JPS582331A - Preparation of aqueous solution of thermosetting resin - Google Patents

Abstract

PURPOSE:To prepare an aqueous solution of a resin useful as a water-resistance improving agent, dry-pick improving agent, ink-receptivity improving agent, etc. for a paper coating composition, by the ammonia-removal condensation of a polyamide polyamine with urea, followed by the reaction of the product successively with epihalohydrin and formaldehyde. CONSTITUTION:A polyamide polyamine obtained by the dehydrative condensation of 1mol of a polyalkylene polyamine and/or polyalkylene polyurea with 0.3-1.0mol of a dibasic carboxylic acid, is subjected to the ammonia-removal reaction with 0.2-0.8mol of urea based on 1 equivalent of the secondary amino group of the polyamide polyamine. The resultant polyamide polyurea is dissolved in water and made to react with epihalohydrin and/or 1,3-dihalo-2-propanol at 3.5-11pH and 40-80 deg.C. The reaction product is further reacted with formaldehyde and/or glyoxal at 40-80 deg.C to obtain the objective resin solution.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is useful as a water resistance agent, a dry/buck improver, an ink receptivity improver, etc. for paper coating compositions, and furthermore, it reduces the generation of odors such as formaldehyde from coated paper. The present invention relates to a method for producing a novel thermosetting resin aqueous solution having excellent properties such as very little or no amount.

Aminoplast resins, such as melamine-formaldehyde resins, are used to impart water resistance and improve ink receptivity to various paper coating compositions consisting of pigments, binders, dispersants and other auxiliaries. Alternatively, it is known to mix and use positive epoxy-modified polyamide resins such as polyamide-ebihalohydrin resin (Japanese Patent Publication No. 35-354'7 or Japanese Patent Publication No. 46-7
607 Specification).

However, the former resin generates a large amount of formaldehyde from the coated paper and has insufficient ink receptivity, while the latter resin has sufficient water resistance for many years, but also significantly increases the viscosity of the coating liquid. It has the disadvantage that it is unsuitable as a highly concentrated coating liquid because it reduces the workability of electrical work.

Furthermore, although the water-soluble polyamide resins described in Japanese Patent Publication No. 44-115167 or Japanese Unexamined Patent Publication No. 55-31837 generate a small amount of formaldehyde, when the I)H of the coating liquid is high, There is a drawback that the water resistance effect (resistance to wet bumps and wet rubs) during ffl moisturizing of the wet brush is reduced.

However, regardless of the I)H of the coating liquid of the present inventors, the water resistance effect is excellent, the amount of formaldehyde generated from grave paper is extremely small or not at all, and the ink receptivity during printing is excellent. Moreover, as a result of intensive studies to obtain a paper coating resin composition with further improved coating workability, the present invention was completed.

That is, the present invention provides polyalkylene polyamines and/or
Alternatively, a polyamide polyamine produced by dehydration condensation of a polyalkylene polyurea and a dibasic carboxylic acid is deammoniated with urea, and then the resulting polyamide "
A helohydrinated polyamide polyurea resin is obtained by reacting polyurea with shrimp halohydrin and/or 1,3-shiba o-2-propatol in an aqueous solution, and then the halogenated resin is reacted with formaldehyde and/or under acidic or alkaline conditions. A method for producing an aqueous thermosetting resin solution comprising reacting it with/or glyoxal is provided.

From the viewpoint of the manufacturing process, the method of the present invention includes (1) first stage reaction; dehydration condensation reaction of polyalkylene polyamine and/or polyalkylene polyurea with dichloric carboxylic acid; (2) second stage reaction! Deammonification reaction between the first stage reaction product and urea (3) Third stage reaction; Reaction between the second stage reaction product and shrimp halohydrin and/or 1,3-shiba c2-2-propanol (4) Fourth stage Stage reactions: Reactions between the third stage reaction product and formaldehyde and/or glyoxal can be divided into four stages.

Here, the above-described polyalkylene polyamine or polyalkylene polyurea refers to a compound having 1c2 primary amino groups and at least one secondary amino group in the molecule, respectively. It is represented by the general formula (1) or [■].

H2N -R1-NH2HgN-12-NHCONH-
R3-NH2C1) (II
) Hereinafter, the polyalkylene polyamine represented by the formula [13] and the polyalkylene polyurea represented by the formula Ill5 may be collectively abbreviated as the general formula [■].

I(2N -X -NI(2(Ill)) First, representative polyalkylene polyamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, and 3-azahexane-1,6-diamine. , 4.7-cyazadecane-1.10-diamine or 〒-azatrideca7-1.1
Examples of the polyalkylene polyurea include deammoniated reaction products of the above-mentioned polyalkylene polyamines and urea. Each of these polyalkylene polyamines or polyalkylene polyureas can be used not only as a single type, but also as a mixture of two or more types.

On the other hand, it refers to a compound having two carboxyl groups with the dihydrocarboxylic acid and ri, or an ester derivative thereof, such as succinic acid, glutaric acid, adipic acid, sepadino acid, maleic acid or fumaric acid. Typical examples are aliphatic carboxylic acids such as aliphatic carboxylic acids or esters thereof; or aromatic carboxylic acids such as isophthalic acid or terephthalic acid or esters thereof, and these can be used not only alone but also as a mixture of two or more. .

The above-mentioned first stage reaction in the method of the present invention involves the above-mentioned polyalkylene polyamine and/or polyalkylene polyurea (hereinafter, these two compounds are also collectively referred to as "polyamine") and the above-mentioned dibasic carboxylic acid (hereinafter referred to as "polyamine"). , which is referred to as H(IV') when expressed in the general formula), to obtain a polyamide polyamine (V) according to the following reaction formula (+).

ll3N -X -NH2+ HOOC-R4-C0
OH[■][Me→+HN-X-NHCO-R4-Co-)n(1)[■ And, the amount of dibasic carboxylic acid in this reaction is α3 to 13 moles per mole of polyamine, Preferably haα
A range of 5 to LO moles is suitable. Reaction'MA Wlu
l o o~300℃, preferably 140~220℃
1 to 1 while removing the generated water from the system.
The reaction is carried out for 0 hours.

Next, in the second stage reaction, the polyamide polyamine (V) obtained in the first stage reaction is deammoniated with urea, and through this reaction, the primary in the polyamide polyamine (V) is removed. Urea is added to the amino group and/or the secondary amino group, and a polyamide polyurea (b) is obtained according to the following reaction formula (it).

[Leopard + αH2NC0NHg -1 → [■] The amount of urea in this reaction is 9- per secondary amino group in the polyamide polyamine (V) obtained in the first stage reaction. /c, preferably 1 mol or less, preferably 02
~08 moles. Reaction temperature ij: 90-15
The reaction is carried out at 0°C, preferably from 110 to 130°C, for 5 to 5 hours while removing the generated ammonia from the system.

In the third step of the reaction in the method of the present invention, the polyamide polyurea (Vi) obtained as described above is dissolved in t-water, and then added to it.
It is a book that reacts with il, 3-dihalo-2-propanol, and shrimp cumylhydrin or shrimp bromohydrin are typical examples of shrimp halohi dorino.On the other hand, 1. Representative examples of r5-dihalo-2-propanol include 1,3-dichloro-2-propanol or 1,3-dibromo-2-propanol, which can be used alone or in combination. I can do it. And the reaction at this time is lI & 20~70% by weight, -1
〇- Preferably in an aqueous solution of ij30 to 60% by weight, &δ~1
α5 with a reaction temperature of 40 to 80°C at a pH in the range of 1
Do this for ~5 hours. Taking the case of epichlorohydrin as an example, the following reaction formula (ji) is used to obtain a chlorohydrinated polyamide polyurea resin (b) [■] 10βCH2-CH-CH2-Cn ---→\
1 and epihalohydrin or/in such reactions.
and f of the 1,3-dihalo-2-propatol is 15 mol or less per equivalent of the secondary amino group remaining in the unreacted -11 in the second reaction step, Preferably, a range of α7 to L3 moles is appropriate.

Next, in the fourth step reaction described above, the product (b) obtained in the third step reaction is reacted with formaldehyde and/or glyoxal, and this reaction is carried out at a concentration of 20 to 7 oz., preferably is carried out in a 30-60% by weight aqueous solution at a reaction temperature of 40-80°C for 1-10 hours. The amount of formaldehyde and/or glyoxal at this time is determined by the amount of polyamide polyurea (vI
L5 per mole of total urea used to synthesize L5
A suitable amount is less than 1 mole, preferably α2 to 10 moles. After completion of the reaction, an alkali such as caustic soda, caustic potash or ammonia, or an acid such as hydrochloric acid, sulfuric acid or formic acid may be added to stabilize the product, pHf 3-8.
, preferably adjusted to 4-6. The acid or alkaline acid used can be used alone or in combination with a certain amount of irradiation.

As described above, the present invention involves (1) dehydrating and condensing a polyamine and a dibasic carboxylic acid, and then (2)! After partially removing ammonia from the R element, a step of further reacting with (1) halogen, phosphorus and/or 1,3-dihalo-2-propanol, and then (3) reacting with formaldehyde and/or glyoxal. shall be mandatory.

In other words, if, for example, the second step II of these is omitted, the final product will not be a collection of the coating solution taI, and the result will be a significant deterioration of the coating operation and properties. C, M, T, if you omit the third step, tt
I Water resistance effect (resistance to wet,...1 pick and wet rub), Ink receptivity will be reduced, especially if the coating liquid is
If H is 4z or m, these decreases will be significant, and the amount of formaldehyde generated from the coated paper will also increase.

Thus, the thermosetting resin produced by the method of the present invention has excellent water resistance and ink receptivity, as well as
Since the amount of formaldehyde generated is small or not at all, it can be advantageously used as a paper coating composition with good coating workability.

Next, the present invention will be specifically explained using Examples, Comparative Examples, and Application Examples.

In the following, all numbers (@) without special [J] and "H" and "parts" refer to weight 14. Example 1 In a four-necked flask equipped with a reflux condenser and a stirring bar, diethylenetetramine 206f (2 mol) and adipine were added. Add acid 1469 (1 mol) and heat to 160-165℃
The feeding reaction was carried out for 3 hours, and the generated water was removed from the system.

After cooling to 120° C., 120 r (2 mol) of urea was added, and a deammonia reaction was performed at 125 to 130° C. for 2 hours.

Thereafter, 40 Of water was gradually added to obtain an aqueous solution of polyamide polyurea.

Next, Shrimp Chlorophyll 71851' (2 mol) was added and stirred at 50° C. for 1 hour while keeping it warm. After that, 30℃
Cool at 1, add 37 thiformin 60f (α75 mol), adjust the pH to 5 with 50% sulfuric acid aqueous solution, and heat at 60°C.
The mixture was stirred while keeping the temperature at VC for 3 hours. The mixture was then cooled to 25° C., and the pH was adjusted to 4.5 with a 30% caustic soda aqueous solution to obtain a thermosetting resin aqueous solution with a solid content of 50%.

Example 2 After adding 37% formalin, first adjust the pH to 9 with 30% caustic soda, stir at 60°C for 3 hours to retain moisture, cool to 25°C, and then add 37% hydrochloric acid to I )
Example 1 except that H was adjusted to 4.0.
In the same manner as above, a thermosetting resin aqueous solution having a solid content of 50% was poured.

Example 3 Change the amount of urea to 18'0p (3 mol), the amount of epichlorohydrin f92.5 f (1 mol) iIc, the amount of phosphorus 'f, (9L2f ('1125 mol) K) Other than that, the same procedure as in Example 1 was carried out to obtain a thermosetting resin aqueous solution having a solid content of 50%.

In the same apparatus as in Example 1, triethylenetetramine 29
2F (2 mol) and adipic acid 146f (1 mol) were charged, and a feeding reaction was carried out at 160 to 165°C for 3 hours with stirring, and the generated water was removed from the system. Then 12
After cooling to 0°C, urine 1A180f (3 mol) was added and ammonia removal reaction was performed at 121 to 130°C for 2 hours. Thereafter, water of 7401 was gradually added to obtain an aqueous solution of polyamide polyurea.

Next, epichlorohydrin 27'7.5F (3 mol) was processed and kept at 50°C for 1 hour while stirring. After that, it was cooled to 30°C and 37% formalin 912f (L
125 mol) and I) H't with 501 sulfuric acid aqueous solution.
After adjusting the temperature to 5, the mixture was stirred at 60° C. for 3 hours while keeping it warm. Next, it was cooled to 25°C and diluted with a 30% caustic soda aqueous solution.
H to 4. ．． A thermosetting resin aqueous solution having a solid content of 50 cm was obtained. ' □Example 5 The amount of urea was set to 240 f (4 mol), the amount of epichlorohydrin was -1 to 185 f (2 mol) ic, the amount of 37% formalin was 1
12L6f (15 mol) Except for changing the VC, the same procedure as in Example 4 was carried out to obtain a thermosetting resin aqueous solution with a solid content of 50%.

Example 6 In an apparatus similar to Example 1, diethylenetriamine 206
f (2 mol) and urea 60r (1 mol) and total preparation, 14
Ammonia removal reaction was carried out at 5 to 150°C for 2 hours, and then 1462 mmoles of adipic acid was added and 16'O to 165
Dehydration condensation was carried out at ℃ for 3 hours without removing the generated water.

After cooling to 120°C, urea aovti mol) was added and deammonization was carried out at 125-130°C for 2 hours. Thereafter, 350 tons of water was gradually added to obtain an aqueous solution of polyamide polyurea.

Next, 92.5 f (1 mol) of epichlorohydrin was added and stirred at 50° C. for 1 hour. After that, 37% formala l8-rif 30.41F (0375 mol) was added and then 50%
The pH was adjusted to 5 with an aqueous sulfuric acid solution, and the mixture was stirred at 60° C. for 3 hours.

Next, it was cooled in a 25° C. cabinet and adjusted to p)(i5.5) with a 30% caustic soda aqueous solution to obtain a thermosetting resin aqueous solution having a solid content of bO%.

Example 7 In an apparatus similar to Example 1, triethylenetetramine 29
22 (2 mol) and urea 60r (1 mol) were prepared, and 1
Ammonia removal reaction was carried out at 45-150°C for 2 hours, and then adipic acid 1461F (1 mol) was added to 160-1
The mixture was dehydrated at 65° C. for 3 hours to remove generated water. 1
After cooling to 20℃, urea 120? (2 mol) was added to carry out a deammoniation reaction at 125-130°C for 2 hours. Thereafter, 4.50□2 of water was gradually added to obtain an aqueous solution of polyamide polyurea.

Next, Shrimp Chlorophyte 7185F (2 mol) was processed and stirred at 50° C. for 1 hour. Next, 60.8 r [0.75 mol] of 37% formalin was added, and the pH was adjusted to 5 with a 50% aqueous sulfuric acid solution, followed by stirring at 60° C. for 3 hours. Thereafter, it was cooled in a 25° C. cabinet and adjusted to a total pH of 5.0 with a 30% caustic soda aqueous solution to obtain a thermosetting resin aqueous solution with a solid content of 50%. Amount of epichlorohydrin (z92.FM (1 mol) Ic13'7%Other than changing the amount of formalin to 9122 (1,125 mol), the same procedure as in Example F was carried out to obtain a thermosetting resin aqueous solution with a solid content of 50%. Ta.

Example 9' Urea fii60f (1% l), epichlorohydrin amount 27'7.59 (3 mol), 37% formaly y
A thermosetting resin aqueous solution having a solid content of 50% was obtained in the same manner as in Example 7 except that l was changed to 3α4t (α375 mol).

Example 10 1,3-dichloro-2 instead of epichlorohydrin
- Except for using PropaTool 2B59 (2 mol),
A thermosetting resin aqueous solution having a solid content of 50% was obtained in the same manner as in Example 7.

Example 11 In place of 37% formalin, add E, 40% glyoxal 290F (2 mol), and adjust pH with 6N HClIC.
Comparative Example 1 The same reaction as in Example 1 was carried out in the same manner as in Example 7, except that the mixture was adjusted to 6 and then stirred at 50°C for 2 hours. Add 1 diethylenetriamine to the device.
12.5f (1,09 mol) and adipic acid 146F
(, 1 mol) was charged, a dehydration reaction was carried out at 170°C for 3 hours, and the distilled water was removed from the system. After cooling at 120°C, 120r (2 mol) of urea was added, and then at 130°C.
The mixture was stirred at a temperature of 25 hours to carry out a deammonification reaction.

1c500 t of water was added to the obtained reaction product, and 162f (2 mol) of 37% formaldehyde was added thereto. After adjusting the pH to 11o with a 30% aqueous sodium hydroxide solution, the mixture was stirred at a temperature of 60° C. for 2 hours. After that, 30
After adding 0f of water and further cooling to 25°C, 1) H was adjusted to 8 with 35% hydrochloric acid to obtain a thermosetting resin aqueous solution with a solid content of 30%.

Comparative Example 2 Triethylenetetramine 22-292F (2 moles) and urea 60F (1 mole) were charged in a reaction apparatus similar to that in Example 1, and ammonia removal reaction was carried out at 150°C for 3 hours, followed by adipic acid 146F (1 mole). 1 mol) was added and dehydration condensation was carried out at 160°C for 5 hours.Next, after cooling to 130°C, 240p (4 mol) of urea was added, and deammonification was carried out at 130°C for 2 hours.Thereafter, 550f of water was gradually added to obtain a polyurea polyamide aqueous solution.

Then 37% formalin 12.1.5 r (1,5
mol) and adjust the pH to 4 with 2ON-sulfuric acid to 7.
The mixture was stirred at 0° C. for 4 hours. Thereafter, the mixture was cooled at 30° C. and adjusted to I) Hka of 5 with a 30% aqueous solution of caustic soda to obtain an aqueous thermosetting resin solution with a solid content of 50%.

Comparative Example 3 In a reactor similar to Example 1, triethylenetetramine 160F (1,096 mol) and adipic acid 146f (1
Mol) was reacted at 190°C for 4 hours under a nitrogen stream to form a polyamide, which was then briefly treated under reduced pressure and then water was added to give a concentration of 12%, and this polyamide aqueous solution 5
'70 f' with Ebichlorhuman 'phosphorus 50f (0,54
mol) was added and reacted at 70°C for 3 hours. After that, this was cooled to 40°C, and then treated with hydrochloric acid (I) H4,5.
Adjustment 1-7 was carried out and water was further added to obtain a thermosetting resin aqueous solution having a concentration of 1O.

Application Examples 1 to 11 and Comparative Application Example 1-, S Example 1-1
．． The various thermosetting resin aqueous solutions obtained in 1 and Comparative Examples 1 to 3 were used as water resistant agents, and mixed according to the coating/color mixing ratios shown in Table 1, and then water was added to the solution so that the concentration was 55%. In addition, the pH was adjusted to 9Vc with 30% caustic soda to prepare a paper coating composition.

Table 1 The above coating composition was applied to a base paper having a basis weight of 75 f/rrl using applicator t-2 in a coating weight of approximately 20 f/d.
One side was coated so that Immediately after that? :'1
After drying at 00°C for 1 minute at 25°C in a hot air dryer, it was calendered twice at a temperature of 50°C and a gauze pressure of 80 kglon. The obtained single-sided coated paper was subjected to contizoning for 24 hours at 20° C. and 65% R, H, and then the water resistance, formaldehyde generation amount, and ink receptivity of the coated paper were measured.

However, when measuring the amount of formaldehyde generated, the sample was immediately sealed in a polyethylene bag after hot air drying to prevent migration from other sources, and used for quantitative analysis.

The results of the measurements are shown in Table 2.

In addition, each test method is as follows.

l) Ink receptivity RI tester was turned on, the coated surface was moistened with a water supply roll, then printed and the ink receptivity was observed with the naked eye.
The following is a step-by-step evaluation of grades ranging from ~Poor.

2) Water resistance 26-1) Wet pick (Wθ-t, pick) method RI
Using a testing machine, the coated surface was moistened with a water supply roll, then printed, and the state of paper peeling was observed with the naked eye to determine "water resistance excellent 5 to poor 1".

11) Wet e-Rub (W8t rub) method: Drop approximately α1rnt of ion-exchanged water onto the coated surface and apply with your fingertips three times.
After abrasion 5 times, 10 times, 15 times and 20 times, the eluted portion corresponding to each number of times was transferred to black paper, and the amount of eluted water was observed with the naked eye. A judgment was made.

3) Print with a dry pick (Dr7 pick) R1 tester, observe the paper picking condition with the naked eye, and judge whether it is "dry, pick resistance excellent 5 to poor 1". 84) Quantification of Formaldehyde 2.59 f coated paper samples were collected and quantified according to JIS L1041-1976 liquid phase extraction method (2) Acetyl 2'7-' 2nd Seventon Method (Method A).

5] Coating liquid viscosity Using a BM type viscometer and &30 rotor, all Table Application Examples 12 to 15 and Comparative Application Feeding, δ Example 1.4
．． Comparison with 6 and 7 Various thermosetting resin aqueous solutions obtained in side numbers and 5 were used as waterproofing agents, and mixed according to the proportions shown in Table 1, and then water was added so that the concentration was 55%. Further, add 30% caustic soda to each p
Coating compositions for paper were prepared with H of 8.9 and 10.

Thereafter, the same procedure as in Application Example 1 was carried out, and a comparison was made using coating liquid 1)H.

130-

Claims (1)

[Claims] A polyamide polyamine obtained from a polyalkylene polyamine and/or a polyalkylene polyurea and a dibasic carboxylic acid is enriched with urea through a deammonification reaction, and then this is added in an aqueous solution to shrimp halohydrin and/or 1.
1. A method for producing an aqueous thermosetting resin solution, which comprises carrying out a 3-shiba o -2-foluto reaction and then reacting with formaldehyde and/or glyoxal.