JPH0735428B2 - Resin manufacturing method - Google Patents

Description

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

<Prior Art> Conventionally, for the purpose of imparting water resistance to various paper coating compositions comprising a pigment, an adhesive, a dispersant and other auxiliary agents, or for the purpose of improving ink acceptability, It is known to use resins such as melamine-formaldehyde resin, urea-formaldehyde resin or polyamide polyurea-formaldehyde resin, polyamide polyurea-formaldehyde-epihalohydrin resin (eg JP-B-44-11667, JP-B-59-32597). , JP-A-58-4
0322).

<Problems to be Solved by the Invention> However, in the former formaldehyde-based resin, harmful formaldehyde is generated from the coated paper, and in the latter resin, harmful components are less generated, but in recent years, As the demands for ink receptivity and water resistance of craft paper have become more sophisticated, it has become impossible to meet those demands. Therefore, the present invention provides a method for producing a resin useful as a resin for paper coating which exhibits unprecedented excellent water resistance and ink acceptability.

<Means for Solving the Problem> The inventors of the present invention aim to obtain a resin for paper coating which is particularly excellent in water resistance effect and ink acceptability, and does not have or has a bad odor such as formaldehyde from coated paper. As a result of intensive studies, the present invention has been completed.

That is, the present invention provides: (a) polyalkylene polyamine (b) alicyclic dibasic carboxylic acid and / or reaction product having a free carboxyl group obtained by reaction of alicyclic dibasic carboxylic acid and glycols ( (c) Ureas (d) Alkylating agent and, if desired, (e) Formaldehyde and / or glyoxal are reacted to provide a process for producing a resin useful as a resin for paper coating.

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, 4,7
-Diazadecane-1,10-diamine and the like. These polyalkylene polyamines can be used not only as one kind but also as a mixture of two or more kinds. Also, aliphatic diamines such as ethylenediamine and propylenediamine,
It does not hinder the combined use with the above polyalkylene polyamine insofar as the object of the present invention is not impaired.

The component (b) alicyclic dibasic carboxylic acid used in the present invention includes compounds having two carboxyl groups in the molecule, esters thereof, and acid anhydrides thereof. The representative ones of such alicyclic dibasic carboxylic acids are as follows.

Carboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane-1,4-dicarboxylic acid, 4-methyltetrahydrophthalic acid and their esters, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4- Methyl tetrahydrophthalic anhydride,
Acid anhydrides such as 4-methylhexahydrophthalic anhydride, Δ ⁴ -tetrahydrophthalic anhydride and 4-methyl Δ ⁴ -tetrahydrophthalic anhydride.

These may be only one kind or a combination of two or more kinds,
Further, together with 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, to the extent that the effects of the present invention are not impaired. An acid may be used in combination.

The glycols used in the present invention include alkylene glycols such as ethylene glycol, propylene glycol and butanediol, cycloalkylene glycols such as cyclopentanediol and cyclohexanediol, alkenylene glycols such as butenediol and octenediol. , Polyethylene glycols such as diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, and polytetramethylene glycol, ethylene oxide adducts of bisphenol A, ethylene oxide adducts of hydrogenated bisphenol A, and the like.

Further, as the reaction product having a free carboxyl group obtained by the reaction of the alicyclic dibasic carboxylic acid of component (b) and the glycol, the alicyclic dibasic carboxylic acid and the glycol are 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 the alicyclic dibasic carboxylic acid and glycols is usually carried out in the presence or absence of a catalyst.
It is carried out by heating at ~ 200 ° C for 30 minutes to 2 hours.

The (c) ureas include urea, thiourea, guanylurea, methylurea, dimethylurea, etc., but urea is preferable from the industrial viewpoint.

The following various compounds can be used as the alkylating agent of the component (d).

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

(2) General formula (R ₂ O) ₂ SO _v (wherein R ₂ is a lower alkyl group, v
Indicates 1 or 2. ) Dialkyl sulphate and dialkyl sulphate represented by Preferred examples include dimethyl sulphate, diethyl sulphate, dimethyl sulphate, diethyl sulphate and the like.

(3) General formula [In the formula, R ₃ represents a hydrogen atom, a lower alkyl group, a hydroxyalkyl group or a phenyl group. ] The ethylene oxide derivative represented by these. Preferred examples include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, glycidol and the like.

(4) General formula [In formula, X shows a halogen atom and w shows 1, 2 or 3. ] Epihalohydrin represented by. Preferred examples include epichlorohydrin and epipromohydrin.

(5) A monohalohydrin represented by the general formula HOCH ₂ (CH ₂ ) _w X (wherein X and w are the same as above). Preferred examples include ethylene chlorohydrin and ethylene bromohydrin.

(6) General formula [Wherein X is the same as above, Y is a halogen atom or an OH group, and Z is an OH group when Y is a halogen atom, and Y is an OH group.
When it is a group, it represents a halogen atom. ] A dihalohydrin represented by. 1,3-
Dichloro-2-propanol, 2,3-dichloro-1-propanol and the like can be mentioned. Among the above, epichlorohydrin is particularly preferable.

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 the viscosity of an aqueous solution having a resin solid content of 50% by weight is usually 5 to 1000 centipoise (hereinafter abbreviated as cp) at 25 ° C. Those with a very low viscosity tend to have a low effect of adding the resin as a paper coating composition, and those with a high viscosity generally increase the viscosity of the prepared paper coating composition. There are some drawbacks, so it is practically 10 to 500 cp, particularly preferably 20 to 2 cp.
Those in the viscosity range of 00 cp are preferably used.

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

First of all, the components (a) and (b) can be reacted and then the component (c) can be reacted. Components (a) and (b)
At a temperature of 120 to 250 ° C, preferably 130 to 200 ° C,
It is carried out in 2 to 12 hours while removing the produced water out of the system. The carboxyl group in the component (b) is reacted in a ratio of 0.4 to 4 equivalents, preferably 0.8 to 3 equivalents, relative to 1 mol of the polyalkylene polyamine of the component (a). The reaction between the dehydration condensation reaction product thus obtained and the urea of the component (c) is carried out at a temperature of 100 to 180 ° C, preferably 110 to 160 ° C.
Then, it is carried out for 1 to 6 hours while removing the generated ammonia out of the system. The amount of the component (c) used is 1 with respect to 1 equivalent of the amino group in the component (a), that is, the primary and secondary amino groups.
It is an equivalent or less, preferably 0.1 to 0.8 equivalent.

Alternatively, first react components (a) and (c),
Then, the component (b) can be reacted, and further the component (c) can be reacted. Component (c) is used in an amount of 0.2 to 1 mol, preferably 0.3 to 0.8 mol, per 1 mol of component (a), at a temperature of 100 to 180 ° C., preferably 110 to 160 ° C.
Deammonification reaction is carried out for an hour. The reaction of the reaction product thus obtained with the component (b) is carried out at a temperature of 120 to 250 ° C.
It is preferably carried out at 130 to 200 ° C. for 2 to 12 hours while removing generated water out of the system. The component (b) is the component (a)
It is used in the range of 0.2 to 2 equivalents, preferably 0.3 to 1.8 equivalents, per mol. The step of reacting the reaction products of the components (a), (b) and (c) thus obtained with the component (c) again is carried out at a temperature of 100 to 180 ° C, preferably 110 to 160 ° C. It is performed for 1 to 6 hours. The amount of the component (c) used is 2 with respect to 1 equivalent of the secondary amino group in the component (a).
The amount is not more than the equivalent, preferably in the range of 0.1 to 1.5 equivalents.

As another method, the components (a), (b) and (c) are simultaneously reacted, and the resulting reaction product is further supplemented with the component (c).
Can also be reacted. First component (a), (b)
The reaction of (c) is carried out at a temperature of 100 to 200 ° C., preferably 110
It is carried out at ˜180 ° C. for 2 to 12 hours while removing generated ammonia and water out of the system. The proportion of each component used in this step is 0.2 to 2 equivalents, preferably 0.3 to 1.8 equivalents of the carboxyl group of component (b), 0.2 to 1 mol of component (c), and preferably 1 to 1 mol of component (a). 0.3 to 0.8 mol is suitable. The step of further reacting the component (c) with the reaction product thus obtained is carried out at a temperature of 100 to 180 ° C., preferably 110 to 160 ° C. for 1 to 6 hours. The amount of the component (c) used is 2 equivalents or less, preferably 0.1 to 1.5 equivalents, relative to the equivalent of the secondary amino group of the component (a).

Components (a) and (b) obtained by various methods as described above
And the reaction products of (c) are both dissolved in water, then the alkylating agent of (d) and, if desired, (e)
React with formaldehyde and / or glyoxal. The reaction with the alkylating agent is carried out in an aqueous solution having a concentration of 20 to 80% by weight, preferably 30 to 70% by weight, at a pH of 3 to 12, at a reaction temperature of 20 to 80 ° C. for 1 to 10 hours. The amount of the alkylating agent used is appropriately 2 equivalents or less, preferably 0.1 to 1.5 equivalents, relative to 1 equivalent of the secondary amino group in the component (a).

In the present invention, component (e) can be reacted, if desired. The reaction order of the reaction products of the components (a), (b) and (c) with the components (d) and (e) is arbitrary,
The object of the present invention can be achieved by any method of the reaction of (d), the reaction of (e), the reaction of (e), the reaction of (d), and the simultaneous reaction of (d) and (e). The reaction of component (e) has a concentration of 20
It 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 amount of (e) used is 1 mol or less, preferably 0.1 mol, relative to 1 mol of (c).
~ 0.8 mol is suitable. The reaction pH is pH 5 to 8 when glyoxal is used, and pH 3 when formaldehyde is used.
~ 7 are preferred. After the completion of the reaction, if necessary, the target compound of the present invention is obtained by adjusting the pH to 4 to 8 with an alkali such as caustic soda and caustic potash, or an acid such as hydrochloric acid, sulfuric acid and formic acid.

As explained in detail above, the method of the present invention is obtained by (a) polyalkylene polyamine (b) reaction of alicyclic dibasic carboxylic acid and / or alicyclic dibasic carboxylic acid with glycols. A reaction product having a free carboxyl group (c) ureas (d) an alkylating agent and, if desired, (e) formaldehyde and / or glyoxal. When used as, excellent ink acceptability,
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 the conventionally used aliphatic or aromatic dibasic carboxylic acid is used. Compared to paper coating resins obtained from carboxylic acids,
The resin obtained according to the present invention is remarkably improved in performance.

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

<Example> Example-1 Triethylenetetramine 58.5 parts (0.4 mol) and urea 1 were placed in a four-necked flask equipped with a thermometer, a reflux condenser and a stirring rod.
2.0 parts (0.2 mol) was charged and heated at an internal temperature of 120 to 140 ° C. for 3 hours to carry out a deammonification reaction. After that, 34.4 parts (0.2 mol) of hexahydrophthalic acid was charged and the internal temperature was 150 to 160 ° C.
The dehydration amidation reaction was carried out for 5 hours. Then the internal temperature
Cool to 130 ° C and charge 48.0 parts (0.8 mol) of urea at a temperature of 12
The deammonification reaction was performed at 0 to 130 ° C. for 2 hours. Then 10
It was cooled to 0 ° 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. Then cool to 25 ℃,
Adjust the pH to 7 with 35% hydrochloric acid and add water to obtain a concentration of 50%,
A resin liquid having a viscosity of 52 cp (25 ° C.) was obtained. This is referred to as resin liquid A.

Example-2 Triethylenetetramine 29.2 in a container similar to Example-1
Part (0.2 mol) was charged, and 30.8 parts (0.2 mol) of hexahydrophthalic anhydride was added thereto, and the temperature was raised to 150-155.
Dehydration amidation was performed at ° C. Then cool to 130 ° C,
Charge 12 parts (0.2 mol) of urea and hold at 125-130 ℃ for 2 hours.
A deammonification reaction was performed. Then, this was cooled to 60 ° C., and water was added to dilute it to obtain a 50% aqueous solution. Next, 18.5 parts (0.2 mol) of epichlorohydrin and 15.4 parts of diethylsulfate
Parts (0.1 mol) were charged and the reaction was carried out at 60 ° C. for 7 hours. Then, it was cooled to 25 ° C., pH was adjusted to 6 with 20% sulfuric acid, and water was added to obtain a resin liquid having a concentration of 50% and a viscosity of 63 cp (25 ° C.).
This is referred to as resin liquid B.

Example-3 Triethylenetetramine 58.5 was placed in a container similar to Example-1.
Parts (0.4 mol) and tetrahydrophthalic anhydride 30.4
Parts (0.2 mol) and 12 parts (0.2 mol) of urea were charged at the same time, and the temperature was raised to perform dehydration amidation and deammonification reaction at 150 to 155 ° C. for 5 hours at the same time. Then, the mixture was cooled to 130 ° C., 12 parts (0.2 mol) of urea was further charged, and a deammonification reaction was carried out at 125 to 130 ° C. for 2 hours. Dilute by adding water to this
It was a 50% aqueous solution.

Next, 23.2 parts (0.4 mol) of propylene oxide was charged and the reaction was carried out at 25 ° C for 6 hours. Then, add 9.3 parts (0.1 mol) of epichlorohydrin, react at 60 ° C for 3 hours, cool to 30 ° C, adjust the pH to 6 with 35% hydrochloric acid, add water to give a concentration of 50% and a viscosity of 55cp. A resin liquid of (25 ° C) was obtained. This is referred to as a resin liquid C.

Example-4 Triethylenetetramine 58.5 in a container similar to Example-1
14 parts (0.4 mol) and 12 parts of urea (0.2 mol) were charged, 145-1
The deammonification reaction was carried out at 50 ° C. for 4 hours. In another container, mix 60.8 parts (0.4 mol) of tetrahydrophthalic anhydride and 15.2 parts (0.2 mol) of propylene glycol,
Polyester was obtained by heating at 150 ° C. for 2 hours. The entire amount of this polyester was charged into a container in which the above deammonification reaction had been completed, and the internal temperature was heated at 150 to 155 ° C. for 4 hours for dehydration and deammonification reaction. Then cool to 130 ° C and add urea 1
2 parts (0.2 mol) was added and a deammonification reaction was carried out at 125 to 130 ° C. for 2 hours. Then, water was added to make a 50% aqueous solution.

Next, charge 18.5 parts (0.2 mol) of epichlorohydrin 6
After reacting at 5 ℃ for 2 hours, 37% formalin 8.1 parts (0.1
Mol) was added and the pH was adjusted to 5 with 70% sulfuric acid, and the mixture was reacted at 65 ° C. for 4 hours. Then cool to 25 ° C, adjust the pH to 7 with 28% caustic soda solution, and adjust the concentration to 50% and the viscosity to 48cp (25
To obtain a resin liquid (° C.). This is referred to as resin liquid D.

Example-5 In the same container as in Example-1, 12.4 parts (0.2 mol) of ethylene glycol and 60.8 parts (0.4 mol) of tetrahydrophthalic anhydride were used.
Mol) was charged and heated at 140 ° C. for 2 hours to obtain a reaction product having a free carboxyl group. To this was further charged 12.0 parts (0.2 mol) of urea, and 58.5 parts (0.4 mol) of triethylenetetramine was added with stirring at 110 to 120 ° C.

This was subjected to deammonification reaction and dehydration amidation reaction at 150 ° C. for 5 hours. This is cooled to 130 ° C and urea 12.0 is added.
Part (0.2 mol) was added, and a deammonification reaction was performed at a temperature of 120 to 130 ° C. for 2 hours. Then, it was cooled to 100 ° C., and water was added to make a 50% aqueous solution. Then, 77 parts of diethyl sulfate (0.5
(Mol) and charged at 60 ° C. for 4 hours. Then 25 ° C
After cooling to pH 7, the pH was adjusted to 7 with 20% sulfuric acid, and water was added to obtain a resin liquid having a concentration of 50% and a viscosity of 43 cp (25 ° C). This is referred to as a resin liquid E.

Example-6 In Example-4, 14.5 parts (0.1 mol) of 40% glyoxal was used instead of 8.1 parts of 37% formalin.
% Sulfuric acid, the pH was adjusted to 6, and the reaction was carried out at 55 ° C. for 4 hours.
%, A resin solution having a viscosity of 51 cp (25 ° C.) was obtained. This is resin liquid F
Called.

Comparative Example-1 According to Example-1, 29.6 parts (0.2 mol) of phthalic anhydride was used instead of hexahydrophthalic anhydride of Example-1.
All were synthesized under the same conditions and under the same conditions except that was used to finally obtain a resin liquid having a concentration of 50% and a viscosity of 49 cp (25 ° C.). This is referred to as a resin liquid G.

Comparative Example-2 According to Example-1, except that 29.2 parts (0.2 mol) of adipic acid was used instead of hexahydrophthalic anhydride of Example-1, the same raw materials were synthesized under the same conditions, Finally, a resin liquid having a concentration of 50% and a viscosity of 58 cp (25 ° C) was obtained. This is called a resin liquid H.

Comparative Example-3 According to Example-5, first, 58.5 parts (0.4 mol) of adipic acid.
And ethylene glycol 12.4 parts (0.2 mol) to 160-18
It was heated at 0 ° C. for 3 hours to be dehydrated and esterified to obtain a polyester having a carboxyl group at the terminal. To this was further added 12.0 parts (0.2 mol) of urea, and 58.5 parts (0.4 mol) of triethylenetetramine was added with stirring at 110 to 120 ° C.
This was subjected to deammonification and dehydration amidation reaction at 150 ° C. for 5 hours. This was cooled to 130 ° C and 12.0 parts of urea (0.2
Mol) was added and the deammonification reaction was carried out at a temperature of 120 to 130 ° C. for 2 hours. Then, water was added to make a 50% aqueous solution. Then, 77 parts (0.5 mol) of diethyl sulfuric acid was charged and reacted at 60 ° C. for 4 hours.

Thereafter, the mixture was cooled to 25 ° C., pH was adjusted to 7 with 20% sulfuric acid, and water was added to obtain a resin liquid having a concentration of 50% and a viscosity of 57 cp (25 ° C.). This is referred to as resin liquid I.

Application Example Using the resin aqueous solutions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 and Sumirez Resin 613 (a melamine / formaldehyde resin manufactured by Sumitomo Chemical Co., Ltd.), papers having the formulations shown in Table 1 were used. A coating composition for use was prepared.

The prepared coating composition for paper has a total solid content of 60% and a pH of about 8.
After adjusting with water and 10% caustic soda aqueous solution to 5 respectively, it was applied on one side of a high quality paper with a basis weight of 80 g / m ² using a wire rod so that the coating amount was 14 g / m ² . . Immediately after coating, dry with hot air at 120 ° C for 30 seconds, then 20
After humidity control at 65 ° C and 65% RH for 16 hours, temperature 60 ° C, linear pressure 60kg
Supercalendering was performed twice under the condition of / cm to obtain a coated paper. The coated paper thus obtained was tested for water resistance, ink acceptability, and formaldehyde determination. The test results are shown in Table 2 as Examples 1 to 6 and Comparative Examples 1 to 4.

The test method is as follows.

○ Water resistance (a) Wet rub method Approximately 0.1 ml of ion-exchanged water was dropped on the coated surface, and the water was applied with a fingertip.
After rubbing once, the elution amount was transferred to black paper, and the elution amount was visually evaluated.

The criteria for judgment were as follows.

Water resistance (poor) 1 to 5 (excellent) (b) Wet topic method Using a RI tester, wet the coated surface with a water supply roll and then print, and observe the peeled state with the naked eye to check the water resistance (poor). ) 1
A judgment of ~ 5 (excellent) was made.

○ Ink acceptability (a) Method A A RI tester (Mitsu Seisakusho) was used to wet the coated surface with a water supply roll, and then printing was performed to observe the acceptability of the ink.

The ink acceptability (poor) is 1 to 5 (excellent).

(B) Method B Using an RI tester, printing was performed while kneading water into the ink, and the ink acceptability was observed.

The ink acceptability (poor) is 1 to 5 (excellent).

○ Quantification of formaldehyde Coated paper sample according to JIS-L1041-1976 Liquid phase extraction method (2) Acetylacetone method (A method)
2.5 g was sampled and quantified.

Claims (2)

[Claims] 1. A reaction product having a free carboxyl group obtained by the reaction of (a) polyalkylene polyamine, (b) alicyclic dibasic carboxylic acid and / or alicyclic dibasic carboxylic acid and glycols. A method for producing a resin for paper coating, which comprises reacting a resin, (c) urea, and (d) alkylating agent. 2. A reaction product having a free carboxyl group obtained by the reaction of (a) a polyalkylene polyamine, (b) an alicyclic dibasic carboxylic acid and / or an alicyclic dibasic carboxylic acid and a glycol. And (e) formaldehyde and / or glyoxal. (C) ureas, (d) alkylating agent, and (e) formaldehyde and / or glyoxal.