JPH032177B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for producing a paper coating resin used in a paper coating composition. (Prior Art) Conventionally, various paper coating compositions consisting of pigments, adhesives, dispersants, and other auxiliary agents have been used to improve the water resistance of paper coated with them, or to improve the ink receptivity of the paper. Melamine-
It is known to use coating compositions containing formaldehyde resins, such as formaldehyde resins, urea-formaldehyde resins or polyamide-urea-formaldehyde resins, or cationic epoxy-modified polyamide resins, such as polyamide-epihalohydrin resins. (Problem to be solved by the invention) However, in the case of the former formaldehyde-based resin, harmful formaldehyde is generated from the coated paper, and in the case of the latter resin, although no harmful components are generated, the resin itself Since it is cationic, it increases the viscosity of the coating composition, which has the drawback of significantly impairing coating workability. (Means for Solving the Problems) However, the present inventors have developed a paper coating resin that is particularly excellent in water resistance, ink receptivity, and coating workability, and does not emit bad odors such as formaldehyde than coated paper. As a result of careful consideration,
We have completed the present invention. That is, the present invention provides a reaction product obtained by reacting a polyalkylene polyamine and/or a polyalkylene polyurea with a dibasic carboxylic acid compound, and the viscosity of a 50% aqueous solution thereof is
A polyamide polyamine and/or polyurea polyamide having a particle size of 300 centipoise or less, and the following general formula [] [However, in the formula, R represents a hydrogen atom, an aliphatic group, an aromatic group, or -NR'R'' (where R' and R'' each represent a hydrogen atom, an aliphatic group, or an aromatic group). , Y represents an oxygen atom or a sulfur atom. ] The reaction product is then reacted with epihalohydrin and/or 1,3-dihalohydrin in an aqueous solution, and the pH of the resin obtained by this reaction is
The degree of cationization at 8 or more is 1.0meq/g or less, and the viscosity of a 30% by weight aqueous solution of this resin is
The present invention provides a method for producing a resin for paper coating, which is characterized in that the resin has a viscosity of 100 centipoise or less. The reaction product obtained by reacting the above polyalkylene polyamine and/or polyalkylene polyurea with a dibasic carboxylic acid compound can be obtained by reaction in the presence of an amino compound and/or a monobasic carboxylic acid compound. It is also preferable that the In carrying out the method of the present invention, first, each polyalkylene polyamine or polyalkylene polyurea used when reacting the polyalkylene polyamine and/or polyalkylene polyurea with the dibasic carboxylic acid compound. refers to a compound having at least two primary amino groups and at least one secondary amino group (imino group) in the molecule,
Each has the general formula H ₂ N−R ¹ −NH ₂ [] or the general formula H ₂ N−R ² −NHCONH−R ³ −NH ₂ [] [However, R ¹ , R ² and R ³ in the formula are respectively,
It represents a divalent aliphatic group and/or an aromatic group having at least one secondary amino group in the main chain. ] It is expressed as . In the following, these polyalkylene polyamines and polyalkylene polyureas are collectively represented by the general formula H ₂ N-X-NH ₂ [] [However, X in the formula is the above-mentioned R ¹ or R ² -
NHCONH-R ³ is represented, and R ¹ , R ² and R ₃ are each as described above. ] May also be displayed. Here, typical examples of the polyalkylene polyamine include polyethylene polyamine, polypropylene polyamine, and polybutylene polyamine, among which polyethylene polyamine is preferred, and diethylene triamine, triethylene tetramine, and tetraethylene pentaamine are particularly preferred. Min is most preferred. On the other hand, typical examples of the polyalkylene polyurea include the deammoniated reaction products of polyalkylene polyamines and urea as listed above. Of course, each of these polyalkylene polyamines or polyalkylene polyureas may be used alone or in combination of two or more types, and even if these two substances are used in combination with each other. good. Furthermore, there is nothing to prevent the use of aliphatic diamines such as ethylene diamine, propylene diamine, hexamethylene diamine, etc. in an amount of 50 mol % or less in combination with these polyalkylene polyamines and/or polyalkylene polyureas. The dibasic carboxylic acid compound described above is a general term that includes compounds having two carboxyl groups in the molecule, their esters, and even their acid anhydrides. Typical dibasic carboxylic acid compounds include succinic acid, glutamic acid, adipic acid or sebacic acid, aliphatic dibasic carboxylic acids such as maleic acid or fumaric acid, and their esters, or isophthalic acid or terephthalic acid. There are aromatic dibasic carboxylic acids such as acids and their esters, and acid anhydrides such as succinic anhydride and maleic anhydride, but these can be used alone or in combination of two or more. Of course. In addition, the above-mentioned amino compound means 1 in the molecule.
Although this refers to a compound having one primary amino group, it may also contain one or more secondary amino groups (imino groups) or tertiary amino groups. Typical such amino compounds include aliphatic amines such as laurylamine, stearylamine, monoethanolamine, diethylaminoethylamine, methylaminopropylamine or N-aminoethylpiperazine, or aliphatic amines such as benzylamine or β-phenethylamine. There are aromatic amines such as Furthermore, the above-mentioned monobasic carboxylic acid compound is a general term for compounds having one carboxyl group in the molecule and their esters, among which representative ones include formic acid, acetic acid,
Alternatively, there may be aliphatic carboxylic acids such as lauric acid and their esters, or aromatic carboxylic acids such as benzoic acid or phenethyl acid and their esters. The step of preparing the polyamide polyamine or polyurea polyamide, which can also be referred to as the first reaction in the method of the present invention, is a process in which the polyalkylene polyamine and/or polyalkylene polyurea (hereinafter, these are combined with the compound ( This is a reaction in which a dibasic carboxylic acid compound (hereinafter sometimes referred to as (b)) is dehydrated and condensed.
At this time, in the presence of an amino compound (hereinafter sometimes referred to as compound (c)) and/or a monobasic carboxylic acid compound (hereinafter sometimes referred to as compound (d)). A dehydration condensation reaction may also be carried out, which proceeds according to the following reaction formula [], [] or []. ^H _{2 N-} ^_ _{_ _} NH ₂ +HOOC− R ⁴ (b)−COOH +R ⁵ − (c) NH ₂ →(−HN−X−NHCO− R ⁴ (f)−CO)− _n NH−R ⁵ [] H ₂ N− a) -NH ₂ +HOOC- R ⁴ (b) -COOH +R ⁶ - COOH (d) → R ⁶ -CO (-HN-X- NHCO (g) -R ⁴ -CO) - _o [] [However, the formula R ⁴ and R ⁵ each represent a monovalent aliphatic group and/or an aromatic group, R ⁶ represents a hydrogen atom, a monovalent aliphatic group and/or an aromatic group, and l, m and n are both natural numbers. ] 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 compound [compound (b)]. A suitable range is 0.5 to 4.0 mol, preferably 1.0 to 3.0 mol, based on the amino compound [compound
(c)] and/or the monobasic carboxylic acid compound [compound (d)] is appropriate in the range of 0 to 1.0 mol, preferably 0.1 to 0.5 mol, per 1 mol of compound (b). be. In addition, the appropriate reaction temperature at this time is 100 to 300°C, preferably 140 to 220°C, and if the reaction is carried out for 1 to 10 hours while removing the produced water from the system, 50% of the weight The viscosity of the % aqueous solution at 25°C is 300 centipoise (cps) or less when measured with a BM type viscometer (60 rpm), preferably
A polyamide polyamine and/or polyurea polyamide, which is a product of the reaction formula [], [] and/or [], having a relatively low molecular weight of 200 cps or less is obtained. When carrying out the subsequent reaction using polyamide polyamine and/or polyurea polyamide in a high molecular weight region exceeding 300 cps, it is difficult to suppress the molecular weight range to an extent that the resulting coating solution does not increase in viscosity. Moreover, the effects of coated paper, such as ink receptivity and water resistance, cannot be achieved. In other words, when a high molecular weight substance is used, it becomes impossible to prepare a desired resin having a sufficient amount of epoxy groups, halohydrin groups, or azetidinium rings to exhibit these effects. Next, in the second step reaction in the method of the present invention, the low molecular weight polyamide polyamine and/or polyurea polyamide obtained in the so-called first step reaction (dehydration condensation reaction) as described above is (e), (f), (g) and the compound represented by the above general formula [] are deammoniated according to the reaction formula [] as described later, and through this reaction, polyamide polyamine and/or the primary and/or secondary amino groups in the polyurea polyamide that are active towards the epihalohydrin and/or 1,3-dihalohydrin to be subsequently reacted in the third stage are inert to these. Partially converted to amide bond. Among the deammoniation reactions (e), (f), and (g) above, (e)
If you display it as an example, it will look like the following. (e) of (−
NH-X-NHCO-R ⁴ -CO)- _l is X for example

Expressed by [formula], Therefore, becomes. [However, B in the formula represents a divalent aliphatic group and/or aromatic group that may or may not contain -NHC (=0)NH-, and p and q are each natural numbers, e, X, Y, R, R ⁴
is as mentioned above. ] Here, the compound represented by the above general formula [] has one or more N-unsubstituted amino groups that can undergo a deammonia reaction with a primary amino group or a secondary amino group (imino group) in the molecule. It also includes those referring to compounds that have. Typical examples include ureas such as urea, thiourea or phenyl urea, aliphatic amides such as acetamide or propionamide, or aromatic amides such as benzamide or phenyl acetate amide. The amount of the compound represented by the above general formula [] to be used is determined based on the primary amino groups and secondary 2 equivalents or less per equivalent of amine group (imino group),
A suitable range is preferably 0.2 to 1.0 equivalents.
In addition, the reaction temperature is 90-200℃, preferably 110-200℃
A temperature range of 130° C. is suitable, and the reaction may be carried out at a temperature within this range for 0.5 to 5 hours while removing the generated ammonia from the system. Thereafter, the third stage reaction in the method of the present invention is carried out, which involves dissolving the deammonification product obtained in the so-called second stage reaction, for example the substance (h) above, in water, This is then reacted with epihalohydrin and/or 1,3-dihalohydrin, and typical epihalohydrins include epichlorohydrin, epibromohydrin, etc.
On the other hand, typical 1,3-dihalohydrins include 1,3-dichloro-2-propanol,
Examples include 1,3-dibromo-2-propanol, which may be used alone or in combination. In this case, the reaction is carried out in an aqueous solution of the deammonification product at a concentration of 20 to 70% by weight, preferably 30 to 60% by weight, that is, in an aqueous solution of the deammonification product, e.g. With a pH in the range of 11,
That is, it is preferable to carry out the reaction in all the ranges of alkaline, neutral or acidic conditions, at a temperature of 20 DEG to 90 DEG C., and for a reaction time of 0.5 to 5 hours. When epichlorohydrin is used, the desired chlorohydrinated polyamide resin (i) can be obtained according to the reaction formula [] below in the case of the substance (h). [However, Y, B and R in the formula, and p,
Both q and l are as described above. ] The amount of epihalohydrin and/or 1,3-dihalohydrin used is 0.1 to 2.0 equivalents per equivalent of primary and secondary amino groups in the deammonification product (for example, the substance (h) above). The following structure is appropriate. If it is less than 0.1 equivalent, the effect will be small, and conversely, if it exceeds 2.0 equivalent, it will not be possible to obtain a resin with a degree of cationization of 1.0 meq/g or less by colloid titration at pH 8 or higher. I also don't like it. As detailed above, the method of the present invention involves combining a polyalkylene polyamine and/or a polyalkylene polyurea with a dibasic carboxylic acid compound in the absence or presence of an amino compound and/or a monobasic carboxylic acid compound. A dehydration condensation reaction is carried out with the compound to obtain the low molecular weight polyamide polyamine and/or polyurea polyamide specified as above, and then these polyamide polyamine and/or polyurea polyamide are combined with the compound represented by the above general formula []. to partially convert the active primary and secondary amino groups into inactive amide bonds, and then add epihalohydrin and/or 1,3-dihalohydrin to the deammoniated product. At the very least, the desired resin with low cationic properties and low molecular weight as specified below can be obtained.
In other words, the resin targeted by the present invention has the above-described degree of cationization of 1.0 meq/g or less, preferably
0.5meq/g or less and at 25℃
The viscosity of the 30% by weight aqueous solution, when measured with a BM type viscometer (60 rpm), needs to be 100 cps or less, preferably 50 cps or less, more preferably 30 cps or less. (Effects of the invention) The coated paper of the coating composition containing the resin obtained by the method of the present invention not only has excellent ink receptivity and water resistance, but also does not generate bad odors such as formaldehyde. In addition, the coating composition has excellent coating workability, making it extremely useful. Furthermore, since the resin used in this coating composition undergoes an ammonia removal process, the reaction temperature can be lowered, making it easier to manufacture the resin. (Examples) Next, the present invention will be explained in detail with reference to Examples, Comparative Examples, and Applied Examples. In the following, all parts and percentages are based on weight unless otherwise specified. Example 1 292 g of triethylenetetramine was added to a four-necked flask equipped with a thermometer, reflux condenser, and stir bar.
(2 mol) and 37.1 g (0.2 mol) of laurylamine
and 116.8 g (0.8 mol) of adipic acid and 19.6 g (0.2 mol) of maleic anhydride were added sequentially and a condensation reaction was carried out at 160 to 170°C for 3 hours, and the generated water was removed from the system. did. The viscosity of a 50% aqueous solution of the reaction product obtained here (at 25℃
Measured using a BM type viscometer (60 rpm) (the same applies hereafter)
was 90cps. Next, after cooling this to 120°C, 189 g (3.2 mol) of acetamide was added and a deammonia reaction was carried out at 120 to 130°C for 3 hours. Then, 380 g of water was gradually added to this, and then 296 g (3.2 mol) of epichlorohydrin was added, and the mixture was kept at 60-80°C for 2 hours with stirring.
Next, the pH was adjusted to 4.0 with a 50% aqueous sulfuric acid solution, and water was further added to obtain an aqueous resin solution with a solid content of 50%. The viscosity of a 30% aqueous solution of this is 20 cps,
The degree of cationization at pH 8 was 0.4 meq/g. Hereinafter, this resin solution will be abbreviated as "-1". Example 2 292 g (2 moles) of triethylenetetramine and 60 g (1 mole) of urea were placed in the same reaction vessel as in Example 1, and a deammonification reaction was carried out at 130 to 160°C for 3 hours with stirring. . Then this
After cooling to 100°C, 146 g (1 mol) of adivic acid was added and the condensation reaction was carried out at 160-170°C for 3 hours. The generated water was removed from the system to create a 50% aqueous solution of the reaction product. The viscosity was 70 cps. After cooling this to 120°C, a second deammonification reaction is performed using 120 g (2 moles) of urea instead of acetamide, the amount of water to be added is 350 g, and The same operation as in Example 1 was repeated except that the amount of epichlorohydrin used was 185 g (2 moles), and 30
An aqueous resin solution having a solid content of 50% and a viscosity of 10 cps and a degree of cationization at pH 8 of 0.4 meq/g was obtained. Hereinafter, this resin solution will be abbreviated as "-2". Example 3 Into the same container as in Example 1, 155 g (1.5 mol) of diethylene triamine was charged, and 100 g (1 mol) of succinic anhydride was added, and a condensation reaction was carried out at 160 to 170°C for 3 hours. When water was removed from the system, a reaction product with a 50% aqueous solution viscosity of 140 cps was obtained. Next, this was cooled to 120°C, 95.2g (1.25 mol) of thiourea was added thereto, and ammonia removal reaction was carried out at 120-130°C for 3 hours, and then 210g of water was gradually added. From now on, the amount of epichlorohydrin used is 116g (1.25mol).
The same operation as in Example 1 was repeated except that the viscosity of the 30% aqueous solution was 8 cps, and the pH was
An aqueous resin solution with a solid content of 50% and a cationization degree of 0.5 meq/g in Example 8 was obtained. Hereinafter, this resin solution will be abbreviated as "-3". Example 4 In a container similar to Example 1, 103 g (1 mol) of diethylenetriamine and 146 g of triethylenetetramine were added.
(1 mol) and 60 g (1 mol) of urea were charged, and the deammonia reaction was carried out at 130 to 160° C. for 3 hours with stirring. Next, after cooling this to 100°C, 73 g (0.5 mol) of adipic acid and 61.1 g (0.5 mol) of benzoic acid were added.
A condensation reaction was carried out at 160-170° C. for 3 hours, and the generated water was removed from the system. The resulting reaction product had a viscosity of 50 cps as a 50% aqueous solution. Then, after cooling to 120℃, add 72g of urea.
(1.2 mol) was added and deammoniated reaction was carried out at 120-130°C for 3 hours, and 290 g of water was gradually added.
Next, 166.5 g (1.8 moles) of epichlorohydrin
After stirring was continued at 60 to 80°C for 2 hours, the pH was adjusted to 4.5 with concentrated sulfuric acid, and water was further added to obtain an aqueous resin solution with a solid content of 50%. The viscosity of a 30% aqueous solution of this product was 8 cps, and the degree of cationization at pH 8 was 0.3 meq/g. Hereinafter, this resin solution will be abbreviated as "-4". Comparative Example 1 In a container similar to Example 1, 92.9 (0.9 mol) of diethylenetriamine was charged, and adipic acid was added.
After adding 146 g (1 mol) and causing a condensation reaction at 160 to 170°C for 3 hours, the generated water was removed from the system.
A reaction product with a viscosity of 550 cps as a 50% aqueous solution was obtained. Next, this was cooled to 120°C, 30g (0.5 mol) of urea was added, and ammonia removal reaction was carried out at 120-130°C for 3 hours, then 160g of water was gradually added, and 46.3g of epichlorohydrin was added.
(When 0.5 mol was added and stirred at 60 to 80°C, gelation occurred in 0.5 hours.) Comparative Example 2 Same as Example 2 except that the second deammonization reaction was completely absent. After repeating the operation, 30
An aqueous resin solution with a solid content of 50% and a viscosity of 10 cps and a degree of cationization at pH 8 of 1.5 meq/g was obtained. Below, this resin solution is
(1)". Comparative Example 3 The same operation as in Example 2 was repeated except that the amount of epichlorohydrin used was changed to 41.3 g (3.5 mol), and the viscosity of a 30% aqueous solution was 8 cps.
The degree of cationization at PH8 is 1.2meq/g.
An aqueous resin solution with a solid content of 50% was obtained. Hereinafter, this resin solution will be abbreviated as "-(2)". Comparative Example 4 The same operation as in Comparative Example 1 was repeated except that the amount of diethylenetriamine used was changed to 103 g (1 mol), and the viscosity of the 50% aqueous solution of the first stage condensation reaction product was 450 cps. The resin obtained after reacting with epichlorohydrin had a viscosity of 30% aqueous solution.
250cps and cationization degree at PH8
It was an aqueous solution with a solid content of 0.5 meq/g and a solid content of 50%.
Hereinafter, this resin solution will be abbreviated as "-(3)". Application Examples 1 to 4 and Comparative Application Examples 1 to 5 Each resin aqueous solution obtained in Examples 1 to 4 and Comparative Examples 2 to 4 and two commercially available paper coating resins (formaldehyde resin aqueous solution) were combined. After each coating liquid was mixed as a printability improver according to the proportions shown below, water was added to make the concentration 55%, and the pH was further adjusted to 9 with a 30% caustic soda aqueous solution. Various paper coating compositions were prepared. "Ultra White 90" 85 parts (clay manufactured by Engelhard Minerals, USA) "Shiraika PX" 15 parts (calcium carbonate manufactured by Shiroishi Kogyo Co., Ltd.) "JSR-0616" 12 parts (latex manufactured by Japan Synthetic Rubber Co., Ltd.) "Aron T-40" 0.4 parts (Dispersant manufactured by Toagosei Chemical Industry Co., Ltd.) Solar Eclipse MS-4600 6 parts (Starch manufactured by Nippon Shokuhin Kako Co., Ltd.) Printability improver 0.5 parts The "part" above is All are solid weights. The above coating composition was coated on one side of a base paper having a basis weight of 75 g/m ² using an applicator so that the coating amount was approximately 20 g/m ² . then immediately 100
Dry in a hot air dryer for 1 minute at
Calendar treatment was performed twice at 50°C and a linear pressure of 80 kg/cm. The resulting single-sided coated paper was heated at 20°C and 65% R.
After conditioning the coated paper for 24 hours under the following conditions, 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 and subjected to quantitative analysis. The measurement results are shown in Table 1. In addition, each test method is as follows. (1) Ink receptivity Using an RI tester, the coated surface was moistened with a water roll, printed, and the ink receptivity was observed with the naked eye to determine the grades ranging from excellent 5 to poor 1. (2) Water resistance (i) Wet pick method Using an RI tester, the coated surface is moistened with a water supply roll, printed, and the state of peeling is observed with the naked eye. The score was rated as 5 to poor 1. (ii) Wet rub method Drop approximately 0.1ml of ion-exchanged water onto the coated surface and rub it with your fingertips 3, 5, 10, 15 and 20 times, depending on the number of times. Transfer the eluted portion to black paper and observe the amount eluted with the naked eye.
The water resistance was evaluated as "Excellent 5 to Poor 1". (3) Dry pick The paper was printed using the RI test, and the paper peeling condition was observed with the naked eye, and a judgment was made of "dry pick resistance excellent 5 to poor 1". (4) Quantification of formaldehyde Coated paper sample 2.5 times according to JIS L1041-1976 liquid phase extraction method (2) acetylacetone method (method A)
g was collected and quantified. (5) Viscosity of coating liquids The viscosity of all coating liquids was measured at 25°C using a No. 3 rotor at 60 rpm using a BM type viscometer.

【table】

Claims (1)

[Scope of Claims] 1. A reaction product obtained by reacting a polyalkylene polyamine and/or polyalkylene polyurea with a dibasic carboxylic acid compound, wherein the viscosity of a 50% aqueous solution thereof is 300 centipoise or less. A certain polyamide polyamine and/or polyurea polyamide and the following general formula [] [However, in the formula, R represents a hydrogen atom, an aliphatic group, an aromatic group, or -NR'R'' (where R' and R'' each represent a hydrogen atom, an aliphatic group, or an aromatic group). , Y represents an oxygen atom or a sulfur atom. ] The reaction product is then reacted with epihalohydrin and/or 1,3-dihalohydrin in an aqueous solution, and the pH of the resin obtained by this reaction is
The degree of cationization at 8 or more is 1.0meq/g or less, and the viscosity of a 30% by weight aqueous solution of this resin is
A method for producing a resin for paper coating, characterized in that the resin is 100 centipoise or less. 2. The reaction product obtained by reacting a polyalkylene polyamine and/or polyalkylene polyurea with a dibasic carboxylic acid compound is reacted in the presence of an amino compound and/or a monobasic carboxylic acid compound. A method for producing a paper coating resin according to claim 1, wherein the paper coating resin is obtained. 3. The method for producing a paper coating resin according to claim 1 or 2, wherein the compound of general formula [] is urea. 4. The method for producing a paper coating resin according to claim 1 or 2, wherein the compound of general formula [] is thiourea. 5. Claim 1 or 2, characterized in that the compound of general formula [] is acetamide.
A method for producing a paper coating resin as described in Section 1.