JPH02102226A - Preparation of resin for paper coating and composition for paper coating - Google Patents

Abstract

PURPOSE:To prepare a resin for paper coating with excellent ink receptivity, water resistance and blister resistance by reacting a polyalkylenepolyamine, a dibasic carboxylic acid compd. and ureas together and reacting the reaction product with an epihalohydrin. CONSTITUTION:A polyalkylenepolyamine (A) (e.g., triethylenetetramine), a dibasic carboxylic acid compd. (B) and one of ureas (C) are incorporated as reactive components, where the component B contains 40mol% or more diester of a dibasic carboxylic acid (e.g., dimethyl adipate). The reaction process comprises a process wherein 1mol of component A, 0.1-2mol of component B and 0.5-5mol of component C are reacted together and another process wherein reactive groups are introduced by reacting the reaction mixture with at least one of epihalohydrins, formaldehyde and dialdehydes. A resin for paper coating with excellent ink receptivity and water resistance as well as excellent blister resistance is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a resin that improves the printing performance of coated printing paper.

[Conventional technology]

Uncoated paper such as newspaper is also used as printing paper, but coated paper is also often used to achieve beautiful printing. This coated paper is made by coating paper with a composition mainly consisting of pigments such as clay and calcium carbonate, and adhesives such as latex and starch.

By the way, in recent years, printing has become faster in order to improve productivity, and the printing image quality has also become more precise due to the demand for high-quality images such as photographs, and furthermore, the demand for color tone has also become higher. As printing paper becomes more and more multi-colored, printing coated paper is required to have increasingly higher performance. These performances include, for example, ink receptivity, which indicates the state of ink adhesion during printing, water resistance to dampening water during offset printing, and blister resistance, which is required during ink drying in rotary printing. .

In order to impart the properties necessary for such printing to coated paper, polyamide-urea-formaldehyde resin (Japanese Patent Publication No. 667 (1983)) and polyamide-urea-ebihalohydrin-formaldehyde resin (Japanese Patent Publication No. 61-42
931) is known to be used. Also,
In resins similar to these, an example is described in which a dibasic carboxylic acid diester is used as the acid component of polyamide (Japanese Patent Application Laid-open No. 152731/1983), and this is based on 20 moles of dibasic carboxylic acid. % was replaced with dibasic carboxylic acid diester.

[Problem to be solved by the invention]

However, even the resins described in the above-mentioned publications do not have sufficient performance, and there is a desire to develop a resin that has even better blister resistance.

[Means to solve the problem]

As a result of intensive studies to solve the above problems, the present inventors discovered a method for producing a paper coating resin that not only has excellent ink receptivity and water resistance, but also has excellent blister resistance. The present invention has now been completed.

That is, the present invention contains a polyalkylene polyamine, a dibasic carboxylic acid compound, and ureas as reactive components, and the dibasic carboxylic acid compound contains 40 mol% or more of a dibasic carboxylic acid diester. The above reaction components are reacted at a ratio of 0.1 to 2 moles of a dibasic carboxylic acid compound and 0.5 to 5 moles of urea per mole of polyalkylene polyamine, and further a step of reacting epihalohydrin, formaldehyde and The present invention provides a method for producing a paper coating resin, which comprises a step of introducing a reactive group by reacting with at least one type of dialdehyde.

The polyalkylene polyamine used in the present invention is preferably a compound having at least two primary amine groups and at least one 27th amino group in the molecule, and typical examples include polyethylene polyamine, Examples include polypropylene polyamine and polybutylene polyamine, among which polyethylene polyamine is preferred, and diethylene triamine, triethylene tetramine, and tetraethylene pentamine are more preferred.

Of course, these polyalkylene polyamines may be used alone or in combination of two or more types.

Further, diamines such as ethylene diamine, propylene diamine, or hexamethylene diamine, and monoamines such as dimethylamine, monoethanolamine, benzylamine, etc. are used in combination with these polyalkylene polyamines in an amount of 60 mol or less per 100 mol of the polyalkylene polyamine. You can also do that.

Further, in the present invention, dibasic carboxylic acid compounds include dibasic carboxylic acids, half esters and diesters thereof. Dibasic carboxylic acid diesters include aliphatic dibasic carboxylic acid diesters such as dimethyl succinate, dimethyl glutarate, dimethyl adipate, and diethyl adipate, and aromatic dibasic diesters such as dimethyl isophthalate and dioctyl terephthalate. Among them, esters of lower alcohols having 1 to 3 carbon atoms are particularly preferred. Of course, these may be used alone or in combination of two or more.

In addition, dibasic carboxylic acids include succinic acid, glutaric acid, adipic acid, maleic acid, isophthalic acid, phthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane-1,4-dicarboxylic acid,
Dibasic carboxylic acids such as methyltetrahydrophthalic acid and methylhexahydrophthalic acid and their anhydrides can be mentioned. Examples of half esters of dibasic carboxylic acids include the above half esters of dibasic carboxylic acids.

Furthermore, monobasic carboxylic acids such as acetic acid, stearic acid, and benzoic acid and/or esters thereof can also be used in combination.

In the present invention, the dibasic carboxylic acid diester is contained in at least 40 mol% of the dibasic carboxylic acid compounds, and the remaining 60 mol% or less is dibasic carboxylic acid half ester, dibasic carboxylic acid diester, etc. It is. When the content of the dibasic carboxylic acid diester is less than 40 mol%, the effect is not significant. Further, the -basic carboxylic acid and/or its ester may be contained in an amount of up to 50 mol % based on the dibasic carboxylic acid compound.

In the present invention, ureas include urea, 1,000 urea, guanylurea, methyl urea, dimethyl urea, etc., but urea is preferred.

The polyalkylene polyamine, dibasic carboxylic acid diester, and urea can be reacted in any order.

For example, polyalkylene polyamine and dibasic carboxylic acid diester are heated at 60 to 300°C, preferably 80 to 20°C.
A dealcoholization condensation reaction is carried out by reacting at 0°C for 1 to 10 hours. Urea can then be added and the deammonification reaction can be carried out at 90-180°C for 0.5-10 hours. Alternatively, a polyalkylene polyamine and urea are deammoniated at 90 to 180°C for 0.5 to 10 hours, and then a dibasic carboxylic acid diester is added to react the polyalkylene polyamine and urea at 60 to 300°C, preferably 80 to 200°C.
The alcohol condensation reaction can also be carried out for 1 to 10 hours at <RTIgt;C.

Moreover, the polyalkylene polyamine, dibasic carboxylic acid diester, and urea can be reacted separately. That is, for example, after a polyalkylene polyamine and urea are subjected to a deammonification reaction, a dibasic carboxylic acid diester is added to perform a dealcoholization condensation reaction, and then urea is added again to perform a deammonification reaction, or After performing a dealcoholization condensation reaction with a polyalkylene polyamine and a dibasic carboxylic acid diester, urea may be added to perform a deammonization reaction, and then a dibasic carboxylic acid diester may be added again to perform a dealcoholization condensation reaction. can.

After dissolving the polyalkylene polyamine-dibasic carboxylic acid diester-urea condensate obtained as above in water, epihalohydrin, formaldehyde, and a dialdehyde such as glyoxal or glutaraldehyde are reacted by a known method. , introduces a reactive group. Epihalohydrin, formaldehyde, and dialdehyde may be used alone (or two or more types may be used in combination). Examples of epihalohydrin include epichlorohydrin and epibromhydrin, but they cannot be used alone. In this case, the amount used is preferably 0.1 to 3 mol per mol of polyalkylene polyamine as a raw material.In addition, the amount of formaldehyde or dialdehyde used alone is 0.1 to 3 mol per mol of polyalkylene polyamine as a raw material. ) to 3 mol is preferred. Further, when two or more types are used in combination, the amount used is preferably 0.1 to 4 mol per 1 mol of polyalkylene polyamine.

Also, cationizing agents such as 3-chloro-2-hydroxypropyltrimethylammonium chloride,
Anionizing agents such as sodium sulfite can also be reacted in known manner.

The feature of the present invention is that 40 mol% of dibasic carboxylic acid diester is used instead of the conventionally used dibasic carboxylic acid.
Compared to resins obtained from dibasic carboxylic acids, the above-mentioned resins not only have excellent water resistance and ink receptivity, but also show a dramatic improvement in blister resistance in particular.

This can also be said for the resin described in JP-A-61-152731 etc. in which 20 mol% of the dibasic carboxylic acid is replaced with a monobasic carboxylic acid diester. We were able to develop a paper coating resin with outstanding performance.

Next, the present invention will be explained based on examples.

Example 1 292 g (2 mol) of triethylenetetramine and 209 g (1.2 mol) of dimethyl adipate were added to a four-bottle flask equipped with a thermometer, condenser and stirring bar, and heated at 140-160'C for 2-4 hours. A condensation reaction was carried out, and the generated methanol was removed from the system. Then add this to 12
After cooling to 0"C, 360g (6 moles) of urea was added and 1) a deammonization reaction was carried out at 0 to 140C for 1 to 4 hours. Thereafter, water was added to this to make a 50% aqueous solution. Next, 162 g (2 moles) of 37% formalin and 38 g (0.3 moles) of sodium sulfite were added, and 50%
Adjust the pH to 6 with an aqueous sulfuric acid solution and incubate at 60-80°C.
The mixture was kept under stirring for 5 hours. Further water was added to obtain a water-soluble resin with a solid content of 30%. Below, this resin aqueous solution is
-I Abbreviated as J.

Example 2 In a reaction vessel similar to Example 1, diethylenetriamine 1
03g (1 mol), triethylenetetramine 146g
(1 mol) and 60 g (1 mol) of urea were charged, and the deammonia reaction was carried out at 130 to 160° C. for 2 to 4 hours while stirring. Next, this was cooled to 100°C, 87 g (0.5 mol) of dimethyl adipate and 50 g (0.5 mol) of succinic anhydride were added, and a pressure reaction was carried out at 130 to 150°C for 2 to 4 hours. The generated methanol and water were removed from the system.

Next, after cooling this to 120°C, 238g of urea (
3.96 g) was added and 1) a deammonia reaction was performed at 0 to 140°C for 1 to 4 hours. Thereafter, water was added to this to make a 50% aqueous solution.

Next, 321 g (3.96 mol) of 37% formalin was processed, the pH was adjusted to 9 with a 30% aqueous sodium hydroxide solution, and the mixture was maintained at 60 to 80° C. with stirring for 2 to 5 hours. Further water was added to obtain a water-soluble resin with a solid content of 30%.

Hereinafter, this resin aqueous solution will be abbreviated as ri-24.

Example 3 In a reaction vessel similar to Example 1, diethylenetriamine 2
06g (2 moles) and 1252g of monoethanolamine
(0.2 mol) and further added 194 g (1 mol) of dimethyl terephthalate and heated to 130-140°C for 2-
Pressure reaction was carried out for 4 hours, and the generated methanol was removed from the system. Then, after cooling it to 120°C, urea 17
Add 6g (2,93 mol) and heat at 120-140℃ for 2~
Ammonia removal reaction was carried out for 4 hours. Thereafter, water was added to this to make a 60% aqueous solution. Next, 7 g (1.26 mol) of epichlorohydrin 1) was added and the reaction was continued at 50 to 60°C for 2 hours. Afterwards, cool to 30℃ and
Add 68g (0.84 mol) of 7% formalin, 50%
The pH was adjusted to 4 with an aqueous sulfuric acid solution, and the mixture was stirred while being maintained at 60 to 70°C for 3 hours. Furthermore, water was added to obtain a water-soluble resin with a solid content of 50%. Hereinafter, this aqueous resin solution will be abbreviated as "3".

Example 4 In a reaction vessel similar to Example 1, diethylenetriamine 1
) 3g (1,1 mol) and 160g dimethyl glutarate (
1 mol) was added thereto, pressure reaction was carried out at 130-140°C for 2-4 hours, and the generated methanol was removed from the system. Next, after cooling this to 120°C, 120g of urea
(2 mol) was added and 1) a deammoniation reaction was performed at 0 to 140°C for 1 to 4 hours. Thereafter, water was added to this to make a 50% aqueous solution. Next, 81g of 37% formalin (1
mol) and 73 g (0,5 mol) of 40% glyoxal
was added, the pH was adjusted to 8 with a 30% aqueous sodium hydroxide solution, and the mixture was maintained at 60 to 80°C with stirring for 2 to 5 hours. Further water was added to obtain a water-soluble resin with a solid content of 30%. This resin aqueous solution will be abbreviated as "i4" hereinafter.

Example 5 292 g (2 moles) of triethylenetetramine and 300 g (5 moles) of urea were placed in the same reaction vessel as in Example 1, and while stirring 1) Deammonification reaction was carried out at 0 to 130°C for 2 to 4 hours. Ta. Then dimethyl adipate 17
4 g (1 mol) was added thereto, pressure reaction was carried out at 100 to 120°C for 2 to 4 hours, and the generated methanol was removed from the system. Thereafter, water was added to this to make a 60% aqueous solution.

Next, add 93 g (1 mol) of epichlorohydrin and
After continuing the reaction at 0 to 60° C. for 2 hours, 52 g (0.5 mol) of sodium bisulfite and water were added to obtain a water-soluble resin with a solid content of 50%. Hereinafter, this resin aqueous solution will be abbreviated as ri-54.

Example 6 In a reaction vessel similar to Example 1, diethylenetriamine 1
24 g (1.2 mol) and 6 g (0.8 mol) of methylbis-(3-aminopropylamine) 1) were charged, and further 70 g (0.4 mol) of dimethyl adipate and 88 g (0.6 mol) of adipic acid were charged. 2 at 140-160℃
Pressure reaction was carried out for ~4 hours, and generated methanol and water were removed from the system. Next, after cooling this to 120°C, 192 g (3.2 mol) of urea was added, and 1) 0 to 1
Deammonification reaction was carried out at 40°C for 1 to 4 hours.

Thereafter, water was added to this to make a 60% aqueous solution.

Next, a 60% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride (trade name: Evinox 5C-60 manufactured by Dick Vercules) 63
g (0.2 mol) and maintained at 60-80'C with stirring for 1-4 hours. Plus 37% Polmarine 81
g (1 mol) was added thereto, the pH was adjusted to 4 with a 50% aqueous sulfuric acid solution, and the mixture was maintained at 60 to 80°C under stirring for 2 to 5 hours.

Further water was added to obtain a water-soluble resin with a solid content of 50%.

Hereinafter, this resin aqueous solution will be abbreviated as ri-6J.

Example 7 In a reaction vessel similar to Example 1, diethylenetriamine 2
58 g (2.5 mol) was charged, and further 155 g (0.8 mol) of dimethyl terephthalate and 25 g (0.2 mol) of tetrahydrophthalic anhydride were added to carry out a condensation reaction at 140 to 160°C for 2 to 4 hours. The generated methanol and water were removed from the system. Next, after cooling this to 120°C, 270g (4.5 mol) of urea was added and the mixture was heated to 120°C.
Deammonification reaction was carried out at 140°C for 2 to 4 hours. Thereafter, water was added to this to make a 60% aqueous solution. Next 3
81 g (1 mole) of 7% formalin and then 93 g (1 mole) of epichlorohydrin were added, the pH was adjusted to 5 with a 50% aqueous sulfuric acid solution, and the mixture was stirred while being maintained at 60 to 70° C. for 3 hours. Further water was added to obtain a water-soluble resin with a solid content of 50%. Hereinafter, this resin aqueous solution will be abbreviated as "17".

Comparative Example 1 The same reaction as in Example 1 was carried out except that 175 g (1.2 mol) of adipic acid was used instead of 209 g (1.2 mol) of dimethyl adipate, and a water-soluble resin with a solid content of 30% was used. Obtained. Hereinafter, this resin aqueous solution will be abbreviated as rr-IJ.

Comparative Example 2 The same reaction as in Example 1 except that 45.6 g (0.24 mol) of dimethyl adipate and 140 g (0.96 mol) of adipic acid were used instead of 209 g (1.2 mol) of dimethyl adipate. A water-soluble resin with a solid content of 30% was obtained. Hereinafter, this resin aqueous solution will be abbreviated as rr-2J.

Preparation of coating composition for paper and its evaluation Aqueous resin solutions obtained above (Examples 1 to 7, Comparative Example 1.
2) and a commercially available product (Evinox P-9006, manufactured by Day7 Vercules) (Comparative Example 3, abbreviated as r-3) were mixed as a printing permeability improver according to the coating liquid formulation ratio shown below. After drying, water was added to give a concentration of 60%, and the pl+ was adjusted to 9 with a 30% aqueous sodium hydroxide solution to prepare various paper coating compositions. In addition,
Paper coating composition containing no printability improver (Comparative Example 4)
, r-4) were similarly prepared.

[Ultra White 90 J 85
(clay manufactured by Engelhardt Minerals, USA) [Carbital 90J 15 parts (calcium carbonate manufactured by ECC Japan) rJS
R-0692J 10 parts (latex made by Japan Synthetic Rubber) "Eclipse MS-4600J 5
Department (Nippon Shokuhin Kako ■ Starch) [Aron T-40J O, 4
parts (dispersant manufactured by Toagosei Kagaku Kogyo ■) Printability improver 0.8 parts The above "parts" are all solid weights.

The coating composition thus obtained was applied to a base paper with a basis weight of 75 g/m using an applicator in an amount of approximately 14 coats per side.
Coating was carried out on one side and both sides so as to give a coating weight of 100 g/m. 10
Dry in a hot air dryer for 1 minute at 0°C, then reduce to temperature 6.
Calendar treatment was performed twice under the conditions of 0° C. and a linear pressure of 15 kg 7 cm. The obtained coated paper was conditioned for 24 hours at 20°C and 65% relative humidity, and then R1 printability such as ink receptivity, wet pick, dry pick, etc. was measured using single-sided coated paper. . Blister resistance was also measured using double-sided coated paper. Furthermore, the viscosity of the coating liquid was determined immediately after manufacturing and at room temperature.
Measurements were made after the sample had been allowed to stand for 4 hours. The results of these measurements are shown in Table 1. Each test method is as follows.

■ Viscosity of the coating liquid Using a B-type viscometer (model 78M, Tokyo Keiki Seisakusho Layer), the viscosity of the coating liquid was measured at 60 rpm immediately after preparation of the coating liquid and after standing at room temperature for 24 hours at 25°C. It was measured with

■ Ink receptivity Using an R1 printing tester (manufactured by Mei Seisakusho), the coated surface is moistened with a water supply roll, then printed, and the ink receptivity is observed with the naked eye, with grades ranging from Excellent 5 to Poor 1. was judged step by step.

■ Wet pick 1? Using an I printing tester, moisten the coated surface with a water roll, print, and visually observe the peeling condition.
Grades ranging from excellent 5 to poor 1 were determined in stages.

(2) Printing was carried out using a Dry Pink R1 printing tester, and the state of paper peeling was observed with the naked eye, and grades ranging from excellent 5 to poor 1 were determined in stages.

■ Blister resistance Using an RI printing tester, the ink for off-circle was printed on both sides of double-sided coated paper, and then immersed in a constant temperature bath filled with silicone oil at 30°C for 3 seconds. The state of blister formation at this time was observed with the naked eye, and grades ranging from excellent 5 to poor 1 were determined in stages.

From the above results, the Examples have good performance in all respects, and in particular, ink receptivity, wet pick resistance, and blister resistance are significantly improved.

〔Effect of the invention〕

According to the present invention, a dibasic carboxylic acid compound is used as the acid component of the polyamide, and 40 mol% or more of the dibasic carboxylic acid diester is used, so that a coating composition for paper using the resulting resin can be obtained. Coated paper exhibits excellent performance and can meet today's strict demands.

October 1, 1988

Claims (2)

[Claims] (1) Contains a polyalkylene polyamine, a dibasic carboxylic acid compound, and ureas as reactive components, and the dibasic carboxylic acid compound contains 40 mol% or more of a dibasic carboxylic acid diester, and Regarding the above reaction components, there is a step of reacting the dibasic carboxylic acid compound at a ratio of 0.1 to 2 moles and urea at a ratio of 0.5 to 5 moles per mole of polyalkylene polyamine, and a further step of reacting the dibasic carboxylic acid compound at a ratio of 0.5 to 5 moles with respect to 1 mole of polyalkylene polyamine. A method for producing a paper coating resin, comprising a step of introducing a reactive group by reacting with at least one of the resins. (2) A paper coating composition comprising a step of obtaining a paper coating resin by the method according to claim 1 and a step of obtaining a paper coating composition using this paper coating resin. Production method.