JPS62121727A - Production of thermosetting resin - Google Patents

Abstract

PURPOSE:To produce a thermosetting resin which can give coated paper excellent in water resistance, ink receptivity, etc., by reacting a polyalkylenepolyamine with a specified reaction product, a urea and an aldehyde. CONSTITUTION:An alicyclic dibasic carboxylic acid and/or its mixture with a glycol are reacted at 80-200 deg.C for 30min-2hr in the presence (absence) of a catalyst to obtain a reaction product (B) containing free carboxyl groups. 1mol of a polyalkylene polyamine (A) is reacted with 0.4-4 equivalent of the carboxyl groups of component B at 120-250 deg.C for 1-12hr, a urea (C) in an amount of 1 equivalent or below per equivalent of the amino groups in component A is added to the reaction mixture and reacted at 100-180 deg.C for 1-6hr. The obtained reaction product is dissolved in water so that the concentration of the resulting solution may be 20-70wt%. To this solution, 0.05-1.0mol of a polyaldehyde (D) and 0.1-1.0mol of, optionally, a monoaldehyde (E) per mol of component C are added and reacted at 40-80 deg.C for 1-10hr.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a novel thermosetting resin that can impart excellent printability and printing effects to coated paper.

<Prior art> Coated paper, which is obtained by applying a paper coating composition mainly consisting of pigments and an aqueous binder to paper and performing necessary processes such as drying and calendering, has excellent printing effects, etc. Due to its characteristics, coated paper is widely used in commercial printed matter, magazines, books, etc., but as quality requirements become more sophisticated and printing speeds increase, efforts are being made to improve the quality of coated paper. In particular, in offset printing, which accounts for the majority of printing, improvements in ink receptivity under the influence of dampening water, water resistance in wet picks and wet rubs, blister resistance in rotary printing,
Improvement is a key challenge for the industry.

Conventionally, to solve these problems, melamine-formaldehyde resin, urea-formaldehyde resin or polyamide polyurea-formaldehyde resin, such as
4-11667, Japanese Patent Publication No. 59-32597, etc., methods are known in which the problem is solved by adding a waterproofing agent or the like.

<Problems to be Solved by the Invention> However, while all of the conventionally used water-resisting agents have effective properties, they have serious drawbacks and are therefore unsatisfactory in practice.

For example, melamine-formaldehyde ffl fat and urea-
Aminoplast resins such as formaldehyde resin not only generate a lot of formaldehyde during operation and from coated paper, but also have little effect on improving ink receptivity and blister resistance, and the water resistance effect depends on the coating composition. When the pH of a substance becomes high, it becomes extremely difficult to obtain it. Furthermore, polyamide polyurea-formaldehyde resin is effective in improving water resistance as well as ink receptivity and blister resistance, but the degree of improvement is still insufficient in response to recent demands for higher quality coated paper. This is sufficient, and there is a demand for even higher performance. The purpose of the present invention is to meet such demands by providing a novel method for producing a thermosetting resin that can impart high water resistance, ink receptivity, etc. to coated paper that could not be obtained using conventional techniques. It is in.

<Means for Solving the Problem> As a result of intensive studies by the present inventors in order to obtain a thermosetting resin that imparts high water resistance, ink receptivity, etc. to coated paper, (a) polyalkylene polyamine (b) ) A reaction product having a free carboxyl group obtained by the reaction of an alicyclic dibasic carboxylic acid and/or an alicyclic dibasic carboxylic acid with a glycol.

We have discovered that thermosetting resins reacted with (c) ureas, (d) polyvalent aldehydes, and, if desired, (e) monovalent aldehydes, are extremely effective in improving the performance of coated paper. Completed the invention. The present invention is characterized by using the above-mentioned reaction components (a) to (e), and furthermore, the reaction components (
A feature of b) is the use of a reaction product having a free carboxyl group obtained by the reaction of an alicyclic dibasic carboxylic acid and/or an alicyclic carboxylic acid with a glycol.

The content of the present invention will be explained in further detail.

The polyalkylene polyamine (a) used in the present invention is a compound having two primary amino groups and at least one secondary amino group in the molecule, and specifically, for example, diethylenetriamine, triethylenetetramine, Tetraethylenepentamine, iminobispropylamine, 3-azahexane-1,6-diamine, 4.
Examples include 7-cyazadecane-1.10 diamine.

These polyalkylene polyamines can be used not only alone but also as a mixture of two or more. Furthermore, there is no hindrance to the use of aliphatic diamines such as ethylene diamine and propylene diamine in combination with the above-mentioned polyalkylene polyamines within the range that does not impede the object of the present invention.

Next, (b) alicyclic dibasic carboxylic acid is a general term that includes compounds having two carboxyl groups in the molecule, their esters, and their acid anhydrides, Representative examples of such alicyclic dibasic carboxylic acids include the following.

Carboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane-1,4-dicarboxylic acid, 4-methyltetrahydrophthalic acid, and their esters, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4- These are acid anhydrides such as methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, Δ4-tetrahydrophthalic anhydride, and 4-methylΔ4-tetrahydrophthalic anhydride.

These may be used alone or in combination of two or more.
Furthermore, in addition to these dibasic carboxylic acids, other dibasic carboxylic acids such as aliphatic dicarboxylic acids such as adipic acid and glutaric acid, or aromatic dicarboxylic acids such as terephthalic acid and phthalic acid may be used as long as the effects of the present invention are not impaired. It may be used in combination with an acid.

Glycols include alkylene glycols such as ethylene glycol, propylene glycol, butanediol, cycloalkylene glycols such as butynediol, cyclobentanediol, and cyclohexanediol, alkenylene glycols such as octenediol, diethylene glycol, and dipropylene glycol. ,
Polyalkylene glycols such as triethylene glycol, polyethylene glycol, and polytetramethylene glycol, ethylene oxide adducts of bisphenol A,
Examples include ethylene oxide adducts of hydrogenated bisphenol A.

Furthermore, as a reaction product having a free carboxyl group obtained by the reaction of an alicyclic dibasic carboxylic acid and a glycol, the alicyclic dibasic carboxylic acid and the glycol are combined with an excess molar amount of carboxylic acid. It is a polyester having a carboxyl group at the end of the molecule, which is obtained by reacting at a specific temperature. The reaction between this alicyclic dibasic carboxylic acid and glycols is usually carried out at 80 to 200°C in the presence or absence of a catalyst.
This is done by heating for 30 minutes to 2 hours.

The ureas (c) include urea, thiourea, guanylurea, methylurea, dimethylurea, etc., but urea is preferred from an industrial standpoint.

Next, examples of the polyvalent aldehyde (d) include glyoxal and glutaraldehyde.

Examples of the monovalent aldehyde (e) include formaldehyde, acetaldehyde, propionaldehyde, acrolein, glyoxylic acid, and glycolaldehyde, with formaldehyde being preferred from an industrial standpoint.

Next, each component (a), (b), (c), (d) and (e)
The reaction method is described below. The resin of the present invention can be produced, for example, by reacting the reaction products of components (a), (b) and (c) with (6) and, if desired, (e). The reaction of components (a), (c) and (c) is
The reactions can be carried out in any order.

First of all, components (a) and (c) can be reacted and then component (c) can be reacted. Components (a) and (b)
The reaction is carried out at a temperature of 120-250°C, preferably 130-250°C.
2 to 12 hours at 200℃ while removing the generated water from the system.
done in time. The carboxyl group in component (b) is 0.1 mole per mole of polyalkylene polyamine of component (a).
The reaction is carried out at a ratio of 4 to 4 equivalents, preferably 0.8 to 3 equivalents. The dehydration condensation reaction product thus obtained,
The reaction of component (e) with ureas is carried out at a temperature of 100 to 180°C.
Preferably, the reaction is carried out at 110 to 160° C. for 1 to 6 hours while removing generated ammonia from the system. The amount of component (c) to be used is 1 equivalent or less, preferably 0.1 equivalent to 1 equivalent of amino groups, that is, primary and secondary amino groups in component (a).
It is 1 to 0.8 equivalent.

Alternatively, components (a) and (c) are first reacted,
Component (b) can then be reacted, and then component (c) can be reacted. For 1 mole of component (a), component (
c) is used in an amount of 0.2 to 1 mol, preferably 0.3 to 0.8 mol, and the temperature is 100 to 180°C, preferably 110 to 1 mol.
The deammoniation reaction is carried out at 60° C. for 1 to 6 hours.

The reaction between the reaction product thus obtained and component (c) is carried out at a temperature of 120 to 250°C, preferably 130 to 250°C.
2 to 12 hours at 00℃ while removing the generated water from the system.
Time is done. Components et al.) per mole of component (a),
It is used in a range of 0.2 to 2 equivalents, preferably 0.3 to 1.8 equivalents. Ingredients (a), et al. thus obtained
The step of reacting the reaction product of (c) with component (c) again is carried out at a temperature of 100 to 180°C, preferably 11
It is carried out at 0-160°C for 1-6 hours. The amount of component (e) to be used is at most 2 equivalents, preferably in the range of 0.1 to 1.5 equivalents, per 1 equivalent of the secondary amino group in component (a).

Yet another method is to react components (a), (b) and (c) simultaneously, and further add component (c) to the resulting reaction product.
It is also possible to react. First component (a), (b)
The reaction (e) is carried out at a temperature of 100 to 200°C, preferably 110 to 180°C, for 2 to 12 hours while removing generated ammonia and water from the system. The ratio of each component used in this step is 0.2 to 2 equivalents of the carboxyl group of component (c), preferably 0.3 to 1 mole of component (a).
~1.8 equivalents, 0.2 to 1 mole of component (c), preferably 0.3 to 0.8 mole are suitable. The step of further reacting the reaction product thus obtained with component (c) is carried out at a temperature of 100 to 180°C, preferably 110 to 160°C.
It is held for 1 to 6 hours. The amount of component (c) used is
The appropriate amount is 2 equivalents or less, preferably 0.1 to 1.5 equivalents, per 1 equivalent of the secondary amino group in a).

Components (a) and (b) obtained by various methods as above
The reaction products of (c) are both dissolved in water and then reacted with a polyhydric aldehyde and, if desired, a monohydric aldehyde. This reaction is carried out in an aqueous solution with a concentration of 20-70% by weight, preferably 30-60% by weight, at a temperature of 40-80°C.
The event lasts from 1 to 10 hours.

The amount of polyhydric aldehyde at this time is component (c) 1
0.05 to 1.0 mol, preferably 0°1
~0.8 mol is suitable. The amount of monovalent aldehyde is suitably 0.1 to 1.0 mol, preferably 0.2 to 0.7 mol, per 1 mol of component (c). After the reaction is complete,
If necessary, the pH is adjusted to 4 to 7 by adding an alkali such as caustic soda or potassium hydroxide, or an acid such as hydrochloric acid or sulfuric acid.

The resin thus obtained is obtained in the form of an aqueous solution, and usually has a viscosity of 5 to 1000 centiboise (hereinafter abbreviated as Cp) at 25°C of an aqueous solution with a resin solid content concentration of 50% by weight. If the viscosity is extremely low, the effect of adding it as a paper coating resin tends to be low, and if the viscosity is high, the viscosity of the prepared paper coating composition will increase, resulting in generally undesirable disadvantages. Practically speaking, it is 10 to 500 cp, particularly preferably 2
Preferably, the viscosity range is from 0 to 200 cp.

As explained in detail above, the method of the present invention can be obtained by reacting (a) a polyalkylene polyamine (b) an alicyclic dibasic carboxylic acid and/or an alicyclic dibasic carboxylic acid with a glycol. reaction product with free carboxyl groups.

This is achieved by reacting (c) ureas, (d) polyhydric aldehydes and, if desired, (e) monohydric aldehydes, and the resulting thermosetting resin is excellent when used as a paper coating resin. It has ink receptivity and water resistance, making it extremely useful. The feature of the present invention is that a specific dibasic carboxylic acid, that is, an alicyclic dibasic carboxylic acid is used as the dibasic carboxylic acid, and aliphatic or aromatic dibasic Compared to paper coating resins obtained from carboxylic acids, the resins obtained by the present invention are recognized to have dramatically improved performance.

<Examples> Next, the present invention will be specifically explained using Examples and Comparative Examples. In the following, all parts and percentages are based on weight unless otherwise specified.

Example-1 58.5 parts (0.4 mol) of triethylenetetramine was placed in a four-piece flask equipped with a thermometer, reflux condenser, and stirring bar.
and 12.0 parts (0.2 mol) of urea, and the internal temperature was 120 ~
The mixture was heated at 140° C. for 3 hours to perform a deammonia reaction.

Thereafter, 34.4 parts (0.2 mol) of hexahydrophthalic acid was added, and the dehydration and amidation reaction was carried out at an internal temperature of 150 to 160° C. for 5 hours.

Thereafter, the internal temperature was cooled to 130°C, and 48.0 parts of urea (0,
8 mol) was charged and the deammoniation reaction was carried out at a temperature of 120°C to 130°C for 2 hours. Thereafter, it was cooled to 100°C and water was added to make a 50% aqueous solution. Next, 58 parts (0.4 mol) of 40% glyoxal was added, and the pH was adjusted to 6 with 35% hydrochloric acid.
After adjusting the temperature, the mixture was reacted at 50°C for 3 hours. 25 days after reaction
It was cooled to 0.degree. C. to obtain a resin liquid having a concentration of 47% and a viscosity of 46 cp (25.degree. C.). This is called resin liquid Δ.

Example-2 Triethylenetetramine 58 was placed in the same container as in Example-1.
．． 5 parts (0.4 mol) and 12.0 parts (0.2 mol) of urea
was charged and heated at an internal temperature of 120 to 140°C for 3 hours to perform a deammonia reaction. After that, 33.2 parts (0.2 mol) of HN-2200 (manufactured by Hitachi Chemical Q Kosha, alicyclic acid anhydride, formula below) was added, and the internal temperature was 150-160.
The dehydration and amidation reaction was carried out at ℃ for 5 hours.

After that, the internal temperature was cooled to 130°C and 12.0 parts of urea (0°2
mol) was charged, and a deammonification reaction was carried out at a temperature of 120 to 130°C for 2 hours. Thereafter, it was cooled to 100°C and water was added to make a 50% aqueous solution.

Next, 29 parts (0.2 mol) of 40% glyoxal was charged, the pH was adjusted to 6.5 with 70% sulfuric acid, the temperature was raised to 60°C, and the mixture was reacted at 60°C for 4 hours. After that 2
Cooled to 5°C, concentration 48.5%, viscosity 47 cp (25
℃) was obtained. This is called resin liquid B.

Example-3 Triethylenetetramine 58 in the same container as Example-1
．． 5 parts (0.4 mol) and 30.4 parts (0.2 mol) of tetrahydrophthalic anhydride and 12 parts (0.2 mol) of urea were simultaneously charged and the temperature was raised to dehydrate and amidate at 150 to 155°C for 5 hours. , deammonification reaction was performed simultaneously. It was then cooled to 130°C and further added with 12 parts (0.2 mol) of urea.
was charged, and a deammonification reaction was carried out at 125 to 130°C for 2 hours. This was diluted by adding water to obtain an aqueous solution with a concentration of 50%.

Next, 80 parts of 25% glutaraldehyde aqueous solution (0.2
After adjusting the pH to 6.5 with 70% sulfuric acid, the mixture was reacted at 55°C for 7 hours. Thereafter, it was cooled to 25°C to obtain a resin liquid having a concentration of 45% and a viscosity of 42 cp (25°C). This is called resin liquid C.

Example-4 Triethylenetetramine 29 in the same container as Example-1
．． 2 parts (0.2 mol) were charged, and 30.8 parts (0.2 mol) of hexahydrophthalic anhydride was added thereto, the temperature was raised, and dehydration and amidation were performed at 150 to 155°C. The mixture was then cooled to 130°C, 12 parts (0.2 mol) of urea was charged, and ammonia removal reaction was carried out at 125-130°C for 2 hours. Next, this was cooled to 60°C and diluted with water to make a 50% aqueous solution.

Then 14.5 parts (0.1 mol) of 40% glyoxal
After adjusting the pH to 6 with 35% hydrochloric acid,
The reaction was carried out at ℃ for 2 hours. Thereafter, it was cooled to 25°C to obtain a resin liquid having a concentration of 48.5% and a viscosity of 58 cp (25°C).

This is called resin liquid.

Example-5 Ethylene glycol 12.4 in the same container as Example-1
(0.2 mol) and 60.0 parts (0.2 mol) of tetrahydrophthalic anhydride.
Pour 8 parts (0.4 mol) and heat at 140°C for 2 hours.
A reaction product with free carboxyl groups was obtained. Add 12.0 parts (0.2 mol) of urea to this and add 110 to 1
Triethylenetetramine 58.5 while stirring at 20°C
(0.4 mol) was added.

This was subjected to deammonia reaction and dehydration amidation reaction at 150° C. for 5 hours. This was cooled to 130°C, 12.0 parts (0.2 mol) of urea was added, and the temperature was 120-130°C.
Ammonia removal reaction was carried out at ℃ for 2 hours. Thereafter, it was cooled to 100°C and water was added to make a 50% aqueous solution.

Then 14.5 parts (0.1 mol) of 40% glyoxal
After adjusting the pH to 7 with 70% sulfuric acid,
The reaction was carried out at 0°C for 2 hours. Thereafter, it was cooled to 25° C. to obtain a resin liquid having a concentration of 49% and a viscosity of 49 cp (25° C.). This is called resin liquid E.

Example-6 Triethylenetetramine 58 in the same container as Example-1
．． 5 parts (0.4 mol) and 12.0 parts (0.2 mol) of urea
was charged and heated at an internal temperature of 120 to 140°C for 3 hours to perform a deammonia reaction. After that, 30.4 parts (0.2 mol) of tetrahydrophthalic anhydride was added, and the internal temperature was 150~150.
The dehydration amidation reaction was carried out at 160°C for 5 hours. Thereafter, the internal temperature was cooled to 130°C, 48 parts (0.8 mol) of urea was charged, and ammonia removal reaction was carried out at a temperature of 120 to 130°C for 2 hours. Thereafter, it was cooled to 100°C and water was added to make a 50% aqueous solution.

Next, 29 parts (0.2 mol) of 40% glyoxal was added, the pH was adjusted to 6 with 70% sulfuric acid, and then the pH was adjusted to 6 at 60°C.
Allowed time to react. Thereafter, 16.2 parts (0.2 mol) of 37% formalin was added, the pH was adjusted to 5 with 70% sulfuric acid, and the mixture was reacted again at 60° C. for 3 hours. After the reaction is complete, 2
The mixture was cooled to 5° C., and the pH was adjusted to 6 with 28% caustic soda to obtain a resin liquid having a concentration of 48% and a viscosity of 56 cp (25° C.). This is called resin liquid F.

Example-7 Triethylenetetramine 58 was placed in the same container as Example-1.
．． 5 parts (0.4 mol) and 12 parts (0.2 mol) of urea were charged, and the deammonia reaction was carried out at 145 to 150°C for 4 hours. In another container, add 60% of tetrahydrophthalic anhydride.
．． 8 parts (0.4 mol) and 15.2 parts of propylene glycol
R (0.2 mol) was mixed with L and heated at 140 to 150°C for 2 hours to obtain a polyester. The entire amount of this polyester was charged into a container that had undergone the above-described deammonization reaction, and heated at an internal temperature of 150 to 155° C. for 4 hours to perform dehydration and deammonia reaction. The mixture was then cooled to 130°C, 12 parts (0.2 mol) of urea was added, and ammonia removal reaction was carried out at 125-130°C for 2 hours. After that, water was added to make a 50% aqueous solution, and 40 parts of a 25% glutaraldehyde aqueous solution (0
, 1 mol) and 4 parts (0.05 mol) of 37% forma phosphorus were added, and then the pH was adjusted to 5.5 with 70% sulfuric acid. This was heated to 70°C, reacted at 70°C for 4 hours, cooled to 25°C, and adjusted to pH with 28% caustic soda.
was adjusted to 6.5. Concentration 47.5%, viscosity 46cp (
A resin liquid was obtained at a temperature of 25°C. This is called resin liquid G.

Comparative Example-1 According to Example-1, 29°6 parts of phthalic anhydride (0,2
The resin liquid was synthesized using the same raw materials and under the same conditions except for the one used (mol), and finally a resin liquid with a concentration of 47% and a viscosity of 44 cp (25°C) was obtained.

This is called resin liquid H.

Comparative Example 2 Synthesized according to Example 1 using the same raw materials and under the same conditions except that 29.2 parts (0.2 mol) of adipic acid was used instead of hexahydrophthalic anhydride in Example 1. , R A resin liquid having a final concentration of 47% and a viscosity of 51 cp was obtained.

This is called resin liquid I.

Comparative Example-3 According to Example-5, 58.5 parts of adipic acid (0.4 parts
mol) and 12.4 parts (0.2 mol) of ethylene glycol
The mixture was then heated at 160 to 180°C for 3 hours to undergo dehydration and esterification to obtain a polyester having carboxyl groups at the terminals. Further, 12.0 parts (0.2 mol) of urea was added to this,
The mixture was stirred at 110-120°C and 58.5 parts (0.4 mol) of triethylenetetramine was added. This was subjected to deammonia and dehydration amidation reactions at 150° C. for 5 hours.

Cool this to 130°C and make urea 12.0 parts (0.2 mol).
was added, and ammonia removal reaction was carried out at a temperature of 120 to 130°C for 2 hours. Thereafter, water was added to make a 50% aqueous solution.

Then 14.5 parts (0.1 mol) of 40% glyoxal
After adjusting the pH of the system to 7 with 70% sulfuric acid,
The reaction was carried out at 60°C for 3 hours. Then cool to 25℃,
A resin liquid having a concentration of 49% and a viscosity of 46 cp (25°C) was obtained.

This is called resin liquid J.

Application Examples 1 to 7 Thermosetting resin aqueous solutions obtained in Examples 1 to 7 and Comparative Examples 1 to 3 and Sumirezu Resin 613 (manufactured by Sumima Chemical Industry Co., Ltd.)
A paper coating composition having the formulation shown in Table 1 was prepared using a melamine/formaldehyde resin.

(Note) ■Ultra White 90 (clay manufactured by Engel Hard Minerals, Inc., USA) ■Chikara-Vital 90 (calcium carbonate manufactured by Fuji Kaolin Q1) ■Violet Resin DS-10 (polyacrylic acid pigment manufactured by Sumitomo Chemical Co., Ltd.) Dispersant) ■5N-307 (styrene-butadiene latex manufactured by Sumitomo Nogatatsuta G Kosha) ■Tamago Ace A (oxidized starch manufactured by Tamago National Starch ■) 0 parts by weight represents the solid content weight.

The prepared paper coating composition was adjusted with water and a 10% caustic soda aqueous solution so that the total solid content was 60% and the pH was about 8.5, and then mixed with a wire rod to give a weight of 80 g per grammage.
/m'' high-quality paper was coated on one side at a coating weight of 14 g/m''. Immediately after application, it was dried with hot air at 120°C for 30 seconds, then conditioned at 20°C and 65% RH for 16 hours, and then supercalendered twice at a temperature of 60°C and a linear pressure of 60 kg/cm. , a coated paper was obtained.

The coated paper thus obtained was subjected to tests for water resistance, ink receptivity, and formaldehyde quantification. The test results are shown in Table 2.

The test method is as follows.

○Water resistance (a) Wet rub method Apply approximately 0.1 m of ion-exchanged water to the coated surface! !・Drop it, rub it with your fingertips 7 times, transfer the elution amount to black paper, and judge the elution amount with the naked eye.

The evaluation criteria were as follows.

Water resistance (poor) 1 to 5 (excellent) (b) Using a wet pick method RI tester, moisten the coated surface with a water supply roll, print, and visually observe the peeling condition to determine water resistance (poor). )
A rating of 1 to 5 (excellent) was made.

○ Ink receptivity (a) Using A method RI testing machine (Mei Seisakusho), the coated surface was moistened with a water supply roll and then printed, and the ink receptivity was observed.

Ink acceptability (poor) 1 to 5 (excellent).

(b) Method B Using a R1 tester, printing was carried out while kneading water into the ink, and the ink receptivity was observed.

Ink acceptability (poor) 1 to 5 (excellent).

○ Quantification of formaldehyde 2.5 g of coated paper sample was taken and quantified according to JIS-L1041-1976 liquid phase extraction method C) acetylacetone method (method A).

Claims (1)

[Scope of Claims] (a) Polyalkylene polyamine (b) A reaction product having a free carboxyl group obtained by the reaction of an alicyclic dibasic carboxylic acid and/or an alicyclic dibasic carboxylic acid with a glycol. thing. A method for producing a thermosetting resin, comprising reacting (c) a urea, (d) a polyvalent aldehyde, and, if desired, (e) a monovalent aldehyde.