JPH0672398B2 - 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 Huosset 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.

For these purposes, various kinds of waterproofing agents have been added to paper coating compositions, mainly pigments and aqueous binders, to improve the quality of coated papers. Although all the agents have effective properties, they are not satisfactory in practice because they have 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 polyurea-formaldehyde resin also remarkably deteriorates its efficacy, especially 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,
The reaction product [II] or [II] obtained by reacting the reaction product [I] of polyalkylene polyamine or / and alkylene diamine with epihalohydrin or / and alkylene dihalide with a quaternizing agent It has been found that the above object can be achieved by adding the reaction product [III] obtained by the reaction, and the present invention has been completed.

That is, the present invention is obtained by reacting a reaction product [I] of (a) a pigment, (b) an aqueous binder and (c) a polyalkylene polyamine or / and an alkylene diamine with epihalohydrin or / and an alkylene dihalide with an epoxy compound. A coating composition for paper characterized by containing the reaction product [II] or the reaction product [III] obtained by further reacting the reaction product [II] with a quaternizing agent.

Examples of the polyalkylene polyamine in the present invention include diethylene triamine, triethylene tetramine,
Examples thereof include tetraethylenepentamine, pentaethylenehexamine, heptaethyleneoctamine, nonaethylenedecamine, 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. Further, monoamines such as diethylamine and dipropylamine may be mixed and used for the purpose of controlling or modifying the molecular weight.

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

As the alkylene dihalide, ethylene dichloride,
Propylene dichloride and the like can be mentioned.

The reaction product [I] of polyalkylenepolyamine or / and alkylenediamine and epihalohydrin is obtained by reacting polyalkylenepolyamine or / and alkylenediamine and epihalohydrin at a temperature of 20 to 80 ° C. for about 30 minutes to 10 hours. .

The epoxy compound in the present invention, unlike the above epihalohydrin, does not have a reactive functional group other than an epoxy group, for example, ethylene oxide, propylene oxide, butyl glycidyl ether, styrene oxide, phenyl glycidyl ether, glycidyl alcohol, Examples thereof include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, octylene oxide, cyclohexene oxide, diethylene glycol diglycidyl ether, polyethylene diglycidyl ether and the like.

The reaction product [II] is usually obtained as an aqueous solution having a solid content concentration of 20 to 80% by reacting the reaction product [I] with an epoxy compound at a temperature of 0 ° C to 100 ° C for about 30 minutes to 10 hours. To be

Examples of the quaternizing agent in the present invention include the following compounds.

Methyl chloride, methyl bromide, ethyl chloride, methyl iodide, ethyl chloroacetate, acrylic chloride, ethylene chlorohydrin, benzyl chloride, dimethyl sulfate, diethyl sulfate, 2-chlorotriethylamine, 3-chloro-2-oxypropyltrimethylammonium chloride .

The reaction product [III] is usually obtained as a 20 to 80 wt% aqueous solution by reacting the reaction product [II] with a quaternizing agent at a temperature of 10 ° C to 100 ° C for about 30 minutes to 10 hours. To be

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 composed of 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 methacrylate. Water-emulsified binders such as resins may be used alone or in combination of two or more.

The composition ratio of the paper coating composition of the present invention is 1 to 50 parts by weight, preferably 6 parts by weight of the aqueous binder to 100 parts by weight of the pigment.
~ 40 parts by weight, the reaction product of the present invention [II] or [III] 0.0
It is 5 to 5 parts by weight, preferably 0.1 to 2 parts by weight. Also,
The solid content concentration of the coating composition is 20 to 70% by weight, preferably 30
~ 65% by weight.

The paper coating composition of the present invention requires a dispersant, a viscosity, a fluidity modifier, an antifoaming agent, an antiseptic, 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.

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 1 mol of diethylenetriamine and 1 mol of epichlorohydrin
Moles were reacted in the presence of water at 60 ° C. for about 4 hours to obtain a diethylenetriamine-epichlorohydrin reaction product.

Then, 0.6 mol of ethylene oxide was reacted at 15 ° C. for 4 hours to obtain a diethylenetriamine-epichlorohydrin / ethylene oxide reaction product. This is designated as reaction product A. The viscosity of the 50% aqueous solution of A at 25 ° C. was 25 centipoise (B-type viscometer 12 rpm).

This reaction product A was further mixed with 0.2 mol of dimethyl sulfate at 20 ° C.
At room temperature for 2 hours to obtain a quaternized cationic polymer. This is designated as reaction product B. The viscosity of a 50% aqueous solution of B at 25 ° C. was 20 centipoise.

Using the reaction products A and B thus obtained, a coating composition for paper was prepared 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 −10
(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. Oji Ace A (oxidized starch manufactured by Oji National Co., Ltd.) pre-gelatinized to this pigment slurry
6 parts, SN-307 (Sumitomo Nogatak SB latex) 1
After adding 2 parts and stirring well, 0.5 part of the reaction product A of diethylenetriamine-epichlorohydrin / ethylene oxide was mixed and stirred, and further adjusted to pH = 11 with a caustic soda aqueous solution and water to a total solid content of 55% and used for paper. Coating composition A
Got

In the same manner, 0.5 part of the cationic polymer B obtained by further quaternizing the reaction product A of diethylenetriamine-epichlorohydrin / ethylene oxide with dimethylsulfate was mixed and stirred, and further, pH = 11 with a caustic soda aqueous solution and water, total solid content 55% To a coating composition B for paper.

For paper coating composition A, coating B so as to have a coating weight 13 g / m ² on a high-quality paper of a basis weight amount 80 g / m ² using a laboratory coating rod, immediately 120 ° C., oven dried for 30 seconds I went to
Then, this coated paper was conditioned at 20 ° C. and 65% RH for 16 hours, and then subjected to a super calender treatment 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 ° C. 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 Ming Seisakusho), then print to observe the picking occurrence state. It was judged. The criterion is the same as the wet lab method.

(2) Ink Receiving Method (a) Method A Using a RI tester, the coated surface was wetted with water and then printed to observe the acceptability of the ink for 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 Quantitated according to the liquid phase extraction 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 1 mol of ethylenediamine was reacted with 1 mol of epichlorohydrin in the presence of water at 60 ° C. for about 4 hours to obtain an ethylenediamine-epichlorohydrin reaction product. Then, 1.0 mol of propylene oxide was reacted at 15 ° C. for 4 hours to obtain an ethylenediamine-epichlorohydrin / propylene oxide reaction product. This is designated as reaction product C.
This reaction product C was further pigmented according to the formulation described in Example 1,
By mixing with an aqueous binder, a coating composition C for paper was obtained. This coating composition C for paper was applied to 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 1 mol of diethylenetriamine and 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. Then, after reacting 1.0 mol of propylene oxide at 15 ° C for 4 hours, 0.4 mol of benzyl chloride was further added at 4 ° C at 4 ° C.
The reaction was carried out for a time to obtain a quaternized cationic polymer. This is called reaction product D. Using this reaction product D, 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 1 mol of tetraethylenepentamine was reacted with 1 mol of ethylene dichloride in the presence of water at 70 ° C to 100 ° C for about 10 hours to obtain a reaction product of tetraethylenepentamine-ethylenedichloride. Then, 1.0 mol of propylene oxide was reacted at 15 ° C for 4 hours to give tetraethylenepentamine-
An ethylene dichloride / propylene oxide reaction product was obtained. 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 diethylenetriamine-epichlorohydrin / ethylene oxide reaction product, 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 diethylenetriamine-epichlorohydrin / ethylene oxide reaction product, Sumirez Resin 633 was used.
A coating composition for paper was obtained in the same manner as in Example 1 except that (Polyamide-polyurea-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 test results are shown in Table 1.

Comparative Example 3 A coating composition for paper was prepared according to Example 1 by using only the pigment and the aqueous binder according to Example 1 without using any cationic polymer, 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.

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Claims (1)

[Claims] 1. A reaction product [I] of (a) a pigment, (b) an aqueous binder, and (c) a polyalkylene polyamine or / and an alkylene diamine and an epihalohydrin or / and an alkylene dihalide, and another reactive functional group. Paper containing a reaction product [II] obtained by reacting with an epoxy compound having no group, or a reaction product [III] obtained by further reacting [II] with a quaternizing agent. Coating composition.