JPH068347B2 - Method for producing resin for paper coating - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel and useful method for producing a paper coating resin.

(Prior Art) In recent years, printing has become faster and more precise, and the number of colors has advanced, and it has been demanded that coated paper and art paper have further improved surface strength and print ink acceptability. .

On the other hand, in the manufacturing process of these coated papers and art papers, even in the process of applying the coating liquid to the base paper, high-concentration coating is progressing from the viewpoint of quality improvement, energy cost reduction and productivity improvement. However, in this case, a coating composition having good workability and excellent fluidity is required.

Conventionally, a melamine-formaldehyde resin for the purpose of imparting water resistance to various paper coating compositions comprising pigments, adhesives, dispersants and other auxiliaries or for the purpose of improving ink acceptability. Formaldehyde resin such as urea-formaldehyde resin or polyamide-urea-formaldehyde resin, or polyamide-
It is known to use cationic epoxy modified polyamide resins such as epihalohydrin resins, polyamide-urea-epihalohydrin resins or polyamide-urea-formaldehyde-epihalohydrin resins.

(Problems to be Solved by the Invention) However, these resins are particularly excellent in water resistance and acceptability because the higher the concentration of the coating liquid is, the thicker the coating liquid becomes, which is inconvenient for high-concentration coating. Moreover, there is an urgent need to develop a new additive for a coating composition for paper, which has excellent fluidity of the coating liquid.

(Means for Solving the Problems) As a result of intensive studies, the present inventors have developed a resin for paper coating which is excellent not only in water resistance and ink acceptability but also in fluidity of a coating liquid. It was

The configuration of the present invention will be described below.

That is, the present invention relates to an amino compound having one primary amino group and / or a monobasic carboxylic acid or a monobasic carboxylic acid derivative with respect to 1 mol of a dibasic carboxylic acid or a dibasic carboxylic acid derivative. Of less than 2.0 mol and 0.5 to 5.0 mol of an amino compound having at least two primary amino groups having polyalkylene polyamine and / or polyalkylene polyurea as a component are reacted to form a polyamide polyamine and / or polyurea polyamide resin. 0.1 to 3.0 per mol of the resin and the total of the primary amino group and the secondary amino group in the resin.
Deammonia is carried out by reacting with a molar amount of urea, and the obtained reaction product is reacted with at least one crosslinking agent of epihalohydrin, formaldehyde and dialdehyde and an anion agent for providing an anionic group. Alternatively, the present invention provides a method for producing a resin for paper processing, which comprises reacting the reaction product with the crosslinking agent and then mixing the anionizing agent.

In carrying out the method of the present invention, first, a polyalkylene polyamine and / or a polyalkylene polyurea and a dibasic carboxylic acid or a derivative thereof, and further 1
The polyalkylene polyamine or polyalkylene polyurea used for reacting an amino compound containing one primary amino group and / or a monobasic carboxylic acid or a derivative thereof is at least 2 in the molecule.
A compound having one primary amino group and at least one secondary amino group (imino group), each having the general formula H ₂ N—R ¹ —NH ₂ [I] or the general formula H ₂ N—R ² —NHCONH—R ³ —NH ₂ [II] wherein R ¹ , R ² and R ³ in the formula are each a divalent one having at least one secondary amino group in the main chain. It represents an aliphatic group and / or an aromatic group.

Is displayed.

In the following, these polyalkylene polyamines and polyalkylene polyureas are collectively referred to as a general formula H ₂ N—A—NH ₂ [III] where A in the formula is R ¹ or R ² —NHCONH—R ^{3 described above.} And R ¹ , R ² and R ³ are respectively as described above.

May be displayed with.

Here, typical examples of the polyalkylene polyamine include polyethylene polyamine, polypropylene polyamine, and polybutylene polyamine. Among them, polyethylene polyamine is preferable, and among them, diethylenetriamine, triethylenetetramine, or tetraethylenepentamine is preferable. Most suitable.

On the other hand, a typical example of the polyalkylene polyurea is the deammonification reaction product from the polyalkylene polyamine and urea as described above.

It is needless to say that these polyalkylene polyamines or polyalkylene polyureas may be used alone or in combination of two or more, and may be used in combination with each other. Further, it does not hinder the combined use of aliphatic diamines such as ethylenediamine, propylenediamine or hexamethylenediamine in the range of 50 mol% or less with these polyalkylene polyamines and / or polyalkylene polyureas.

The above-mentioned dibasic carboxylic acid or its derivative,
Compounds having two carboxyl groups in the molecule, or their esters, and their acid anhydrides are also collectively referred to. Succinic acid is representative of such carboxylic acids. Aliphatic dibasic carboxylic acids such as glutaric acid, adipic acid or sebacic acid or maleic acid or fumaric acid and their esters, or aromatic dibasic carboxylic acids such as phthalic acid, isophthalic acid or terephthalic acid and their Esters,
Further, there are acid anhydrides such as succinic anhydride, maleic anhydride and phthalic anhydride, but it goes without saying that these may be used alone or in combination of two or more.

Further, the above-mentioned amino compound containing one primary amino group refers to a compound having one primary amino group in the molecule. In this case, a secondary amino group (imino group) is further added. Alternatively, it may contain one or more tertiary amino groups.

Typical examples of the amino compound are aliphatic amines such as laurylamine, stearylamine, monoethanolamine, diethylaminoethylamine, methylaminepropylamine and N-aminoethylpiperazine, and aromatic compounds such as benzylamine and phenethylamine. Group amines.

Further, the above-mentioned monobasic carboxylic acid or its derivative is a generic term for compounds having one carboxyl group in the molecule and their esters, and among them, formic acid, acetic acid, or These include aliphatic carboxylic acids such as lauric acid and their esters, or aromatic carboxylic acids such as benzoic acid or phenylacetic acid and their esters.

The step of preparing the above-mentioned polyamide polyamine or polyurea polyamide, which should also be called the first step reaction in the method of the present invention, comprises the polyalkylene polyamine and / or polyalkylene polyurea (hereinafter,
These may be referred to as the compound (a). )When,
A dibasic carboxylic acid or a derivative thereof (hereinafter, sometimes referred to as compound (b)) and an amino compound containing one primary amino group (hereinafter, referred to as compound (c)) And / or a monobasic carboxylic acid or a derivative thereof (hereinafter sometimes referred to as compound (d)) in the presence or absence of a dehydration condensation reaction. , According to the following reaction formulas [IV], [V] or [VI].

However, R ⁴ and R ⁵ in the formula each represent a divalent or monovalent aliphatic group and / or aromatic group, and R ⁶ represents a hydrogen atom, a monovalent aliphatic group and / or aromatic group. And
, M and n are all natural numbers. Or A is as described above.

In carrying out such a reaction, the amount of the polyalkylene polyamine and / or polyalkylene polyurea [compound (a)] used is 1 mol of the dibasic carboxylic acid or its derivative [compound (b)]. 0.5 to 5.0 moles, preferably 1.0 to 3.0 moles,
The amount of the amino compound [compound (c)] and / or the monobasic carboxylic acid or its derivative [compound (d)] containing one primary amino group is the same as that of the compound (b).
A suitable range is 0 to 2.0 mol, preferably 0 to 1.0 mol, based on mol.

In addition, the reaction temperature at this time is appropriately in the range of 100 to 300 ° C., preferably 140 to 220 ° C., and the reaction is carried out in the range of 1 to 10 hours while removing the produced water out of the system. The polyamidoamine and / or polyurea polyamide represented by the reaction formulas [IV], [V] and / or [VI] can be obtained.

Next, in the reaction that should be called the second step, the polyamide polyamine and / or polyurea polyamide (e), (f), (g) obtained in the so-called first step reaction (dehydration condensation reaction) as described above is used. ) And urea, a deammonification reaction is carried out according to the reaction formula [VII] as described below. The amount of urea during this reaction is the total of primary and secondary amino groups in the polyamide polyamine and / or polyurea polyamide (e), (f), (g) obtained in the first step reaction. The amount is 0.1 to 3.0 mol, preferably 0.2 to 1.5 mol per mol. Reaction temperature is 90-1
The temperature is 60 ° C., preferably 110 to 140 ° C., and the reaction is carried out at this temperature for 0.5 to 10 hours while removing the generated ammonia out of the system.

Of the deammonification reactions of (e), (f), and (g) above, (e) is displayed as an example, as shown below. (e) Is A, for example When expressed by Therefore, Becomes

However, B in the formula represents a divalent aliphatic group and / or aromatic group containing or not containing -NHC (= O) NH-, p and q are natural numbers, and R ⁴ ,
Is as described above.

The step which should be called the third step reaction in the method of the present invention is to dissolve the deammonification product (h) obtained by the so-called second step reaction in water, and then to add epihalohydrin, formaldehyde and dialdehyde to this. Among them, at least one or more cross-linking reagents are reacted with sodium pyrosulfite and / or sodium bisulfite as an anionizing agent that imparts an anion group, or after reacting with the cross-linking reagent, the anionizing agent is added. Is to mix.

Epichlorohydrin or epibromohydrin is a typical example of epihalohydrin, and the total amount of amino groups in compound (a) and compound (c) used to synthesize compound (h) is 1 equivalent. It is preferable to add it in the range of 4 equivalents or less. In addition, it is appropriate that the amounts of formaldehyde and dialdehyde combined are 2 equivalents or less with respect to 1 equivalent of the total urea used to synthesize the compound (h). On the other hand, the amount of the anionizing agent is preferably 2 equivalents or less with respect to 1 equivalent of the total amount of the crosslinking agents.

Further, examples of the dialdehyde include glyoxal and glutaraldehyde.

The order of addition of these epihalohydrin, formaldehyde, dialdehyde and anionizing agent is not particularly limited, and they may be sequentially added in any order or at the same time, but epihalohydrin and formaldehyde and dialdehyde may be added. It is essential to add one or more reagents selected from the above and one or more reagents selected from the anionizing agents.

The order of addition of the cross-linking agent (denoted as a) and the anionizing agent (denoted as b) is specifically, when both are used as reaction components, a and b are simultaneously treated (see Examples 2 and 4 below). , 6,
Examples in the following are shown in parentheses below), a, then a,
Then, b (Example 3), b, and then b and b are simultaneously (Example 1). When the latter is mixed, B and b are reacted at the same time, and then B is mixed (Example 5). )
From these specific examples and the above general description, when a and b are to be reacted in addition to these,
B, then B, then B, then B, then B, at the same time, B, B at the same time, then B, B, B at the same time, then B at the same time.When mixing B, let B react. In the present invention, "the reaction product is provided with at least one cross-linking reagent and at least one crosslinkable reagent selected from epihalohydrin, formaldehyde, and dialdehyde". The case of reacting an anionizing agent or reacting the reaction product with the crosslinking agent and then mixing the anionizing agent "includes these cases.

The reaction at this time is carried out in an aqueous solution having a concentration of 20 to 80% by weight, preferably 30 to 60% by weight at a pH of 3 to 12 at a reaction temperature of 30 to 90 ° C. for 0.5 to 10 hours. Here, for example, in the case where the reaction is carried out using epichlorohydrin and formalin as the crosslinking agent and sodium bisulfite as the anionizing agent, an anion group is contained as in the following general formula [VIII]. The obtained resin [i] is obtained.

However, R ⁴ , B, P and q in the formula are as described above,
Α is -C (= O) NH ₂ and / or -C (= O) NHCH ₂ OH and / or In addition, B hydrogen atoms and / or --CH ₂ CH (OH) CH ₂
C and / or Represents

(Effect of the Invention) Thus, the resin obtained by the method of the present invention is excellent not only in water resistance but also in ink acceptability, and is extremely important as an additive for a paper coating composition.

(Examples) Next, the present invention will be specifically described with reference to Examples, Comparative Examples, and Application Examples. In the following, all parts and% are based on weight unless otherwise specified.

<Examples 1 to 6 and Comparative Examples 1 to 2> Example 1 In a four-necked flask equipped with a thermometer, a reflux condenser and a stir bar, 206 g (2 mol) of diethylenetriamine and 12.2 g (0.2 mol) of monoethanolamine. Was added, and 146 g (1 mol) of adipic acid was added to add 160 to 17
A condensation reaction was carried out at 0 ° C. for 3 hours to remove generated water out of the system. Then, after cooling this to 120 degreeC, 176 g (2.94 mol) of urea was added and the deammonification reaction was performed at 130-140 degreeC for 3 hours. Then, water was added thereto to obtain a 50% polyamide polyurea aqueous solution. Then add 117 g (1.26 mol) of epichlorohydrin to give 7
The reaction was continued at 0-80 ° C for 2 hours. After that, 30 ℃
Cool to 37% formalin 68g (0.84mol) and sodium bisulfite 43.7g (0.42mol) and add 5
The pH was adjusted to 4 with a 0% aqueous solution of sulfuric acid, and the mixture was stirred at 60 to 70 ° C for 3 hours.

Further, water was added to obtain a water-soluble resin having a solid content of 50%. Hereinafter, this resin aqueous solution is abbreviated as "i-1".

Example 2 In a reaction vessel similar to that in Example 1, diethylenetriamine 1 was added.
03g (1 mol), triethylenetetramine 146g
(1 mol) and 60 g (1 mol) of urea were charged, and a deammonification reaction was carried out at 140 to 150 ° C. for 3 hours while stirring. Then, this was cooled to 100 ° C., and then 102 g (0.7 mol) of adipic acid and 37 g (0.3 mol) of benzoic acid were added.
Mol) was added to carry out a condensation reaction at 160 to 170 ° C. for 3 hours to remove generated water out of the system. Then, this was cooled to 120 ° C., 238 g (3.96 mol) of urea was added, and a deammonification reaction was carried out at 130 to 140 ° C. for 3 hours. Then, water was added thereto to obtain a 50% polyamide polyurea aqueous solution.

Next, 321 g (3.96 mol) of 37% formalin and 208 g (1.65 mol) of sodium sulfite were added, and the pH was adjusted to 11 with a 30% aqueous sodium hydroxide solution to 70-80.
It was kept under stirring for 3 hours at ° C. Further, water was added to obtain an aqueous solution resin having a solid content of 30%. This resin aqueous solution is referred to as "i
-2 ".

Example 3 Triethylenetetramine 2 was placed in the same reaction vessel as in Example 1.
19 g (1.5 mol) and adipic acid 73 g (0.5 mol)
And maleic anhydride 49 g (0.5 mol) were added to give 160
The condensation reaction was carried out at ˜170 ° C. for 3 hours to remove the generated water outside the system. Then after cooling it to 120 ° C.,
216 g (3.6 mol) of urea was added and a deammonification reaction was performed at 130 to 140 ° C. for 3 hours. Then, water was added thereto to obtain an aqueous solution of 60% polyamide polyurea.

Then add 37 g (0.4 mol) of epichlorohydrin and add 6
After reacting at 0 to 70 ° C for 2 hours, 87 g (0.6 mol) of 40% glyoxal aqueous solution was added and the mixture was stirred at 60 to 70 ° C for 4 hours.
It was kept under stirring for an hour.

Next, 38 g (0.2 mol) of sodium pyrosulfite was added, and the pH was adjusted to 4 with a 50% aqueous sulfuric acid solution to 60.
Stir for 4 hours at ~ 70 ° C and add water to add solids 4
0% of water-soluble resin was obtained. This resin aqueous solution is referred to as "i-
3 ”is abbreviated.

Example 4 Triethylenetetramine 2 was placed in the same reaction vessel as in Example 1.
92 g (2 mol) and 146 g (1 mol) of adipic acid were added and a condensation reaction was carried out at 160 to 170 ° C. for 3 hours to remove generated water out of the system. Then, after cooling this to 120 ° C., 216 g (3.6 mol) of urea was added to the mixture to make 130
The deammonification reaction was carried out at ˜140 ° C. for 3 hours. Then, water was added thereto to obtain a 50% polyamide polyurea aqueous solution. 38 g (0.3 mol) of sodium sulfite
And 83 g (0.9 mol) of epichlorohydrin were added and the reaction was continued at 70-80 ° C for 3 hours. Water was added to obtain a water-soluble resin having a solid content of 30%. This resin aqueous solution is referred to as "i
-4 ".

Example 5 Diethylenetriamine 10 was placed in the same reaction vessel as in Example 1.
Charge 3 g (1 mol) and triethyletramine 146 g (1 mol), further add 120 g (1.2 mol) of succinic anhydride and carry out a condensation reaction at 170 to 180 ° C for 3 hours to remove generated water outside the system. did. Then this 120
After cooling to 0 ° C, 221 g (3.68 mol) of urea was added and a deammonification reaction was carried out at 120 to 130 ° C for 3 hours. Then, water was added thereto to obtain a 60% polyamide polyurea aqueous solution. Next, 40% glyoxal aqueous solution 1
67 g (1.15 mol) and 29 g of sodium sulfite (0.
23 mol) and add 30% sodium hydroxide aqueous solution to adjust the pH.
After adjusting to 9, the mixture was stirred at 50 ° C. for 2 hours. Sodium sulfite 29 g (0.23 mol) and water were added to give a solid content of 50%.
A resin aqueous solution of Hereinafter, this resin aqueous solution is referred to as "i-5".
Is abbreviated.

Example 6 A reaction vessel similar to that in Example 1 was charged with diethylenetriamine 3
10 g (3 mol) and 60 g (1 mol) of urea were charged, and a deammonification reaction was carried out at 140 to 150 ° C. for 3 hours while stirring. Then, after cooling this to 100 ° C., 94 g (0.8 mol) of succinic acid and 39 g (0.2 mol) of isophthalic acid dimethyl ester were added, and a condensation reaction was carried out at 170 to 180 ° C. for 4 hours to generate water and methanol. Removed outside. Then, after cooling this to 120 ° C., 360 g (6 mol) of urea was added to 130-140.
The deammonification reaction was carried out at ℃ for 3 hours. After a while,
Water was added to this to obtain a 50% polyamide polyurea aqueous solution. Next, 93 g (1 mol) of epichlorohydrin, 37%
122 g (1.5 mol) of formalin, 145 g (1 mol) of 40% aqueous glyoxal solution and 52 g (0.5 mol) of sodium bisulfite were added at the same time, and the mixture was kept under stirring at 70 to 80 ° C. for 5 hours. Solid content 40 by adding more water
% Aqueous resin was obtained. This resin aqueous solution is referred to as "i-
6 ".

Comparative Example 1 A water-soluble resin having a solid content of 50% was obtained by performing the same reaction as in Example 1 except that sodium hydrogen sulfite was omitted. Hereinafter, this resin aqueous solution is abbreviated as "r-1".

Comparative Example 2 The same reaction as in Example 2 was carried out except that sodium sulfite was omitted to obtain an aqueous resin having a solid content of 30%. Hereinafter, this resin aqueous solution is abbreviated as "r-2".

<Application Examples 1 to 6 and Comparative Application Examples 1 to 4> The resin aqueous solutions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 and commercial products (Epinox P-9007Y, Dick.
Hercules Co., Ltd.) was mixed as a printability improving agent according to the coating liquid blending ratio as shown below, and then water was added so that the concentration became 60%, and the pH was adjusted to 9 with a 30% caustic soda aqueous solution. Then, various coating compositions for paper were prepared. A paper coating composition containing no printability improver was prepared in the same manner.

"Ultra White 90" 85 parts (Clay made by Engelhard Minerals, Inc. in the United States) "Carbital 90" 15〃 (calcium carbonate manufactured by Fuji Kaolin Co., Ltd.) "JSR-0692" 10〃 (manufactured by Japan Synthetic Rubber Co., Ltd.) Latex) "Nissho MS-4600" 5〃 (Starch manufactured by Japan Food Processing Co., Ltd.) "Aron T-40" 0.4〃 (Dispersant manufactured by Toagosei Co., Ltd.) Printability improver 0.8〃 Note) Above All "parts" are solid weights.

Using the applicator, the basis weight of the coating composition is 7
The surface was coated on one side with 5 g / m ² of atom so that the coating amount was about 15 g / m ² . Immediately thereafter, it was dried in a hot air drier at 100 ° C. for 1 minute and then calendered twice under the conditions of a temperature of 50 ° C. and a linear pressure of 8 kg / cm. The obtained single-sided coated paper was conditioned for 24 hours at 20 ° C. and 65% RH, and then the water resistance and ink acceptability of the coated paper were measured. The results of these measurements are shown in Table 1.
Each test method is as a pair.

1) Ink acceptability Using an RI tester, wetting the coating and the surface with a water supply roll, then printing, and observing the ink acceptability with the naked eye.
Grades ranging from to poor 1 were judged in stages.

2) Water resistance i) Wet pick method Using an RI tester, the coated surface is moistened with a water supply roll, printing is performed, and the peeled state is observed with the naked eye. ~ Inferior 1 "was determined.

ii) Wet rub method Ion-exchanged water was dripped on the coated surface by about 0.1 m, and the fingertip was worn 3, 5, 10, 15 and 20 times,
The elution part corresponding to each number of times was transferred to black paper, and the elution amount was observed with the naked eye, and "water resistance excellent 5 to poor 1" was determined.

3) Dry pick (Dry pick) Printing was performed with an RI tester and the state of the paper peeling was visually observed to determine "excellent dry pick resistance 5 to poor 1".

4) Viscosity of coating liquid Using a BM type viscometer, using a spindle of No. 4 60
Immediately after preparation of the coating solution and after standing at room temperature for 24 hours, the viscosity of the coating solution was measured at 25 ° C. by rmp.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location D21H 19/44

Claims (7)

[Claims] 1. An amino compound having one primary amino group and / or a monobasic carboxylic acid or a monobasic carboxylic acid derivative relative to 1 mol of the dibasic carboxylic acid or dibasic carboxylic acid derivative. A resin of polyamide polyamine and / or polyurea polyamide by reacting 2.0 mol or less with 0.5 to 5.0 mol of an amino compound having at least two primary amino groups having polyalkylene polyamine and / or polyalkylene polyurea as a component To give 0.1 to 3.0 mol of urea per 1 mol of the total of the primary amino group and the secondary amino group in the resin for deammonification to obtain the reaction product. Provides at least one crosslinking agent and an anionic group of epihalohydrin, formaldehyde and dialdehyde That either the anionic agent is reacted, or after reacting the crosslinkable agent to the reaction product, the production method of the paper coating resin, characterized in that mixing the anionic agent. 2. An amino compound having one primary amino group and / or 2.0 mol or less of a monobasic carboxylic acid or a monobasic carboxylic acid derivative is 0. A method for producing a resin for paper coating according to the item. 3. The method for producing a paper coating resin according to claim 1 or 2, wherein the anionizing agent is sodium (pyro) sulfite and / or sodium bisulfite. 4. The paper coating according to claim 1, 2 or 3, wherein the amount of the anionizing agent is 2 equivalents or less with respect to 1 equivalent of the total amount of the crosslinking agent. Of manufacturing resin for automobile. 5. The claim 1 or 2 wherein the dialdehyde is glyoxal or glutaraldehyde.
A method for producing a resin for paper coating according to the item. 6. The amount of epihalohydrin in the crosslinking agent is 4 per 1 equivalent of the total amount of amino groups in the amino compound containing one primary amino group and in the polyalkylene polyamine and / or polyalkylene polyurea. The method for producing a resin for paper coating according to claim 1 or 2, which has an equivalent amount or less. 7. An aldehyde compound such as formaldehyde and / or dialdehyde is used as a crosslinking agent, and the total amount used is 2 equivalents or less relative to 1 equivalent of the total amount of urea used in the reaction. Item 2. A method for producing a resin for paper coating according to Item 2 or Item 2.