 4.7 4.8 4.9 4.8 4.7 Method C 4.7 4.8 4.8 4.8 4.8 4.7 4.7 4.7 4.8 4.7 4.8 4.8 4.8 4.8 Whiteness (%) Before heat 80.0 79.9 80.1 79.9 80.0 80.2 79.8 80.1 79.7 79.9 79.9 80.0 79.8 80.2 treatment After heat 78.0 77.9 78.0 78.1 78.1 77.8 78.0 78.0 77.9 78.0 78.0 78.2 78.1 78.0 treatment Blisrer resistance 220 230 240 230 240 230 220 220 230 220 230 230 230 230 ( C) TABLE 3 ------------ Paper Coating Composition ------------------------------------------------------------------------------------------------------ Comparative Comparative Comparative Comparative Comparative Comparative Item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 ----------------------- -------------- ------------ ------------ ------------- ------------ ------------- Compounding formulation Water resistance- No No Resin (A) Resin (A) Resin (B) Resin (B) imparating agent 0.5 0.5 0.5 0.5 (part) Epihalohydrin No No No No No No Alkylenediamine or polyalkylene- No No No No No No polyamine Formulation No. 1 2 1 2 1 2 Physical properties of coating composition Viscosity (cps) Upon prep. 560 470 530 460 550 480 After 24 hrs. 600 510 550 490 590 500 pH (upon prep.) 9.5 9.5 9.6 9.5 9.5 9.5 (cont'd) TABLE 3 ------------- Paper Coating Composition ------------------------------------------------------------------------------------- Comparative Comparative Comparative Comparative Comparative Comparative Item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 --------------------- ------------ ------------ ------------ ------------ ----------- ------------- Properties of coated paper Coaced amount/aide 15.3 15.7 14.8 15.2 14.9 15.0 (g/m2) Water resistance Wet Pick method 1.0 1.0 3.8 3.5 4.2 4.0 Wet Rub method 1.0 1.0 3.8 3.8 4.2 4.0 Amount of released formaldehyde (ppm) 1 1 9 9 8 9 Ink receptivity Method A 1.5 1.5 4.0 4.0 4.3 4.2 Method B 1.5 1.5 4.0 4.0 4.3 4.2 Method C 1.0 1.0 3.5 3.8 4.0 4.0 Whiteness (2) Before best 79.8 79.0 80.0 80.1 80.0 79.9 treatment After heat treatent 77.5 77.0 78.1 78.1 77.9 78.0 Blister resistance 180 180 200 200 210 210 ( C) Examples 17 to 29 Resins obtained in Example 2 were evaluated in the same manner as in Examples 5 to 16. Resins and compounding formulations used are shown in Table 4. Results of tests on their properties are also shown in Table 4. Comparative Examples 7 to 10 Coating solutions were prepared in the same manner as in the Examples using resin (Y-1) or resin (Y-2) as a water resistance-imparting agent to evaluate their properties. Compounding formulations and results of the tests on their properties are shown in Table 5. TABLE 4 (A) Paper Coating Composition Item Ex.17 Ex.18 Ex.19 Ex.20 Ex.21 Ex.22 Ex23 Ex.24 Ex.25 Ex.26 Ex.27 Ex.28 Ex.29 Compounding formulation Water resistance- Resin Resin Resin Resin Resin Resin Resin Resin Resin Resin Resin Resin Resin imparting agent (1) (2) (4) (5) (1) (2) (4) (5) (3) (6) (7) (8) (9) (part) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Formulation No. 1 1 1 1 2 2 2 2 1 1 1 1 1 Physical properties of coating composition Viscosity (cps) Upon prep. 560 570 580 580 470 480 450 460 560 580 560 570 560 After 24 hrs. 570 580 610 600 500 520 490 490 580 590 580 590 590 pH (upon. prep.) 9.4 9.3 9.4 9.4 9.4 9.4 9.4 9.3 9.4 9.4 9.5 9.5 9.5 Properties of coated paper Coated amount/ 15.0 15.2 14.9 15.1 15.1 15.3 15.5 15.0 15.1 14.9 15.0 15.0 15.1 side (g/mê) Water resistance Wet Pick method 4.8 4.9 4.8 4.8 4.9 4.8 4.8 4.8 4.8 4.8 4.7 4.8 4.8 Wet Rub method 4.7 4.8 4.7 4.7 4.8 4.9 4.8 4.8 4.8 4.8 4.8 4.8 4.8 (cont'd) TABLE 4(B) Paper Coating Composition Item Ex.17 Ex.18 Ex.19 Ex.20 Ex.21 Ex.22 Ex.23 Ex.24 Ex.25 Ex.26 Ex.27 Ex.28 Ex.29 Properties of coated paper Amount of released form- 8 8 7 8 8 8 9 8 9 8 8 8 9 aldebyde (ppm) Ink receptibity Method A 4.8 4.8 4.7 4.7 4.8 4.8 4.7 4.7 4.8 4.7 4.8 4.8 4.8 Method B 4.8 4.9 4.7 4.8 4.8 4.7 4.7 4.8 4.8 4.7 4.8 4.8 4.8 Method C 4.7 4.8 4.7 4.7 4.8 4.8 4.7 4.8 4.8 4.9 4.7 4.7 4.8 Whitemess (%) Before heat 79.8 79.7 79.5 80.0 80.0 80.2 79.9 79.9 80.1 80.0 79.8 80.1 80.0 treatment After heat 77.5 78.2 77.8 77.9 78.1 77.9 77.8 78.0 77.9 78.1 77.8 78.0 77.9 treatment Blister resist- 240 240 240 230 230 230 230 230 240 230 230 230 230 ence ( C) TABLE 5 Paper Coating Composition Comp. Comp. Comp. Comp. Ite Ex.7 Ex.8 Ex.9 Ex.10 Compounding formula tion Water resistance- Resin Resin Resin Resin imparting agent (Y-1) (Y-1) (Y-2) (Y-2) (part) 0.5 0.5 0.5 0.5 Formulation No. 1 2 1 2 Physical properties of coating composi tion Viscosity (cps) Upon prep. 540 460 550 470 After 24 hrs. -580 480 570 480 pH (upon prep.) 9.6 9.5 9.5 9.5 Properties of coated paper Coated amount/side 14.9 15.0 15.1 15.1 (g/m2) Water resistance Wet Pick method 3.8 3.5 4.2 4.0 Wet Rub method 3.5 3.5 4.0 3.8 Amount of released formaldehyde (ppm) 8 9 9 9 Ink receptivity Method A 4.0 4.0 4 2 4 2 Method B 4.0 4.0 4.2 4¯0 Method C 3.5 3.5 4.2 4.2 (cont'd) TABLE 5 Paper Coating Composition Comp. Comp. Comp. Comp. Item Ex.7 Ex.8 Ex.9 Ex.10 Properties of coated paper Whiteness (%) Before heat 79 l 78 8 78.5 78.7 treatment After heat 77.1 76.9 77.4 77.2 treatment Blister resistance 200 200 210 210 ( C)

Claims: Claims: 1. A process of preparing a thermosetting resin in aqueous solution, comprising reacting or mixing (a) at least one alkylenediamine or polyalkylenepolyamine, (b) epihalohydrin, and (Y) a water-soluble resin obtained by reacting urea, polyalkylenepolyamine, and dibasic carboxylic acid, and further reacting the resulting polyamidopolyurea with formaldehyde. 2. A process as claimed in Claim 1, wherein said water-soluble resin (Y) was obtained by a deammoniation reaction between urea and polyalkylenepolyamine, then a dehydration condensation between the reaction product and dibasic carboxylic acid, and a deammoniation reaction between the resulting product and urea, and a reaction of the thus obtained polymmidopolyurea with formaldehyde in an aqueous solution under acidic condition, or intially under alkaline condition and then under acidic condition. 3. A process as claimed in Claim 1, wherein said water-soluble resin (Y) was obtained by a dehydration condensation between polyalkylenepolyamine and dibasic carboxylic acid, then a deammoniation reaction between the reaction product and urea, and a reaction of the thus obtained polyamidopolyurea with formaldehyde in an aqueous solution under an acidic condition, or initiallY under alkaline condition and then under acidic condition. 4. A method as claimed in Claim 2, wherein from 1.5 to 2.5 moles of polyalkylenepolyamine per mole of urea is used in the reaction between urea and polyalkylenepoly amine, and subsequently dibasic carboxylic acid is used in an amount of from 0.3 to 0.7 mole per mole of the polyalkylenepolyamine, and subsequently urea is used in an amount of from 0.2 to 1.5 moles per mole of secondary amino group in the polyalkylenepolyamine. 5. A method as claimed in Claim 2 or 4, wherein the temperature during the reaction between urea and poly alkylenepolyamine is maintained at from 1000 to 2000C, the temperature during the reaction between the resulting product and dibasic carboxylic acid is maintained at from 1200 to 2500C, and the temperature during the reaction between the resulting product and urea is maintained at from 1000 to 1800C. 6. A method as claimed in Claim 3, wherein from 1.4 to 3.0 moles of polyalkylenepolyamine is used per mole of dibasic carboxylic acid in the reaction between the dibasic carboxylic acid and the polyalkylenepolyamine, and the amount of urea used is from 0.2 to 1.0 mole per mole of the amino group of polyalkylenepolyamine. 7. A method as claimed in Claim 3 or 6, wherein the temperature during the reaction between the dibasic carboxylic acid and the polyaikylenepolyamine is maintained from 120 to 2500C, and the temperature during the reaction between the resulting product and urea is maintained at from 100 to 1800C. 8. A method as claimed in any of Claims 1 to 7, wherein the amount of formaldehyde is from 0.2 to 1 mole per mole of the total amount of urea used for synthesizing the polyamidopolyurea. 9. A method as claimed in any of Claims 1 to 8, wherein the temperature during the reaction between formaldehyde and polyamidopolyurea is maintained at from 40 to 80 C. 10. A method as claimed in Claim 1, wherein said thermosetting resin aqueous solution is obtained by mixing or simultaneously reacting components (a), (b) and (Y), or by reacting or mixing a reaction product between (Y) and (b) with (a). 11. method as claimed in any of Claims 1 to 10, wherein said thermosetting resin aqueous solution is obtained by reacting or mixing a reaction product (X) between components (a) and (b) with the water-soluble resin (Y). 12. A method as claimed in Claim 10, wherein the amount of (a) is from 0.1 to 3 moles per mole of the dibasic carboxylic acid used for synthesizing (Y). 13. A method as claimed in Claim 10 or 12, wherein the amount of (b) is from 0.1 to 4 moles per mole of (a). 14. A method as claimed in Claim 10, 12 or 13, wherein the temperature during the simultaneous reaction of (y), (a) and (b) is maintained from 30 to 80 C. 15. A method as claimed in Claim 10, 12, 13 or 14, wherein the temperature of the reaction between (Y) and (b) is 300C to reflux temperature, and the temperature of the reaction between the resulting product and (a) is 30 to 100 C. 16. A method as claimed in Claim 11, wherein the amount of (a) is 0.05 to 5 moles per mole of the.dibásic carboxylic acid used for synthesizing (Y). 17. A method as claimed in Claim 11 or 16, wherein the molar ratio of (a) to (b) in (X) is 1:0. 1 to 20. 18. A method as claimed in Clai 11, 16 or 17, wherein the temperature of the reaction between (a) and (b) is 30 to 800C. 19. A method ascIaimed in Claim 11, 16, 17 or 18, wherein the temperature of the reaction between (X) and (Y) is 20 to 80to. 20. A method as claimed in any of Claims 1 to 19, wherein the polyalkylenepolyamine is a compound having two primary amino groups and at least one secondary amino group per molecule. 21. A method as claimed in any of Claims 1 to 20, wherein said dibasic carboxylic acid is an aliphatic dibasic carboxylic acid. 22. A composition for coating onto paper, containing a pigment and an aqueous binder as major components, and further containing a thermosetting resin in aqueous solution, obtained by the method of any of the preceding claims. 23. A composition as claimed in Claim 22, wherein the solids content of the thermosetting resin obtained from (a), (b) and (Y) is 0.05 to 5 weight%, based on the weight of the pigment. 24. A coated paper having coated thereon a paper coating composition as claimed in Claim 22 or 23.

Inventors: IWATA, MIKIO, JINNO, NAOYOSHI, KAWAKAMI, SHIGENAO, SAKA, TERUMASA, TAKAGISHI, HISAO, TOKUGAWA, YOSHIHARU, URA, SHIGERU
Applicants: SUMITOMO CHEMICAL COMPANY, LIMITED
Application year: 1982
Main classification: D21H1
IPC codes: C08G73, C08G71, D21H19, C08G69