JPH07247455A - Drying retarder for aqueous resin composition and retardation of drying of aqueous resin composition - Google Patents

Abstract

PURPOSE:To obtain a drying retarder composed of diethylethanolamine and diethylethanolamine, capable of retarding drying of an extender-containing aqueous resin composition on a plate or a coater without retarding drying on paper. CONSTITUTION:This drying retardant is composed of dimethylethanolamine and/or drethylethanolamine represented by the formula (R<1> and R<2> are each a 1 to 2C alkyl). For retarding drying of an extender-containing aqueous resin composition composed mainly of an extender pigment, a carboxyl group- containing aqueous resin such as a styrene-maleic acid copolymer, a basic compound for neutralizing the resin and water by using this retardant, a volatile basic compound is contained in an amount of >=0.3 time equivalent to the amount required for neutralizing the aqueous resin as the basic compound, and the retardant of the formula as the volatile basic compound is recommendably contained in an amount of >=0.05 times equivalent to the above-mentioned amount required for neutralization in the composition. In addition, a preferable combination of the basic compounds is a combination of ammonia with a drying retardant of the formula.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a drying delay agent for an aqueous resin composition containing an extender pigment and a method for delaying the drying of an aqueous resin composition containing an extender pigment. More specifically, when an aqueous resin composition containing an extender pigment is printed or coated on paper or the like, the extender pigment-containing aqueous resin composition that delays the drying on a plate or a coater and does not prevent the on-paper drying. TECHNICAL FIELD The present invention relates to a drying delay agent and a drying delay method.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for water-based printing ink compositions for printing on paper containers such as cardboard and cartons and various paper bags, and water-based resin compositions for coating on paper and plastic films. .

Further, in order to increase the printing speed and improve the efficiency, there is a demand for a super quick-drying type water-based ink.

These aqueous resin compositions having a high drying property and a good fluidity are mainly composed of a carboxyl group-containing aqueous resin, ammonia and water, and the addition of an extender pigment such as calcium carbonate and precipitated barium sulfate. Is essential.

However, this type of aqueous resin composition has a problem that it is dried on a plate or anilox during printing to cause clogging. Therefore, organic amines such as monoethanolamine and morpholine are used as a drying delay agent, but if the drying on the plate is delayed,
There is a problem that drying on paper becomes slow and high-speed printing cannot be supported.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems of the prior art.
An object of the present invention is to provide a drying delay agent for an extender-containing aqueous resin composition that delays drying on a plate or a coater and does not prevent drying on paper, and a method for delaying drying of the extender-containing aqueous resin composition.

[0007]

Means for Solving the Problems As a result of repeated studies to solve the above problems, the present inventors have found that a basic compound of an aqueous resin composition contains dimethylethanolamine, diethylethanolamine or the like as a drying retarder. It was found that the above problem can be solved by containing the compound as, and the present invention has been completed.

That is, the present invention has the general formula (1):

[0009]

[Chemical 3]

(In the formula, R ¹ and R ² independently have 1 carbon atom.
Alternatively, the present invention relates to a dry retarder for an aqueous resin composition containing an extender pigment, which comprises a compound represented by 2).

Further, the present invention provides an extender pigment, a carboxyl group-containing aqueous resin, a basic compound of at least a neutralizing amount with respect to the carboxyl group-containing aqueous resin, and an aqueous resin composition containing water as a main component. A volatile basic compound is contained as a compound in an amount of 0.3 equivalent or more of the neutralization amount with respect to the carboxyl group-containing aqueous resin, and the volatile basic compound has the general formula (1):

[0012]

[Chemical 4]

(In the formula, R ¹ and R ² independently have 1 carbon atom.
Alternatively, the present invention relates to a method for delaying drying of an extender-pigment-containing aqueous resin composition, characterized by containing 0.03 equivalent or more of the neutralization amount of a drying retarder represented by 2).

The present invention also provides the method of delaying drying, wherein the neutralizing amount of the volatile basic compound is 0.
The present invention relates to a method for delaying drying of an extender pigment-containing aqueous resin composition, wherein 05 to 0.3 equivalent is dimethylethanolamine and / or diethylethanolamine.

[0015]

Functions and Examples One of the effective methods for improving the drying property of the aqueous resin composition is to increase the solid content in the system. At present, two methods have been mainly attempted for that purpose, one is a method of adding a large amount of emulsion resin, and the other is a method of adding an extender pigment. Here, the method of adding a large amount of the emulsion resin is not preferable because it significantly reduces the fluidity of the aqueous resin composition, particularly during printing. On the other hand, the aqueous resin composition containing a large amount of extender pigment is very effective because the fluidity does not decrease. However, an aqueous resin composition having a high drying property is dried on the plate during printing and is not redissolved, causing clogging and the like, and a good printed matter cannot be obtained. When a highly volatile component such as ammonia is used as the basic compound for neutralizing the aqueous resin, it is impossible to prevent the aqueous resin composition from drying on the plate. On the other hand, when monoethanolamine or triethanolamine is used as the basic compound, since these are low-volatile components, drying on the plate can be delayed, but at the same time, drying on the paper is also delayed. Since the drying retardant specified in the present invention is a low volatile component, it delays the drying of the aqueous resin composition on the plate, but since it is a hydrophobic component as compared with monoethanolamine and the like, after being printed on paper. Drains water from the system faster,
It does not impair the drying on paper. The present invention has found that a good printed matter can be printed at high speed by using a drying delay agent that delays the drying property of the aqueous resin composition on a plate and does not prevent the drying on paper.

The present invention will be described in detail below.

The aqueous resin composition of the present invention is mainly composed of a carboxyl group-containing aqueous resin, an extender pigment, a basic compound, and water.

First, as the carboxyl-containing aqueous resin used in the aqueous resin composition of the present invention, an alkali-soluble aqueous resin having an acid value of 10 to 350 or a self-emulsifying aqueous resin can be generally used. Specific examples of the alkali-soluble aqueous resin include styrene-maleic acid copolymer, styrene-acrylic copolymer, styrene-acrylic-maleic acid copolymer, rosin-modified maleic acid resin, acrylic resin, maleic acid resin and the like. Can be illustrated. Also,
The self-emulsifying aqueous resin is a resin that can be self-emulsifying in the presence of a basic compound, and specific examples include styrene-maleic acid copolymers, styrene-acrylic copolymers,
Examples thereof include styrene-acrylic-maleic acid copolymer, rosin-modified maleic acid resin, acrylic resin, maleic acid resin and the like. When the acid value of these carboxyl group-containing aqueous resins is less than 10, dissolution or self-emulsification becomes difficult,
On the other hand, when it exceeds 350, the water resistance is inferior.

Even if the resin has an acid value smaller than the above, it does not hinder the use of a resin having a hydroxyl group or the like introduced into its molecule and capable of being dispersed in water.

As the water-dispersible resin containing no carboxyl group which can be used in combination with the above-mentioned carboxyl group-containing aqueous resin, a carboxyl group obtained by emulsion polymerization of acrylic, styrene or other vinyl monomer is used. A water-dispersible resin that does not contain it can be used.

Next, the basic compound that neutralizes the aqueous resin composition will be described.

As the basic compound for neutralizing the carboxyl group-containing aqueous resin, ammonia, ethylamine,
Highly volatile basic compounds such as diethylamine and triethylamine, low volatile basic compounds such as morpholine, monoethanolamine and diethanolamine, and dry retarders such as dimethylethanolamine and diethylethanolamine represented by the general formula (1) are used. It can be illustrated.

The amount of the volatile basic compound used is 0.3 equivalent or more of the neutralization amount with respect to the carboxyl group-containing aqueous resin, and among them, dimethylethanolamine and / or the compound represented by the general formula (1) is used. A drying retarder such as diethylethanolamine is used as an essential component, and the amount used is 0.03 equivalent or more of the neutralization amount, preferably 0.0
It is 5 equivalents or more.

The amount of the volatile basic compound used is 0.
If the amount is less than 3 equivalents, problems such as deterioration of water resistance and dryness of the aqueous resin composition occur.

When the amount of the dry retarder such as dimethylethanolamine and / or diethylethanolamine represented by the general formula (1) is less than 0.03 equivalent,
There arises a problem of drying on the plate and a problem of lowering the fluidity of the aqueous resin composition.

Further, the total amount of the basic compound for neutralizing the carboxyl group of the carboxyl group-containing aqueous resin may be used as a drying retarder such as dimethylethanolamine and / or diethylethanolamine represented by the general formula (1). However, when the water resistance and the drying property of the water-based resin composition are required, it is preferable to use the neutralization amount of 0.3 equivalent or less.

Further, a non-volatile basic compound such as sodium hydroxide or potassium hydroxide having a neutralization amount of 0.
It can be used together up to about 7 equivalents.

A particularly preferred combination of basic compounds is a combination of ammonia and dimethylethanolamine and / or diethylethanolamine from the viewpoint of excellent water resistance, drying property and drying retardation property on a plate.

The total amount of the basic compound used is 1.0 with respect to the carboxyl groups of the carboxyl group-containing aqueous resin.
Approximately 1.2 equivalents are preferable, and an excess amount can be used, but the effect of dissolving or dispersing the aqueous resin composition in water is not significantly different from the case of using 1.0 to 1.2 equivalents. Will be things.

Finally, as an extender pigment for improving the dryness, water resistance and wettability of water repellent paper of the aqueous resin composition,
Examples thereof include calcium carbonate, magnesium carbonate, precipitated barium sulfate, aluminum hydroxide and the like, and these can be used alone or in combination of two or more kinds.

The aqueous resin composition according to the present invention comprising the above-mentioned various materials is usually 5 to 50% by weight of a carboxyl group-containing aqueous resin and 5 to 60% of an extender pigment as a solid content in the aqueous resin composition. It is the one containing wt%. If the amount of the carboxyl group-containing aqueous resin used is less than 5% by weight, the film forming ability of the aqueous resin composition will be low, and if it exceeds 50% by weight, the fluidity will be reduced. The amount of extender pigment used is
If it is less than 5% by weight, the drying property on paper of the aqueous resin composition is not improved, and if it exceeds 60% by weight, the stability of the aqueous resin composition is lowered.

Various additives such as a colorant, a defoaming agent, a water-miscible solvent, a plasticizer, a pigment dispersant, and a wax can be appropriately used in the aqueous resin composition according to the present invention, if necessary.

The aqueous resin composition according to the present invention is manufactured by neutralizing the carboxyl group-containing aqueous resin with a basic compound and then mixing with an extender pigment, and if necessary, a colorant and various additives, followed by a dispersing machine. It can be performed according to a conventional method using a kneading machine.

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

First, the respective components of the aqueous printing ink compositions used in Examples and Comparative Examples, that is, the carboxyl group-containing aqueous resin, the extender pigment, the basic compound, the colorant, and the defoaming agent will be described.

(1) Basic compound Ammonia, dimethylethanolamine, diethylethanolamine, sodium hydroxide (2) Carboxyl group-containing aqueous resin 1. Alkali-soluble aqueous resin solution Styrene-acrylic resin, John Cryl J-68, manufactured by Johnson Polymer Co. (acid value 195, molecular weight 10,000,
A resin acid value having a glass transition temperature of 70 ° C. and a solid content of 100%) was neutralized using the above basic compound so that the equivalent ratio shown in Table 1 was obtained, and an alkali having a solid content of 25% by weight and a pH of 8.0 was used. Soluble aqueous resin solutions 1 to 17 were obtained.

2. Self-Emulsifying Aqueous Resin Dispersion 1 Styrene-acrylic emulsion, Jonkryl J-7
80, manufactured by Johnson Polymer Co., Ltd. (acid value 49, glass transition temperature 95 ° C., solid content 48% by weight, basic compound: neutralizing amount of ammonia). Self-Emulsifying Aqueous Resin Dispersion 2 Styrene-acrylic emulsion, Jonkryl J-7
4, manufactured by Johnson Polymer (acid value 54, glass transition temperature 28 ° C., solid content 45% by weight, basic compound: neutralizing amount of ammonia) (3) Colorant Fast Gemble-TGR, Dainippon Ink and Chemicals ( Co., Ltd. (4) Extender pigment calcium carbonate, white luster DD, Shiraishi Calcium Co., Ltd. (5) Defoamer Silicone defoamer

[0038]

[Table 1]

Examples 1 to 13 and Comparative Examples 1 to 6 Alkali-soluble aqueous resin solutions 1 to 17, self-emulsifying aqueous resin dispersion 1, self-emulsifying aqueous resin dispersion 2, extender pigment, colorant A defoaming agent and water were kneaded and mixed in a sand mill so that the formulations shown in Table 2 were obtained, to prepare an aqueous printing ink composition. The obtained water-based printing ink composition was subjected to the following tests. The results are shown in Table 2. Table 2
In, the amount of each component is part by weight.

[Test Method] (1) Water Resistance: Each of the aqueous printing ink compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 6 was coated with a coated paper and Rengo CRC (Rengo CRC) using a hand puller. (Made by the company). Using the Gakushin-type dyeing friction fastness tester (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), the developed product was rubbed 5 times with a bleaching cloth soaked in water under a load of 200 g to expose it The evaluation was made based on how much ink was taken in. Evaluation Criteria A: There is no ink stain on the bleached cloth. B: A small amount of ink stains on the bleached cloth. C: A considerably large amount of ink stains on the exposed cloth occur. D: The ink is completely exposed and taken up on the cloth.

(2) Dryability on paper: The water-based printing ink compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 6 were mixed with each other.
A 15 mm bar coater was used to develop color on coated paper, Rengo CRC (manufactured by Rengo Co., Ltd.), and the finger touch test was performed to evaluate the ink removal. Evaluation Criteria A: No ink adhered to a finger at 10 seconds after color development. B: No ink adhered to the finger after 30 seconds from the color development. C: No ink adhered to the finger at 120 seconds after the color development. D: Ink adhered to the finger at 120 seconds after the color development.

(3) Dryability on plate: Each of the aqueous printing ink compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 6 was treated with 0.
A 15 mm bar coater was used to develop the color on the flexographic Sirel plate, and the finger touch test was performed to evaluate the ink removal. Evaluation Criteria A: Those that dry for more than 30 seconds. B: Those that dry in 10 to 30 seconds. C: Drying within 10 seconds.

(4) Flowability: Using each of the aqueous printing ink compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 6, the printing machine was run idle under an atmosphere of 40 ° C. Was continuously circulated for 12 hours (at this time, the liquid amount was made constant by adding water corresponding to the volatile component so that the ink amount in the circulation tank became constant). After that, the viscosity of the ink was measured at 30 rpm using a B type viscometer, and the following viscosity ratio was determined for determination. Viscosity ratio = viscosity of ink after circulation for 12 hours / initial viscosity evaluation criteria A: Viscosity ratio of 1.5 or less. B: A viscosity ratio of more than 1.5 and 2.0 or less. C: A viscosity ratio of more than 2.0 and 4.0 or less. D: A viscosity ratio of more than 4.0.

[0044]

[Table 2]

Next, a preferred embodiment of the present invention will be shown.

(1) A method for delaying drying of an extender pigment-containing aqueous resin composition according to claim 2, wherein the basic compound comprises ammonia and dimethylethanolamine and / or diethylethanolamine.

(2) In the invention described in (1) above, the total amount of ammonia and dimethylethanolamine and / or diethylethanolamine is 0.
3 equivalents or more, dimethylethanolamine and /
Alternatively, the total amount of diethanolamine is 0.
A method for drying an extender-pigment-containing aqueous resin composition having an equivalent weight of 05 to 0.3.

(3) In the invention of claim 2 or the invention of (1) or (2), the carboxyl group-containing aqueous resin is an alkali-soluble aqueous resin having an acid value in the range of 10 to 350, and / or Alternatively, a method for delaying drying of an extender pigment-containing aqueous resin composition which is a self-emulsifying aqueous resin having an acid value in the range of 10 to 350.

(4) Claim 2 or (1),
In the invention of (2) or (3), the extender pigment-containing aqueous resin composition, wherein the extender pigment is at least one selected from the group consisting of calcium carbonate, magnesium carbonate, precipitated barium sulfate, and aluminum hydroxide. How to delay drying of goods.

[0050]

INDUSTRIAL APPLICABILITY According to the present invention, a basic compound of an extender-pigment-containing aqueous resin composition is allowed to contain a drying retardant such as dimethylethanolamine and / or diethylethanolamine, whereby the aqueous resin composition On the plate,
Delays drying on the coater and does not prevent drying on paper.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Masataka, 23-23 Edobori, Nishi-ku, Osaka City, Sakata Inx Co., Ltd. (72) Hideki Nagashima 1-23-37 Edobori, Nishi-ku, Osaka City, Sakata Inx In the company

Claims (3)

[Claims] 1. General formula (1): (In the formula, R ¹ and R ^{2 each} independently represent an alkyl group having 1 or 2 carbon atoms), a dry retarder for an extender pigment-containing aqueous resin composition. 2. An extender pigment, a carboxyl group-containing aqueous resin, a basic compound in an amount at least neutralized with respect to the carboxyl group-containing aqueous resin, and an aqueous resin composition containing water as a main component, wherein the basic compound is: The volatile basic compound is contained in an amount of 0.3 equivalent or more of the neutralization amount with respect to the carboxyl group-containing aqueous resin, and the volatile basic compound is represented by the general formula (1): (In the formula, R ¹ and R ² independently represent an alkyl group having 1 or 2 carbon atoms) 0.03 equivalent or more of the neutralization amount is contained in an extender-containing pigment. A method for delaying drying of an aqueous resin composition. 3. The volatile basic compound, wherein 0.05 to 0.3 equivalents of the neutralized amount is dimethylethanolamine and / or diethylethanolamine. A method for delaying drying of an extender pigment-containing aqueous resin composition.