JPH0713359B2 - Coating composition for paper - Google Patents

Description

The present invention relates to a paper coating composition which provides a coated paper having excellent printability and printing effect.

More specifically, the present invention relates to a paper coating composition which is excellent in ink acceptability, water resistance and blister resistance and provides a coated paper which does not generate a formaldehyde odor.

A coated paper obtained by applying a coating composition for paper mainly composed of a pigment and an aqueous binder to paper and subjecting it to necessary steps such as drying and calendering is a commercial printed product because of its excellent printing effect. Although it is widely used in magazines, books, and so on, efforts have been made to improve the quality of coated paper as quality requirements become higher and printing speed increases. Especially in offset printing, which occupies most of printing, ink acceptability under the influence of squeezing water, water resistance of wet topics and wet rubs, improvement of blister resistance in rotary printing,
Improvement is an important issue for the industry.

Conventionally, for such purposes, various waterproofing agents have been added to a paper coating composition mainly composed of a pigment and an aqueous binder to improve the quality of the coated paper. Although the agents and the like all have effective properties, they are not satisfactory in practice because of serious drawbacks.

For example, aminoplast resins such as melamine-formaldehyde resin and urea-formaldehyde resin not only generate a large amount of formaldehyde at the time of work and coated paper, but also hardly obtain the effect of improving ink acceptability and blister resistance. Also, the water resistance effect becomes extremely difficult to obtain as the pH of the coating composition increases. Glyoxal and other dialdehydes cause the coated paper to be colored, and cannot improve the ink acceptability and blister resistance. Polyvalent metal salts such as zirconium cannot improve the ink acceptability and blister resistance.

Under these circumstances, polyamide polyurea-as an effective agent for improving and improving ink acceptability, water resistance, and blister resistance
At present, formaldehyde resins are widely used. However, the polyamide potaurea-formaldehyde resin also has a marked decrease in its efficacy, particularly ink acceptability and water resistance, when the pH of the coating composition is high. For these reasons, there has been a strong demand for a chemical agent that markedly improves and improves ink acceptability, water resistance, and blister resistance in paper coating compositions, particularly high pH paper coating compositions.

As a result of intensive investigations by the present inventors in view of the present situation, a paper coating composition mainly composed of a pigment and an aqueous binder,
It has been found that the above object can be achieved by adding a reaction product of polyalkylene polyamine or / and alkylene diamine, epihalohydrin or / and alkylene dihalide and dialkyl sulfuric acid, and the present invention has been completed. That is, the present invention provides a reaction product of (A) (a) polyalkylene polyamine or / and alkylene diamine, (b) epihalohydrin or / and alkylene dihalide, (c) dialkyl sulfuric acid, (B) pigment, and (C) A paper coating composition comprising an aqueous binder.
In synthesizing the reaction product (A) used here,
It does not react with epoxy compounds other than epihalohydrin.

Examples of the polyalkylene polyamine in the present invention include diethylene triamine, triethylene tetramine,
Examples thereof include tetraethylenepentamine, pentaethylenehexamine, heptaethyleneoctamine, nonaneethylenedecamine, triethylenebis (trimethylene) hexamine, aminoethylpiperazine and iminobispropylamine. Further, as the alkylenediamine, ethylenediamine, 1,3-diaminopropane, propylenediamine, piperazine, dimethylaminopropylamine,
Mentanediamine, triethylenediamine, hexamethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyl-1,3-butanediamine and the like can be mentioned. These polyalkylene polyamines and alkylene diamines may be used alone or in admixture of two or more.

Examples of epihalohydrin include epichlorohydrin, epibromohydrin, methylepichlorohydrin and the like.

As the alkylene dihalide, ethylene dichloride,
Examples include propylene dichloride and ethylene dibromide.

The reaction product of (a) polyalkylene polyamine or / and alkylene diamine, (b) epihalohydrin or / and alkylene dihalide and (c) dialkyl sulfuric acid is (a) polyalkylene polyamine or / and alkylene diamine and (b) Epihalohydrin and / or alkylenedihalide are reacted at a temperature of 20 to 80 ° C. for about 30 minutes to 10 hours, and then (c) dialkyl sulfuric acid is added to 20 to 80.
It can be obtained by reacting at 30 ° C for about 30 minutes to 10 hours. In this case, it can also be obtained by first reacting the dialkyl sulfuric acid with (a) polyalkylene polyamine or / and alkylene diamine, and then reacting with (b) epihalohydrin or / and alkylene dihalide. In the above reaction, a pH adjusting agent such as acid or base may be added to adjust the reaction rate.

The ratio of the raw materials used to obtain the reaction product is effective in the range of (a) / (b) / (c) = 1 / 0.5 to 3.0 / 0.1 to 2.0, preferably 1 / 0.8-2.0 / 0.3-1.
A molar ratio range of 5 is good.

The pigment in the present invention includes white inorganic pigments such as kaolin, talc, calcium carbonate, aluminum hydroxide, satin white and titanium oxide, and polystyrene and melamine.
Organic synthetic pigments such as formaldehyde resin and urea-formaldehyde resin may be used alone or in combination of two or more.

The aqueous binder in the present invention is a water-soluble binder such as oxidized starch, phosphoric acid esterified starch, polyvinyl alcohol, casein, gelatin, carboxymethyl cellulose, styrene-butadiene resin, vinyl acetate resin, ethylene-vinyl acetate resin, methyl. Water-emulsified binders such as methacrylate-butadiene resins can be used alone or in admixture of two or more.

The composition ratio of the coating composition for paper of the present invention is 1 to 50 parts by weight, preferably 6 to 40 parts by weight of the aqueous binder to 100 parts by weight of the pigment, and the reaction product (A) of 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight. The solid content concentration of the coating composition is 20 to 70 parts by weight, preferably 30 to 65% by weight.

Generally, the reaction product of the present invention is added and mixed with the pigment and the aqueous binder during the preparation of the coating composition for paper, but the effect of the present invention can be obtained by adding and mixing the pigment slurry or the aqueous binder in advance. be able to.

The paper coating composition of the present invention requires a dispersant, a viscosity / fluidity modifier, an antifoaming agent, a preservative, a lubricant, a water retention agent, a dye, a colorant such as a colored pigment, and the like as other components. Can be blended accordingly.

Further, in the process of preparing the coating composition of the present invention, the mixing order of each component is not particularly limited, but dispersion stability as a composition decreases due to different ionicity and the like. Therefore, it is desirable to select the compounding order, the solid content concentration of each component at the time of compounding, the pH of the coating composition, etc., and carry out. It is also possible to add the reaction product of the present invention to an aqueous binder in advance to prepare a coating composition.

The coating composition for paper of the present invention is applied on a paper substrate by a conventionally known method, that is, a blade coater, an air knife coater, a roll coater, a size press coater, a cast coater, or the like, which is usually used. The coated paper can be produced by carrying out the required drying by the above method, and further subjecting it to a super calendering treatment if necessary.

In this way, the coated paper obtained using the coating composition for paper of the present invention has excellent ink acceptability, water resistance, and blister resistance,
It has various excellent and effective properties such as no generation of formaldehyde odor.

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

Hereinafter, the present invention will be described in more detail with reference to examples. All% and parts in the text represent% by weight and parts by weight.

Example 1 103.2 parts of diethylenetriamine was dissolved in 195.7 parts of water to obtain the internal temperature.
While maintaining the temperature at 50 ° C, 120.3 parts of epichlorohydrin was added dropwise over 5 hours for reaction. Next, while maintaining the system pH at 8 to 9 using 23% caustic soda, 92.5 parts of diethylsulfate was gradually added and reacted at a temperature of 40 ° C. for 3 hours.

After the reaction, water was added to adjust the temperature to make a 50% aqueous solution. This is designated as reaction product A. The viscosity of A was 19 centipoise.

The reaction product A thus obtained was used to prepare a paper coating composition as follows.

First, 70 parts of Ultra White 90 (Clay made by Engelhard Minerals, Inc. in the United States), 15 parts of Shiratsuka PZ (light calcium carbonate made by Shiroishi Industry), 15 parts of Super 1500 (heavy calcium carbonate made by Maruo Calcium), Sumireze Resin DS -Ten
(Sumitomo Chemical's sodium polyacrylate dispersant) 0.3
Parts and 0.4 parts of caustic soda were dispersed in an appropriate amount of water to obtain a pigment slurry. This pigment slurry was pre-gelatinized with Oji Ate A (Oji National Oxidized Starch)
6 parts, SN-307 (Sumitomo Nogatak SB latex) 12
After adding well and stirring well, 0.5 parts of the reaction product A of diethylenetriamine-epichlorohydrin / diethylsulfuric acid was added.
Partial mixing and stirring, and pH = with aqueous sodium hydroxide solution and water
11, the total solid content was adjusted to 55% to obtain a coating composition A for paper.

The coating composition A for paper was coated on a high-quality paper weighing 80 gm ² of rice using a laboratory coating rod so that the coating amount was 13 g / m ^2, and immediately subjected to oven drying at 120 ° C. for 30 seconds. Then, this coated paper was conditioned at 20 ° C. and 65% RH for 16 hours, and then subjected to super calendering twice at a roll temperature of 60 ° C. and a roll linear pressure of 60 kg / cm to obtain a coated paper.

These coated papers were conditioned at 20% and 65% RH for 24 hours and then subjected to the following tests.

(1) Water resistance (a) Wet rub method About 0.1 ml of ion-exchanged water was dropped on the surface of coated paper and rubbed with a fingertip, and the elution state of the coating composition was observed and judged. The criteria for judgment are as follows.

Water resistance (excellent) 5 to 1 (poor) (b) Wettopic method Wet the coated surface with water using an RI tester (manufactured by Akira Seisakusho), then print to observe the picking occurrence state. It was judged. The criterion is the same as the wet lab method.

(2) Ink acceptability (b) Method A The ink acceptability of the ink was observed by making a print after moistening the coated surface with a RI tester and making a judgment. The criterion is the same as the wet lab method.

(B) Method B Using an RI tester, printing was performed while dripping water on the ink being kneaded, and the acceptability of the ink was observed and judged. The criterion is the same as the wet lab method.

(3) Blister resistance Double-sided printing was performed on double-sided coated paper using an RI tester, and after drying and wetting, it was immersed in a silicone oil bath and the degree of blistering was observed and judged. The criterion is the same as the wet lab method.

(4) Formaldehyde amount Quantified according to the liquid phase injection method of JIS L-1041-1976 (2) 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 of the B type viscometer at 25 rpm at 60 rpm.

Example 2 60.1 parts of ethylenediamine was reacted with 92.5 parts of epichlorohydrin in the presence of 152.6 parts of water at 60 ° C. for about 4 hours to obtain an ethyleneydiamine-epichlorohydrin reaction product. Then, 77.1 parts of diethyl sulfuric acid was reacted at 40 ° C. for 4 hours to obtain an ethylenediamine-epichlorohydrin / diethyl sulfuric acid reaction product.

This was diluted with water to give a 50% aqueous solution. This is called reaction product B. The reaction product B was further mixed with a pigment and an aqueous binder in the formulation described in Example 1 to prepare a paper coating composition B.
Got This coating composition B for paper was applied to a high-quality paper according to the method of Example 1 to obtain a coated paper, and the same test as in Example 1 was conducted. The results are shown in Table 1.

Example 3 103.2 parts of diethylenetriamine and 1 part of epichlorohydrin
29.5 parts were reacted in the presence of 232.7 parts of water at 60 ° C. for about 4 hours to obtain a diethylenetriamine-epichlorohydrin reaction product. Then, 100.9 parts of dimethylsulfate was reacted at 25 ° C. for 4 hours to obtain a diethylenetriamine-epichlorohydrin / dimethylsulfate reaction product. This was diluted with water to obtain a 50% aqueous solution. This is called reaction product C.

Using this reaction product C, a coated paper for test was obtained in the same manner as in the method of Example 1, and the same test as in Example 1 was performed. The results are shown in Table 1.

Example 4 103.2 parts of diethylenetriamine and 195.7 parts of water were mixed and dissolved, to which 75 parts of 28% caustic soda water was added, and further 92.5 parts of diethylsulfate were gradually added. This was reacted at 40 ° C. for 2 hours. Then, the temperature was raised to 50 ° C., and 120.3 parts of epichlorohydrin was added dropwise over 5 hours for reaction. After reaction, add water 50
% Aqueous solution. This is designated as reaction product D. The viscosity of D was 17 centipoise. Using this product D, a coated paper for test was obtained in the same manner as in Example 1, and the same test as in Example 1 was performed. The results are shown in Table 1.

Example 5 189.3 parts of tetraethylenepentamine was reacted with 98.9 parts of ethylene dichloride in the presence of 288.2 parts of water at 70 ° C to 100 ° C for about 10 hours to obtain a reaction product of tetraethylenepentamine-ethylenedichloride. Then add 92.5 parts of diethylsulfate
The reaction was carried out at 40 ° C. for 4 hours to obtain a reaction product of tetraethylenepentamine-ethylenedichloride / diethylsulfuric acid.
Water was added to this to dilute it to give a 50% aqueous solution. This is called reaction product E. A coated paper was obtained by the method of Example 1 using this reaction product, and the same test as in Example 1 was performed.
The results are shown in Table 1.

Comparative Example 1 Instead of the reaction product of polyalkylene polyamine / epihalohydrin / dialkyl sulfuric acid, Sumirez resin 613 was used.
A coating composition for paper was obtained in the same manner as in Example 1 except that (melamine-formaldehyde resin, manufactured by Sumitomo Chemical Co., Ltd.) was used, 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 shown in Table 1.

Comparative Example 2 Instead of the reaction product of polyalkylene polyamine / epihalohydrin / dialkyl sulfuric acid, Sumirez Resin 633 was used.
A paper coating composition was obtained in the same manner as in Example 1 except that (Sumitomo Chemical Co., Ltd. polyamide-polyurea-formaldehyde resin) was used, and a coated paper was further obtained. The coated paper is as in Example 1.
It was subjected to the same measurement test as. The test results are shown in Table 1.

Comparative Example 3 A coating composition for paper was prepared according to Example 1 without using any cationic polymer, using only a pigment and an aqueous binder, and coated on wood free paper according to Example 1 to obtain a coated paper. The coated paper was subjected to the same measurement test as in Example 1. The test result is the first
Shown in the table.

Front Page Continuation (72) Inventor Haruo Tanaka 3-98 Kasugadinaka, Konohana-ku, Osaka City, Osaka Prefecture Sumitomo Chemical Co., Ltd. (72) Inventor Shigeru Ura 3-chome, Kasuganode, Konohana-ku, Osaka No. 1-98 Sumitomo Chemical Co., Ltd. (56) Reference JP-A-61-252396 (JP, A) US Patent 3725312 (US, A)

Claims (1)

[Claims] 1. A reaction product of (A) (a) polyalkylene polyamine or / and alkylene diamine, (b) epihalohydrin or / and alkylene dihalide, and (c) dialkyl sulfuric acid (provided that epoxy other than epihalohydrin is used. A coating composition for paper, comprising: (a compound which does not react), (B) a pigment, and (C) an aqueous binder.