JPS62116619A - Production of resin - Google Patents

Abstract

PURPOSE:To obtain a paper-coating resin especially, good in water resistance effect and ink receptivity, by reacting a polyalkylenepolyamine with an alicyclic dicarboxylic acid, a urea and an alkylating agent and, optionally, formaldehyde and/or glyoxal. CONSTITUTION:polyalkylenepolyamine (a) is reacted with an alicyclic dicarboxylic acid and/or a free carboxyl group-containing reaction product (b) obtained by a reaction of an alicyclic dicarboxylic acid with a glycol, a urea (C), an alkylating agnet (d) and, optionally, formaldehyde and/or glyoxal (e). By using an alicyclic dicarboxylic acid instead of the conventional aliphatic or aromatic dicarboxylic acid, the performance of the resin can be prominenetly improved. In order to react components (a)-(e) with each other, a reaction product among components (a), (b) and (c) is reacted with component (d) and, optionally, component (e).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a novel resin useful for paper coating and the like.

<Prior art> Conventionally, paper coating compositions composed of pigments, adhesives, dispersants, and other auxiliaries have been used for the purpose of imparting water resistance or improving ink receptivity. It is known to use resins such as , melamine-formaldehyde resin, urea-formaldehyde resin or polyamide polyurea-formaldehyde resin, polyamide polyurea-formaldehyde-epihalophytrine resin (
For example, Special Publication No. 44-11667, Special Publication No. 59-3259
7, Japanese Patent Publication No. 58-40322).

<Problems to be solved by the invention> However, with the former formaldehyde-based resin, harmful formaldehyde is emitted from the coated paper, and with the latter resin, although the generation of harmful components is small, in recent years As demands for paper quality such as ink receptivity and water resistance become more sophisticated, it has become impossible to meet these demands. Therefore, the present invention provides a method for producing a resin useful as a paper coating resin that exhibits unprecedented water resistance and ink receptivity.

Means for Solving the Problems> The present inventors have aimed to obtain a paper coating resin that is particularly excellent in water resistance and ink receptivity, and does not emit or almost no odor such as formaldehyde compared to coated paper. As a result of intensive study, we have completed the present invention.

That is, the present invention provides (a) 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. The present invention provides a method for producing a resin useful as a paper coating resin, which comprises reacting c) ureas, (d) an alkylating agent, and, if desired, (e) formaldehyde and/or glyoxal.

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

Component (b) alicyclic acid dibasic carboxylic acid used in the present invention is a general term that includes compounds having two carboxyl groups in the molecule, their esters, and their acid anhydrides. Typical 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.

In addition, the glycols used in the present invention include alkylene glycols such as ethylene glycol, propylene glycol, butanediol, cycloalkylene glycols such as butynediol, cyclobentanediol, and cyclohexanediol, and alkenylene glycols such as octenediol. , polyalkylene glycols such as diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, and polytetramethylene glycol, ethylene oxide adducts of bisphenol A, and ethylene oxide adducts of hydrogenated bisphenol A.

Furthermore, as the reaction product having a free carboxyl group obtained by the reaction of the alicyclic dibasic carboxylic acid and the glycols as component (b), the reaction product having a free carboxyl group obtained by the reaction of the alicyclic dibasic carboxylic acid and the glycols is , is a polyester having a carboxyl group at the molecular end obtained by reacting with an excess molar ratio of carboxylic acid. The reaction between this alicyclic dibasic carboxylic acid and glycols is usually carried out in the presence or absence of a catalyst.
This is carried out by heating at 0 to 200°C for 30 minutes to 2 hours.

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

Furthermore, the following various alkylating agents can be used as component (d).

(1) A halogen-containing compound represented by the general formula R, -X (wherein R1 is a lower alkyl group, alkenyl group, benzyl group, or phenoxyethyl group, and X represents a halogen atom). Preferred examples include the bromides and iodides corresponding to methyl chloride, ethyl chloride, propyl chloride, allyl chloride, benzyl chloride, phenoxyethyl chloride and the 2-isochloride.

(2) Dialkyl sulfides and dialkyl sulfates represented by the general formula (R20) 230 v (wherein R2 is a lower alkyl group, and ■ represents 1 or 2). Preferred examples include dimethyl sulfate, diethyl sulfate, dimethyl sulfide, diethyl sulfide, and the like.

(3) General Formula [In the formula, R3 represents a hydrogen atom, a lower alkyl group, a hydroxythealkyl group, or a phenyl group. ] Ethylene oxide derivative. Preferred examples include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, glycidol, and the like.

(4) General formula [wherein X represents a halogen atom and W represents 1.2 or 3]. ] Epihalohydrin represented by . Preferred examples include shrimp chlorohydrin and shrimp bromohydrin.

(5) General formula HOCH2 (cH2),
is the same as above. ) Monohalohydrin. Preferred examples include ethylene chlorohydrin and ethylene bromohydrin.

(6) General formula
When is an OH group, it represents a halogen atom. ] Dihalohydrin represented by A preferred example is 1.3
-dichloro-2-propatur, 2,3-dichloro-1
- Examples include property tools. Among the above, particularly preferred is epichlorohydrin.

The compounds used as the alkylating agent may be used alone or in combination of two or more.

The resin obtained by the method of the present invention is obtained in the form of an aqueous solution, and is usually prepared at a temperature of 50% by weight at 25°C.
Those with a viscosity of 5 to 1000 centivoise (hereinafter abbreviated as CP), and those with extremely low viscosity tend to have a low effect of adding resin as a coating composition for paper, and those with high viscosity is practically 10 to 500 cp, since the viscosity of the prepared paper coating composition may be high, which is generally associated with undesirable drawbacks.

Particularly preferably, those having a viscosity in the range of 20 to 200 cp are preferably used.

Next, the reaction method of each component (a), (a), (c), (d) and (e) will be described. The resin of the present invention is composed of, for example, the component (
It can be produced by reacting the reaction products of a), et al. and (c) with (d) and, if desired, with (e). The components (a), (b) and (c) can be reacted in any order.

First of all, components (a) and (b) 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 components (etc.) is 0.4 per mole of polyalkylene polyamine of component (a).
The reaction is carried out in a ratio of ~4 equivalents, preferably 0.8-3 equivalents. The reaction between the dehydration condensation reaction product obtained in this manner and the ureas of component (c) is carried out at a temperature of 100 to 180°C, preferably 110 to 160°C, while removing generated ammonia from the system. It will be held for ~6 hours. The amount of component (c) used is 1 equivalent or less, preferably 0.1 equivalent, per 1 equivalent of amino groups, that is, primary and secondary amino groups in component (a).
~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 (b) is carried out at a temperature of 120 to 250°C, preferably 130 to 20°C.
The reaction is carried out at 0° C. for 2 to 12 hours while removing generated water from the system. Component (b) is, for 1 mole of component (a),
It is used in a range of 0.2 to 2 equivalents, preferably 0.3 to 1.8 equivalents. Components (a) and (b) thus obtained
The step of reacting the reaction products of ) and (c) with component (c) again is carried out at a temperature of 100 to 180°C, preferably 1
It is carried out at 10-160°C for 1-6 hours. The amount of component (c) used is 2 to 1 equivalent of secondary amino group of component (a)+.
The amount is less than equivalent, preferably in the range of 0.1 to 1.5 equivalents.

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 (c) 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 1 mole of component (a) to 1 mole of component (b).
) of 0.2 to 2 carboxyl groups, preferably 0.3
~1.8 equivalents, 0.2 to 1 mol, preferably 0.3 to 0.8 mol of component (c) are suitable. The step of further reacting the reaction product thus obtained with component (c) is as follows:
It is carried out at a temperature of 100 to 180°C, preferably 110 to 160°C, for 1 to 6 hours. The amount of component (c) used is
2 equivalents or less, preferably 0.1 to 1.5 equivalents, based on the equivalent of the secondary amino group in ).

Components (a) and (b) obtained by various methods as above
The reaction products of (c) and (c) are both dissolved in water and then reacted with the alkylating agent (d) and, if desired, formaldehyde and/or glyoxal (e). The reaction with the alkylating agent is carried out at pH 3 in an aqueous solution with a concentration of 20-80% by weight, preferably 30-70% by weight.
-12, and the reaction temperature is 20-80°C for 1-10 hours. The amount of the alkylating agent to be used is 2 equivalents or less, preferably 0.2 equivalents or less, per 1 equivalent of the secondary amino group in component (a).
A range of 1 to 1.5 equivalents is suitable.

In the present invention, component (e) can be reacted if desired. The reaction products of components (a), (b) and (c) and components (d) and (e) may be reacted in any order,
The object of the present invention can be achieved by any of the following methods: reaction (d) followed by reaction (e), reaction (e) followed by reaction (d), ω), and simultaneous reaction (e). The reaction of component (e) takes place at a concentration of 20
The reaction is carried out in an aqueous solution of ~80% by weight, preferably 30-70% by weight, at a reaction temperature of 20-80°C for 1-10 hours. (
The appropriate amount of e) to be used is 1 mol or less, preferably 0.1 to 0.8 mol, per 1 mol of (c). The reaction pH is preferably pH 5 to 8 when glyoxal is used, and pH 3 to 7 when formaldehyde is used.

After the reaction is completed, the object of the present invention is obtained by adjusting the pH to 4 to 8 with an alkali such as caustic soda or potassium hydroxide, or an acid such as hydrochloric acid, sulfuric acid, or formic acid, if necessary.

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. (c) ureas (d) an alkylating agent and, if desired, (e) formaldehyde and/or glyoxal, and the resulting resin is used as a paper coating resin. Excellent ink receptivity when used as
It has water resistance and is 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.

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. All parts and percentages hereinafter are based on weight unless otherwise specified.

<Example> Example-1 58.5 parts (0.4 mol) of triethylenetetramine was placed in a four-way 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 a 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 to 130 t for 2 hours. Thereafter, it was cooled to 100° C. and water was added to make a 50% aqueous solution.

Then, 18.5 parts (0.2 mol) of epichlorohydrin
was charged and reacted at 60°C for 4 hours. Thereafter, it was cooled to 25° C., the pH was adjusted to 7 with 35% hydrochloric acid, and water was added to obtain a resin liquid with a concentration of 50% and a viscosity of 52 cp (25° C.). This is called resin liquid A.

Example-2 Triethylenetetramine 29 was placed in the same container as Example-1.
．． 2ta (0.2 mol) was charged, 30.8 parts (0.2 mol) of hexahydrophthalic anhydride was added thereto, and the temperature was raised to perform dehydration amidation 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. Next, 18.5 parts (0.2 mol) of epichlorohydrin and 15.4 parts (0.2 mol) of diethyl sulfate were added.
0.1 mol) and reacted at 60°C for 7 hours. After that, it was cooled to 25℃, adjusted to pH 6 with 20% sulfuric acid, and water was added to give a concentration of 50% and a viscosity of 63cp (25℃).
A resin liquid 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. Next, the mixture was 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. This was diluted by adding water to obtain an aqueous solution with a concentration of 50%.

Next, 23.2 parts (0.4 mol) of propylene oxide was charged and reacted at 25°C for 6 hours. Next, 9.3 parts (0.1 mol) of epichlorohydrin was charged, and the mixture was heated at 60°C for 3
After reacting for an hour, it was cooled to 30°C, the pH was adjusted to 6 with 35% hydrochloric acid, and water was added to give a concentration of 50% and a viscosity of 55%.
A resin liquid of cp (25°C) was obtained. This is called resin liquid C.

Example-4 Triethylenetetramine 58 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 t for 4 hours. In another container, add tetrahydrophthalic anhydride 6.
0.8 parts (0.4 mol) and propylene glycol 15.
Two parts (0.2 mol) were mixed and heated at 140-150°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 deammonification reaction, and was heated at an internal temperature of 150 to 155° C. for 4 hours to perform dehydration and deammonification reactions. Then cooled to 130°C and added urea 12
(0.2 mol) was added thereto, and the deammonia reaction was carried out at 125 to 130 t: for 2 hours. The drained water was added to make a 50% aqueous solution.

Next, 18.5 parts (0.2 mol) of epichlorohydrin was charged and the reaction was carried out at 65°C for 2 hours. After that, 8.1 parts (0.1 mol) of 37% formalin was added and the pH was adjusted to 5 with 70% sulfuric acid.
The reaction temperature was adjusted to 65° C. for 4 hours. Thereafter, it was cooled to 25° C., and the pH was adjusted to 7 with a 28% aqueous sodium hydroxide solution to obtain a resin liquid with a concentration of 50% and a viscosity of 48 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. Next, 77 parts (0.5 mol) of diethyl sulfuric acid was added, and the mixture was heated at 60°C.
Allowed time to react. After that, it was cooled to 25°C, the pH was adjusted to 7 with 20% sulfuric acid, and water was added to give a concentration of 50% and a viscosity of 4.
A resin liquid of 3 cp (25° C.) was obtained. This is called resin liquid E.

Example-6 In Example-4, instead of 8.1 parts of 37% formalin, 14.5 parts of 40% glyoxal (0°1 mol)
The pH was adjusted to 6 with 70% sulfuric acid, and the pH was adjusted to 4 at 55°C.
A resin liquid having a concentration of 50% and a viscosity of 5 Lcp (25° C.) was obtained in the same manner as in Example 4, except that the reaction was carried out for a certain period of time. This is called resin liquid F.

Comparative Example-1 According to Example-1, 29°6 parts of phthalic anhydride (0,2
The final concentration was 50%, the viscosity was 49cp (25°C
) was obtained. This is called resin liquid G.

Comparative Example-2 According to Example-1, all the same raw materials and the same conditions were used except that 29.2 parts (0.2 mol) of adipic acid was used instead of hexahydrophthalic anhydride in Example-1. The final concentration was 50% and the viscosity was 58cp (25℃).
A resin liquid was obtained. This is called resin liquid H.

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, thereby obtaining a polyester having carboxyl groups at the terminals. Further, 12.0 parts (0.2 mol) of urea was added thereto, and 58.5 m (0.4 mol) of triethylenetetramine was added while stirring at 110 to 120°C. This at 150℃
Deammonification and dehydration amidation reactions were carried out for 5 hours. This was cooled to 130°C, 12.0 parts (0.2 mol) of urea was added, and ammonia removal reaction was carried out at a temperature of 120 to 130°C for 2 hours. The drained water was added to make a 50% aqueous solution. Next, 77 parts (0.5 mol) of diethyl sulfuric acid was added,
The reaction was carried out at 60°C for 4 hours.

After that, it was cooled to 25℃, the pH was adjusted to 7 with 20% sulfuric acid, and water was added to give a concentration of 50% and a viscosity of 57cp (25℃).
A resin liquid was obtained. This is called resin liquid I.

Application Examples Using the aqueous resin solutions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 and Sumiraze Resin 613 (melamine/formaldehyde resin manufactured by Sumitomo Chemical G1), paper coatings were prepared according to the formulations shown in Table 1. A chemical composition was prepared.

ゝ＼, Table - Notes ■Ultra White 90 (clay manufactured by Engel Hard Minerals, USA) ■Carbicle 90 (calcium carbonate manufactured by Fuji Kaolin ■) ■Sumiraizu Resin DS-10 (polymer manufactured by Sumitomo Chemical ■) Acrylic acid pigment dispersant) ■5N-307 (styrene-butadiene latex manufactured by Sumitomo Naugatac ■) ■Tamako Ace A (oxidized starch manufactured by Tamago National Starch ■) The 0-fold portion 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 approximately 8.5, and then the paper coating composition was coated with water and a 10% caustic soda aqueous solution using a wire rod.
80 g/m' high quality paper with a coating weight of 14 g/m
It was coated on one side so that
After conditioning the humidity for 16 hours at a temperature of 60℃ and a linear pressure of 60kg/
A coated paper was obtained by supercalendering twice under the conditions of 0.1 cm. 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 as Examples 1 to 8.

The test method is as follows.

Water Resistance (A) Wet Rub Method Eleven drops of approximately 0.1 m of ion-exchanged water were placed on the coated surface, rubbed 7 times with fingertips, and the amount eluted was transferred to black paper to determine the amount eluted 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 Δ method RI tester (Mei Seisakusho), the coated surface was moistened with a water supply roll and then printed, and the ink receptivity was observed.

Ink receptivity (poor): 1 to 5 (excellent).

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

Ink receptivity (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 (2) 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. A method for producing a resin, which comprises reacting (c) a urea, (d) an alkylating agent and, if desired, (e) formaldehyde and/or glyoxal.