JP2001214397A - Additive for coated paper and coated paper using the same additive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high-performance additive as a coating liquid composition for coated paper. SOLUTION: An additive for coated paper features compounding (a) 100 pts.wt. of a synthesized resin having an N(nitrogen) content of 5-14 wt.% in a molecule obtained by reacting a polyamine-based compound with bisphenol A epoxy resin with (b) 1-30 pts.wt. of an anionic surfactant and (c) 100-1,000 pts.wt. of water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated paper additive having excellent properties, a coating liquid coating composition containing the same, and a coated paper using the same. More specifically, the present invention relates to a coated paper having not only excellent water resistance and excellent ink deposition property when wet, but also excellent surface strength and printing gloss, and a coated paper additive therefor. And a coating liquid composition for coated paper.

[0002]

2. Description of the Related Art In recent years, the production of coated paper or coated paperboard has increased significantly with the rapid increase in demand for magazines, brochures, advertisements, and packaging materials printed in multicolor. In particular, with the speeding up of offset printing,
The requirements for the quality of the coating composition for paper in coated paperboard are also becoming more sophisticated.

For example, in general offset printing,
Surface strength of coated paper / coated paperboard, ie dry pick strength or water resistance involving dampening water, ie wet topic strength, water absorption of coated paper / coated paperboard after dampening water transfer and uniformity of ink It is strongly desired to improve basic properties such as good ink inking property (ink transfer property), drying property of transferred ink (ink setting property), and gloss of printed ink surface (print gloss).

On the other hand, in the production of coated paper and coated paperboard, for example, in coated paper, the tendency to increase the coating speed has become more and more conspicuous. Troubles such as backing rolls and super calendars that become obstacles, or streaks and scratches are frequently occurring. In coated paperboard, the use of casein tends to decrease due to the soaring casein. In this case, machine calendar stains and gloss calendar stains have occurred.

[0005] With respect to the above-mentioned various printing aptitudes and coating operability, studies have been made on pigment binders, especially SB latex, which is the mainstream, and on various additives mainly for waterproofing agents.

For example, there is a method of increasing the amount of SB-based latex to increase the dry pick strength and wet topic strength. In addition, in a SB-based latex, a monomer of a specific type and composition including an ethylenically unsaturated carboxylic acid and an ethylenically unsaturated amine is emulsion-polymerized under special conditions, and a copolymer latex having a gelation point in a specific range. A coating liquid composition for paper using as a pigment binder prevents a decrease in the water absorption of coated paper and coated paperboard, and a coated paper having good ink adhesion for the second and subsequent colors during offset printing. It has been proposed that coated paperboard be obtained (Japanese Patent Publication No. 59-49360). In addition, from the viewpoint of an additive of a paper coating liquid composition, a polyamide polyurea-formaldehyde aqueous solution, a urea-formaldehyde resin aqueous solution, a melamine-formaldehyde resin aqueous solution, an amino compound having 3 to 30 carbon atoms having at least two amino groups, and the like. (JP-B-59-32597, JP-B-61-42931, JP-B-2-607).
No. 98, Japanese Patent Publication No. 3-16439). Furthermore, a water-soluble resin obtained by reacting an amino compound having a primary or secondary amino group and an epoxy compound having at least two epoxy groups in a molecule has been proposed (Japanese Patent Publication No. 6-166994). .

However, when the amount of the SB-based latex used is increased, the dry pick strength and the wet topic strength are certainly improved, but the water absorption, the ink adhesion property, and the ink setting property are significantly reduced. In addition, although SB-based latex modified by various means certainly improves the ink-coating property and the wet topic strength, it has the drawback of significantly increasing the viscosity of the coating liquid, and has a sufficient ink-coating property. In order to obtain the improvement effect, the dry pick strength is reduced. In addition, when the above additives are used, the wet topic strength and the ink inking property are certainly improved, but the dry pick strength is significantly reduced and the viscosity of the coating liquid is increased. In addition, some of them produce formalin during drying, which is also an environmental problem. On the other hand, the present inventors have proposed a water-insoluble resin composite obtained by reacting a polyamine-based compound and a bisphenol A type epoxy resin (Japanese Patent Application No. Hei 09-1997).
No. 525074). However, since this water-insoluble resin compound cannot be sufficiently diluted with water, it has a high viscosity as a product and may cause a problem in handling. In some cases, poor dispersibility in the coating liquid may occur, which may cause unevenness in ink deposition on the coated paper.

[0008]

SUMMARY OF THE INVENTION The present invention relates to Japanese Patent Application No.
In addition to solving the problems of handleability and dispersibility in a coating liquid of a water-insoluble resin compound obtained in JP-A-525074, the water-soluble resin composition is excellent not only in water resistance and ink wetness when wet,
An object of the present invention is to provide a coated paper having excellent properties in surface strength and printing gloss, an additive for the coated paper, and a coating liquid coating composition for the coated paper.

[0009]

Means for Solving the Problems As a result of repeated studies to solve the above-mentioned problems, the present inventors have found that water soluble in water obtained by reacting a specific polyamine compound with a specific bisphenol A type epoxy resin. The present invention has been found to be able to be solubilized in water by adding a specific anionic surfactant to a difficult resin composition, and to be able to reduce the product viscosity to a point where there is no problem in handling. .

That is, the present invention is as follows. (A) N in the molecule obtained by reacting a polyamine compound and a bisphenol A type epoxy resin
Resin composite 10 having (nitrogen) content of 5 to 14% by weight
An additive for coated paper, wherein (b) 1 to 30 parts by weight of an anionic surfactant and (c) 100 to 1000 parts by weight of water are added to 0 part by weight.

The above-mentioned additive for coated paper, wherein the polyamine compound is represented by the following formula (1). H ₂ N— (CH ₂ —CH ₂ —NH) nH (1) (where 1 ≦ n ≦ 4)

The bisphenol A type epoxy resin is represented by the following formula (2).

[0013]

Embedded image

The additive for coated paper according to claim 1, 2 or 3 is used in an amount of 0.01 to 100 parts by weight of the pigment for coated paper.
A coating liquid composition for coated paper, comprising 5.0 parts by weight and 6 to 20 parts by weight of a pigment binder.

A coated paper characterized in that the coating liquid composition for coated paper according to claim 4 is coated on one or both sides of the paper at a thickness of ² to 40 g / m ² .

Hereinafter, the present invention will be described in detail. The resin composite (a) used in the present invention is obtained by reacting a polyamine compound and a bisphenol A type epoxy resin, and has a N (nitrogen) content in the molecule of 5 to 14% by weight. If the N (nitrogen) content in the molecule is less than 5% by weight, the effect of the present invention is not exhibited. On the other hand, when the content exceeds 14% by weight, the viscosity of the coating liquid composition for coated paper of the present invention becomes too high, which causes a problem in operation.

The polyamine compound used in the present invention is a compound having two or more amino groups in one molecule. It is preferably represented by the above formula (1), and n
Is from 1 to 4, preferably from 1 to 2. If the value of n is 1
When it is less than 4, the effect of the present invention is not sufficiently exhibited, and when it exceeds 4, the viscosity of the coating liquid composition for coated paper becomes high, which may cause operational problems.

Specific examples of the polyamine compound include ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine. Preferably, they are ethylenediamine and diethylenetriamine.

The bisphenol A type epoxy resin used in the present invention is preferably represented by the above formula (2), and k is from 0 to 2.5, preferably from 0 to 2.1. . If the value of k exceeds 2.5, the effects of the present invention will not be sufficiently exhibited.

In the present invention, the conditions for carrying out the reaction between the polyamine compound and the bisphenol A type epoxy resin are not particularly limited. The reaction may be carried out only with the polyamine-based compound and the bisphenol A type epoxy resin, or water or an organic solvent may be used as necessary. The organic solvent that can be used is not particularly limited, but examples include methanol, ethanol, isopropyl alcohol, butanol, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether. The additive for coated paper of the present invention may be used while containing an organic solvent, or may be used after heating or distillation under reduced pressure to volatilize the organic solvent.

The reaction temperature and the reaction time are not particularly limited, but may be 50-110 ° C., 0.5-3
Time is desirable.

The anionic surfactant used in the present invention is not particularly limited, but includes fatty acid salts, sulfonates of higher alcohols, sulfates of liquid oils and fats, and sulfonates of dibasic fatty acid esters. , Alkyl allyl sulfonates, formalin condensed naphthalene sulfonates, and the like.

The additive for coated paper of the present invention is a resin composite 1
An aqueous dispersion is prepared by mixing 1 to 30 parts by weight of an anionic surfactant and 100 to 1000 parts by weight of water with respect to 00 parts by weight. If the amount of the anionic surfactant is less than 1 part by weight, phase separation occurs. On the other hand, when the amount exceeds 30 parts by weight, the water resistance of the coating liquid composition for coated paper prepared using this additive is reduced, and the composition is not practical. On the other hand, if the amount of water is less than 100 parts by weight, the water dispersibility of the resin composition is not sufficient, and if it exceeds 1000 parts by weight, there is a problem in storage stability.

The coating liquid composition for coated paper of the present invention is prepared by adding 0.01 to 100 parts by weight of a coated paper pigment to an additive for coated paper.
It is used in an amount of 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight. If the amount of the additive for coated paper is less than 0.01 part by weight, the effect of the present invention is not recognized. Also, 5.
If the amount exceeds 0 parts by weight, the viscosity of the coating composition for coated paper becomes too high, and a problem in operation occurs.

The additive for coated paper of the present invention can be used by being compounded in a coating liquid composition for coated paper, or may be used by being previously mixed with a pigment binder.

The pigment binder used in the present invention includes commonly used pigment binders, for example, synthetic binders such as SB latex, acrylic latex and vinyl acetate latex, and natural binders such as starch and casein. Can be The pigment binder is used in an amount of 6 to 20 parts by weight based on 100 parts by weight of the pigment for coated paper. When the amount is less than 6 parts by weight, the dry pick strength and the wet topic strength are significantly reduced. On the other hand, when the amount exceeds 20 parts by weight, the ink deposition property and the ink setting property are remarkably reduced.

The pigment used in the coating composition for coated paper of the present invention is, for example, commonly used in coating compositions for coated paper such as clay, calcium carbonate, titanium oxide, and satin white. Examples include mineral pigments and organic pigments such as polystyrene-based fine particles called plastic pigments.

Further, the coating composition for coated paper of the present invention comprises:
Various additives commonly used, for example, dispersants, thickeners, neutralizers, bactericides and defoamers can also be used.

Furthermore, the coated paper additive of the present invention may be used in addition to coated paper such as art paper, coated paper, lightweight coated paper, finely coated paper, coated paper such as high-grade paperboard, and coated white ball, as well as cast paper. , Heat-sensitive paper and pressure-sensitive paper.

The coated paper of the present invention can be prepared by applying the coating composition for coated paper to a conventionally known method, for example, a blade coater, an air knife coater, a roll coater, a size press coater, or a cast coater. It can be manufactured by applying to a paper by the method used, performing necessary drying by a usual method, and further performing a super calender treatment as necessary.

[0031]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, each physical property was calculated | required according to the following measuring method.

(1) Viscosity of coating liquid Measured at 25 ° C. by a BL type viscometer (60 rpm, No. 3 spindle).

(2) Dry pick strength Using a RI printing tester (manufactured by Mei Seisakusho), the printing ink (S
D Super Deluxe 50 crimson B; tack value 15, manufactured by Toka Pigment Co., Ltd.) 0.4 cc is overprinted three times, and the picking state appearing on the rubber roll is backed on another backing paper, and the degree is observed. The evaluation was performed by a 5-point relative evaluation method, and the smaller the picking phenomenon, the higher the score.

(3) Wet topic strength Using a RI printing tester, the surface of the coated paper was moistened with a water-absorbing roll, and then the printing ink (SD Super Deluxe 50 red B; tack value 10, manufactured by Toka Pigment Co., Ltd.) 0 .4 cc is printed once, and the picking state appearing on the rubber roll is backed up on another backing paper, and the degree is observed. The evaluation was performed by a 5-point relative evaluation method, and the smaller the picking phenomenon, the higher the score.

(4) Ink Filling Property Using a RI printing tester, water was applied with a Molton roll, followed by solid printing under conditions that did not cause paper peeling, and ink transferability (printed ink density). And visually observe ink unevenness. The evaluation of ink deposition was performed by a 5-point relative evaluation method, and the higher the ink transferability, the higher the score. The evaluation of ink unevenness was evaluated as ○ when there was no unevenness, and x when there was unevenness.

(5) Gloss on white paper The surface of the coated paper was measured with a Murakami GM-26D type gloss meter.
Measured at 5 ° -75 °. The higher the rating, the better.

(6) Printing Gloss Using a RI printing tester, the coated paper was solid-printed with 0.4 cc of printing ink (SD Super Deluxe 50 indigo, manufactured by Toka Pigment Co., Ltd.), dried, and dried, and the Murakami GM-26D type was used. Measured at 60 ° -60 ° with a gloss meter. The higher the rating, the better.

Examples 1 to 10 As polyamine compounds, triethylenetetramine,
Diethylenetriamine, ethylenediamine (manufactured by Sumitomo Seika), Araldite AER260 as epoxy resin
(Asahi Ciba), water as solvent, dipropylene glycol monomethyl ether (manufactured by Nippon Emulsifier), and Neoperex SS-H (manufactured by Kao) as an anionic surfactant. It was synthesized by the method described below to obtain an additive for coated paper.

First, a predetermined part by weight of a polyamine compound and, if necessary, a solvent is charged into a reaction vessel, and the temperature inside the reaction vessel is adjusted to 9%.
The temperature was raised to 0 ° C. When the temperature in the reaction tank reached 90 ° C., a predetermined part by weight of the epoxy resin was fed to the reaction tank over 50 minutes to synthesize. Next, after the completion of tapping, a post-reaction was performed for 10 minutes to obtain a resin composite solution. A predetermined amount of an anionic surfactant and water were added to the obtained resin composition solution, and the mixture was uniformly mixed to obtain a coated paper additive. Next, using the obtained additive for coated paper, a composition having the following composition was prepared by the method described below to obtain a coating liquid composition for coated paper.

[Component Ratio of Coating Liquid for Coated Paper] Clay “Ultracoat, manufactured by EMC” 70 parts by weight Calcium carbonate “Super 1700, manufactured by Maruo Calcium” 30 parts by weight Dispersant: sodium polyacrylate “ARON T-” 40, manufactured by Toa Gosei Co., Ltd. 0.2 parts by weight Neutralizer: caustic soda 0.1 parts by weight Starch "Oji Ace A, manufactured by Oji Constarch" 3 parts by weight Carboxylated SB latex "L1608, manufactured by Asahi Kasei Kogyo" 11 parts by weight Paper additives prescribed parts by weight

First, 70 parts by weight of clay, 30 parts by weight of calcium carbonate, 0.2 part by weight of a dispersant (sodium polyacrylate) and 0.1 part by weight of a neutralizing agent (caustic soda) are dispersed in a predetermined amount of water. A pigment slurry was prepared. Next, 3 parts by weight of starch and 11 parts by weight of carboxylated SB latex, which were previously made into a solution, and a predetermined part by weight (see Table 3) of the synthesized coated paper additive were added thereto, followed by stirring and mixing. Water was added to prepare a paper coating liquid having a final solid content of 65% by weight.

Next, a commercially available high-quality paper was coated with this paper coating solution with a wire bar so as to have a coating amount of 13 g / m ² .
It dried with the hot air dryer (150 degreeC x 30 second). The coated paper is then subjected to a super calender (roll temperature 5
Various measurements were performed on a sample whose temperature and humidity were adjusted in a constant temperature and humidity chamber at 0 ° C., roll linear pressure of 150 kg / cm, and paper passing twice) at a temperature of 23 ° C. and a humidity of 65%. Table 3 shows the results.

Examples 11 to 12 The compound of Example 1 was used as an additive for coated paper. Example 1 The same operation as in Example 1 was carried out except that the composition was changed to 1.5 parts by weight in Example 11 and to 0.08 parts by weight in Example 12, to prepare a coating solution for coated paper, and to carry out various measurements. Was done. Table 3 shows the results.

Comparative Example 1 Each measurement was performed in the same manner as in Example 1 except that the additive for coated paper was not used. Table 4 shows the results.

Comparative Examples 2 and 3 Comparative Example 2 used 0.004 parts by weight of the additive for coated paper of Example 1, and Comparative Example 3 used 5.1 parts by weight. A measurement was made. Table 4 shows the results.

Comparative Examples 4-5 Comparative Example 4 used tetraethylenepentamine as a polyamine-based compound, Comparative Example 5 used pentaethylenehexamine (the above reagent), and the same operation as in Example 1 was carried out according to the formulation in Table 2. To obtain a coated paper additive. Next, various measurements were carried out in the same manner as in Example 1 using the obtained additive for coated paper in accordance with the composition shown in Table 4. Table 4 shows the results. In Table 4, “Thickening” in the practical properties column means
Since the viscosity of the coating liquid is as high as 10,000 cps or more and the paper cannot be coated, it indicates that the evaluation cannot be performed on the coated paper.

Comparative Example 6 Using Araldite AER6032 (manufactured by Asahi Ciba) as an epoxy resin, the same operation as in Example 1 was carried out according to the formulation in Table 2 to obtain an additive for coated paper. Next, various measurements were carried out in the same manner as in Example 1 using the obtained additive for coated paper in accordance with the composition shown in Table 4. Table 4 shows the results.

Comparative Examples 7 to 8 According to the composition shown in Table 2, the same operation as in Example 1 was carried out to obtain a coated paper additive. A measurement was made. Table 4 shows the results.

Comparative Examples 9 to 10 In Comparative Example 8, Newcol 52 was used as a nonionic surfactant.
6 (manufactured by Nippon Emulsifier) and Comparative Example 9 used Amphitol 24B (manufactured by Kao) as a cationic surfactant, and according to the formulation in Table 2, the same operation as in Example 1 was performed to obtain an additive for coated paper. . Next, various measurements were carried out in the same manner as in Example 1 using the obtained additive for coated paper in accordance with the composition shown in Table 4. Table 4 shows the results.

Comparative Examples 11 to 12 Using the additives for coated paper obtained by performing the same operations as in Example 1 in accordance with the formulations in Table 2, and in the same manner as in Example 1 in accordance with the formulations in Table 4, A measurement was made. Table 4 shows the results. In Table 4, "unmeasured" in the practical properties column means that all of the coated paper additives undergo phase separation,
Indicates that evaluation was not performed due to practical problems.

Comparative Examples 13 and 14 Using the coated paper additive of Example 1, SB latex was
Comparative Example 13 used 5 parts by weight, Comparative Example 14 used 22 parts by weight, and performed in the same manner as in Example 1 in accordance with the composition shown in Table 4, and performed various measurements. Table 4 shows the results.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

[Table 4]

[0056]

According to the present invention, the coating liquid composition for a coated paper containing the additive for coated paper obtained in the present invention has an appropriate viscosity of the coating liquid. It not only exerts an effect on the water resistance of the coated paper and coated paperboard and the wetness of the ink when wet, but also has an excellent effect on the surface strength and the printing gloss.

Claims (5)

[Claims] 1. A method comprising reacting (a) a polyamine compound with a bisphenol A type epoxy resin.
(B) 1 to 30 parts by weight of an anionic surfactant and (c) 100 to 1000 parts by weight of water with respect to 100 parts by weight of a resin composition having a N (nitrogen) content of 5 to 14% by weight in the molecule. Additive for coated paper. 2. The additive for coated paper according to claim 1, wherein the polyamine-based compound is represented by the following formula (1). H ₂ N— (CH ₂ —CH ₂ —NH) nH (1) (where 1 ≦ n ≦ 4) 3. The coated paper additive according to claim 1, wherein the bisphenol A type epoxy resin is represented by the following formula (2). Embedded image 4. The coated paper additive according to claim 1, 2 or 3 is used in an amount of 0.01 to 100 parts by weight of the coated paper pigment.
A coating liquid composition for coated paper, comprising 5.0 parts by weight and 6 to 20 parts by weight of a pigment binder. 5. A coated paper, characterized in that one or both sides of the paper are coated with the coating composition for coated paper according to claim 4 at a thickness of ² to 40 g / m ² .