JPS6155286A - Paper coating composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a paper coating composition that provides coated paper with excellent printability and printing effects.

Even more like a teacher? The present invention relates to a paper coating composition that provides coated paper with excellent ink receptivity, water resistance, and blister resistance, and does not generate formaldehyde odor.

Coated paper, which is obtained by applying a paper coating composition consisting mainly of pigments and an aqueous binder to paper and performing necessary processes such as drying and calendering, is popular for commercial printing due to its excellent printing effects. Coated paper is widely used in magazines, books, etc., but as quality requirements become more sophisticated and printing speeds increase, efforts are being made to improve the quality of coated paper. Particularly in offset printing, which accounts for the majority of printing, improvements and improvements in ink receptivity under the influence of dampening water, water resistance in wet picks and wet rubs, and blister resistance in rotary printing are important issues in the industry. This is a challenge.

Conventionally, for this purpose, efforts have been made to improve the quality of coated paper by adding various water-resistant agents to coating compositions for waste paper that mainly consist of pigments and water-based binders. Although all of the water-resisting agents and the like have effective properties, they have serious drawbacks and are therefore unsatisfactory in practice.

For example, melamine-formaldehyde tree jl? Aminoplast resins such as urea-formaldehyde resins not only generate a lot of formaldehyde during operation and from coated paper, but also have little effect on improving ink receptivity or blister resistance, and also have no water resistance effect when coated. As the pH of the composition increases, it becomes extremely difficult to obtain. 7 Dialdehydes such as glyoxal cause coloring of coated paper and cannot improve ink receptivity or blister resistance.

Polyvalent metal salts such as zirconium do not have the effect of improving ink receptivity or blister resistance.

Under these circumstances, polyamide polyurea is an effective agent for improving and improving ink receptivity, water resistance, and blister resistance.
Currently, formaldehyde is widely used. However, the efficacy of polyamide polyurea-formaldehyde resin also decreases when the pH of the coating composition is high.
In particular, ink receptivity and water resistance are significantly reduced.

For these reasons, high PH coating compositions have good ink receptivity.
A drug that significantly improves and improves water resistance and blister resistance has not yet been found.

The present inventors have made extensive studies in view of the current situation, and have developed a paper coating composition mainly consisting of a pigment and an aqueous binder.
The inventors have discovered that the above object can be achieved by using as an additive a reaction product of polyalkylene poly(amino) or alkylene diamine and epichlorohydrin having a specific aqueous solution viscosity and a specific cation equivalent weight, and have completed the present invention. .

That is, the present invention is a reaction product of (a) a pigment, fb) an aqueous binder, and (c) a polyalkylene polyamine or/and an alkylene diamine and an epihalohydrin, and the viscosity of a 50% by weight aqueous solution of the reaction product at 25°C is 10 to 500 centipoise, and the pH is 91.
The cation equivalent in the solution is 0.5 m-eq / /!
5m-ec1/I or less, and has a pH of 1o or more.

Examples of the polyalkylene polyamine in the present invention include diethylenetriamine, triethylenetetramine,
Examples include detraethylenepentamine, pentaethylenehexamine, heptaethyleneoctamine, nonaneethylenedecamine, triethylenebis(trimethylene)hexamine, aminoethylpiperazine, iminobispropy, and luamine. In addition, alkylene diamines include ethylene diamine, 1,3 diaminopropane, propylene diamine, piperazine, dimethylaminopropylamine, menthanediamine, triethylene diamine, hexamethylene diamine, N, N, N', N'-tetramethylethylene diamine, N, N, *, r/〒tetramethyl-
Examples include 41,3-butanediamine. - These polyalkylene polyamines and alkylene diamines may be used alone or in combination of two or more. Furthermore, monoamines such as diethylamine and dipropylamine may also be mixed and used for the purpose of controlling or modifying the molecular weight.

Examples of epihalohydrin include epichlorohydrin, shrimp bromohydrin, and methylepichlorohydrin. The reaction product of polyalkylene polyamine or/and alkylene diamine and epihalohydrin is prepared by reacting polyalkylene polyamine or/and alkylene diamine and epihalohydrin at a temperature of 20 to 80°C for 30 minutes to 10 minutes.
By reacting for about an hour, the solid content concentration is usually 20%.
Obtained as a ~80% by weight aqueous solution.

The reaction product of the polyalkylene polyamine or alkylene diamine of the present invention and epihalohydrin has a viscosity of 10 centipoise or more and 500 centipoise or less at 25°C when the solid content concentration of the aqueous solution is 50% by weight, and a pH of 500 centipoise or less.
The cation equivalent in 9 exceeds 0.5 m-eq/f and 5
It is necessary that it is below m-eq/f. If the viscosity of the reaction product is less than 10 centipoise, the effects of the present invention cannot be obtained. If the viscosity exceeds SOO centipoise, it becomes difficult to prepare the coating composition. Further, if the cation equivalent weight of the reaction product is less than 0.5 m-eq/f, it is difficult to obtain the effects of the present invention, and if it exceeds 5 m-eq/f, it becomes difficult to prepare a coating composition.

It is necessary that the pH of the paper coating composition of the present invention is 10 or more; however, if the pH is less than 10, it is difficult to prepare the coating composition.

The pigments used in the present invention include white amorphous pigments such as kaolin, talc calcium carbonate, aluminum hydroxide, satin white, and titanium oxide, and organic synthetic pigments such as polystyrene, melamine-formaldehyde resin, urea-formaldehyde resin, etc., singly or in combination. The above can be mixed and used.

Further, the water-based binder in the present invention includes water-soluble binders such as oxidized starch, phosphoric acid esterified starch, polyvinyl alcohol, casein, gelatin 1, carboxymethyl cellulose, styrene-butadiene resin, vinyl acetate Hl! , ethylene-vinyl acetate resin, methyl methacrylate resin, etc. may be used alone or in combination of two or more.

The paper coating composition of the present invention may contain other components, colorants, etc. as required.

The paper coating composition of the present invention is applied onto a paper substrate by a conventionally known method, such as a blade coater, an air knife coater, a roll coater, a scythe press coater, or a cast coater. Coated paper can be produced by carrying out necessary drying using a normal method and further performing supercalender treatment if necessary.

The coated paper thus obtained using the paper coating composition of the present invention has excellent ink receptivity, water resistance, and blister resistance,
It has various excellent and effective properties such as no formaldehyde odor.

The term "paper" in the paper coating composition in the first aspect of the present invention has a broad meaning and includes paper and paperboard in a narrow sense.

Hereinafter, the present invention will be explained in more detail with reference to Examples. In the text, both ``part'' and ``part'' refer to % by weight and part by weight.

Example 1 1 mol of diethylenetriamine, 1 mol of epichlorohydrin
The moles were reacted in the presence of water at 60° C. for about 4 hours to obtain a diethylenetriamine-epichlorohydrin reaction product. The viscosity at 25°C of a 50% aqueous solution of the reaction product is B
When measured with a mold patch meter of 12 ram, it was found to be 20 centipoise. In addition, the cation equivalent at pH 9 of the reaction product is 1,3, l In-
It was eq/p.

A paper coating composition was prepared as follows using the diethylenetriamine-epichlor and dorine reaction product thus obtained.

First, 70 parts of Ultra White 90 (clay manufactured by Engelhardt Minerals, USA), 15 parts of Shiroenka PZ (light calcium carbonate from Shiraishi Kogyo Co., Ltd.), 15 parts of Super 1500 (fR heavy calcium carbonate from Maruo Calcium Co., Ltd.), and violet resin DS. -0.3 part of IQ (sodium polyacrylate dispersant manufactured by Sumitomo Chemical Co., Ltd.) and 0.4 part of caustic soda were dispersed in an appropriate amount of water to obtain a pigment slurry. To this pigment slurry, 6 parts of previously gelatinized Tamago Ace A (oxidized starch manufactured by Tamago Nasinal Co., Ltd.) and 12 parts of 5N-307 (SR latex manufactured by Sumitomo Naugatuck Co., Ltd.) were added and stirred well, and then the diethylenetriamine-epichlorohydrin reaction was performed. 0.5 part of the product was added and stirred, and the mixture was further adjusted to pH=11 and total solid content to 55 cm with an aqueous caustic soda solution and water to obtain a paper coating composition.

The paper coating composition was coated at the experimental coating port at 120°C, 3
It was subjected to oven drying for 0 seconds.

Next, this coated paper was conditioned at 20°C and 65% RH for 16 hours, and then heated at a roll temperature of 60°C and a roll linear pressure of 60 Kp/an.
The paper was subjected to supercalender treatment twice to obtain coated paper.

After conditioning this coated paper for 24 hours at 20°C and 65% RH,
It was subjected to the following tests.

(1) Water resistance) Wet rub method Approximately 0.1 drop of ion-exchanged water was dropped on the surface of the coated paper, rubbed with a fingertip, and the elution state of the coating composition was observed and judged.

The judgment criteria are as follows.

Water resistance (excellent) 5 to 1 (poor) (b) The coated surface was soaked in water using the wet pick method RI test 81 (manufactured by Mei Seisakusho).
After moistening, it was printed and the occurrence of picking was observed and determined. The determination Mi4'l is the same as the wet rub method.

(2) Ink receptivity) Using an A-method RI tester, the coated surface was moistened with water and printed, and the ink receptivity was observed and judged. The criteria for evaluation are the same as those for the wet rub method.

(b) Using a B-method RI tester, printing was performed while dropping water onto the ink being mixed in, and the acceptability of the ink was observed and determined. The criteria for evaluation are the same as those for the wet rub method.

(3) Perform double-sided printing on double-sided coated paper using a blister resistance RI tester,
After drying and moistening, the sample was immersed in a silicone oil bath to observe the extent of blistering, and the 0 criteria used for determining 0 was the same as in the wet rub method.

(4) Formaldehyde amount JIS L-1041-1976 liquid phase extraction method (2)
It was determined according to the acetylacetone method (Method A).

The measurement test results are shown in Table 1.

Table 1 shows the pH of the coating composition at 25° C. and the viscosity at 25° C. using a B-type viscometer at 5 Q rpm.

Example 2 A tetraethylenepentamine-epichlorohydrin reaction product was obtained in the same manner as in Example 1 except that 1 mole of tetraethylenepentamine was reacted with 0.8 mole of epichlorohydrin. 2 of a 50% aqueous solution of the reaction product
The viscosity at 5°C is 33 centipoise and the pH is 9.
The cation equivalent weight in was 3.4 m-eq/9. Using the thus obtained tetraethylenepentamine-epichlorohythrin reaction product, a paper coating composition was obtained in the same manner as in Example 1, and further coated paper was obtained. The coated paper was subjected to the same measurement test as in Example 1. The measurement test results are the first
Shown in the table.

Example 3 A triethylenetetramine-epichlorohydrin reaction product was obtained in the same manner as in Example 1, except that 1.4 moles of epichlorohydrin were reacted with 1 mole of triethylenetetramine. The viscosity of a 50% aqueous solution of the reaction product at 25°C is 97 centipoise, and the pH
The cation equivalent weight in 9 was 2.5 +n-c q/f. Using the thus obtained triethylenetetramine-epichlorohydrin reaction product, a paper coating composition was obtained in the same manner as in Example 1, and coated paper was further obtained. The coated paper was subjected to the same measurement test as in Example 1. The measurement test results are shown in Table 1.

Example 4 Using the diethylenetriamine-epichlorohydrin reaction product obtained in Example 1, a paper coating composition was prepared as follows.

First, 90.80 parts of Ultra White, 15 parts of Hakusaku pz, 5 parts of Satin White, violet resin DS-IQ,
1.0 parts of caustic soda and 0.6 parts of caustic soda were dispersed in a amount of water to obtain a pigment slurry. To this pigment slurry were added 6 parts of solar eclipse MS-4600 (phosphate esterified starch manufactured by Nihon Shokuhin Kako Co., Ltd.) and 12 parts of SN-307, which had been gelatinized in advance, and stirred well. 3 parts were added and stirred, and the pH was adjusted to about 11.5 and the total solid content to 55% with an aqueous caustic soda solution and water to obtain a paper coating composition.

Coated paper was obtained in the same manner as in Example 1 using the paper coating composition. The coated paper was subjected to the same measurement test as in Example 1. The measurement test results are shown in Table 2.

Example 5 1 mole of tetraethylenepentamine was reacted with 1.2 mole of epichlorohydrin at 60°C for 4 hours in the presence of water.
A tetraethylenepentamine-epichlorohydrin reaction product was obtained.

The viscosity of a 50% aqueous solution of the reaction product at 25°C is 1
It was 50 centipoise. Moreover, the pH of the reaction product is 9.
The cation equivalent in was 2, (y m-cq/1!) Using the thus obtained tetraethylenepentamine-epichlorohydrin reaction product, a paper coating composition was obtained in the same manner as in Example 4, and further coated. A coated paper was obtained. The coated paper was subjected to the same measurement test as in Example 4. The measurement test results are shown in Table 2.

Comparative Example 1 A diethylene triξ-epichlorohydrin reaction product was obtained in the same manner as in Example 1 except that 1 mole of tetraethylenepentamine was reacted with 1.6 moles of epichlorohydrin. The viscosity of a 50% aqueous solution of the reaction product at 25°C was 540 centipoise, and the cation equivalent at pH 9 was 2.8 m-eC4/f. Although the tetraethylene pentamine thus obtained was tested, it was not possible to obtain a fluid coating composition for paper.

Comparative Example 2 Using the diethylenetriamine-epichlorohydrin reaction product obtained in Example 1, the pH of the paper coating composition was 9.5.
Although an attempt was made to prepare a paper coating composition using the same method as in Example 1 and Example 4 except for the above, it was not possible to obtain a paper coating composition with fluidity.

Comparative Example 3 A paper coating composition was obtained in the same manner as in Example 1, except that the diethylenetriamine-epichlorohydrin reaction product was not used, and coated paper was also obtained. The coated paper was subjected to the same measurement test as in Example 1. The measurement test results are shown in Table 1.

Comparative Example 4 A paper coating composition was obtained in the same manner as in Example 1 for all ponds using violet resin 613 (melamine-formaldehyde resin, manufactured by Sumitomo Chemical Co., Ltd.) instead of the diethylenetriamine-epichlorohydrin reaction product, and further coated. Got paper.

The coated paper was subjected to the same measurement test as in Example 1. The measurement test results are shown in Table 1.

Comparative Example 5 A tetraethylenepentamine-epichlorohydrin reaction product was obtained in the same manner as in Example 1 by adding 0.5 mole of epichlorohydrin to 1 mole of latetetraethylenepentamine. The viscosity of the SOS aqueous solution of the reaction product at 25° C. was 40 centipoise. Further, the cation equivalent at pH 9 was 5.2 m-eq/11. Using the thus obtained tetraethylenepentamine-epichlorohydrin reaction product, an attempt was made to prepare a paper coating composition in the same manner as in Example 1, but it was not possible to obtain a fluid paper coating composition. .

Comparative Example 6 A paper coating composition was obtained in the same manner as in Example 4, except that the diethylenetriamine-epichlorohydrin reaction product was not used, and coated paper was also obtained. The coated paper was subjected to the same measurement test as in Example 1. The measurement test results are shown in Table 2.

Comparative Example 7 1 mole of ethylenediamine was reacted with 0.8 mole of epichlorohydrin under the same conditions as in Example 1 to obtain an ethylenediamine-epichlorohydrin reaction product. The viscosity of a 50% aqueous solution of the reaction product at 25°C is 6.5 centipoise, and the cation equivalent at pH 9 is 3.4.
It was In-ec1/f. Using the ethylenediamine-epichlorohydrin reaction product thus obtained, a paper coating composition was obtained in the same manner as in Example 1, and coated paper was further obtained.

The coated paper was subjected to the same measurement test as in Example 1. The test results are shown in Table 1.

Comparative Example 8 The same procedure as in Example 1 was carried out except that 1 mole of ethylenediamine was reacted with 2.5 moles of epichlorohydrin.
An ethylenediamine-epichlorohydrin reaction product was obtained. The viscosity of a 50% aqueous solution of the reaction product at 25° C. was 150 centipoise, and the cation equivalent at pH 9 was 0.4 m-eq/f. Using the ethylenediamine-epichlorohydrin reaction product thus obtained, a paper coating composition was obtained in the same manner as in Example 4, and coated paper was further obtained. The coated paper was subjected to the same measurement test as in Example 1. The measurement test results are shown in Table 2.

Comparative Example 9 A paper coating composition was obtained in the same manner as in Example 4 except that violet resin 633 (polyamide polyurea-formaldehyde resin manufactured by Sumitomo Chemical Co., Ltd.) was used instead of the diethylenetriamine-epichlorohydrin reaction product. Furthermore, coated paper was obtained. The coated paper was subjected to the same measurement test as in Example 1. The test results are shown in Table 2.

Claims (1)

[Claims] (a) a pigment, (b) an aqueous binder, and (c) a reaction product of a polyalkylene polyamine or/and an alkylene diamine and an epihalohydrin, and a 50% by weight aqueous solution of the reaction product has a viscosity of 10 to 500 at 25°C. Contains (a), (b), and (c) with a cation equivalent of more than 0.5 m-eq/g and less than 5 m-eq/g at pH 9 in centipoise, and has a pH of 10 or more. Coating composition for paper.