JP3223752B2 - Aqueous coating composition, method for producing the same, and aqueous printing ink - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to storage stability, pigment dispersibility, and the like used for coating metal, wood, paper, leather, glass, fiber, plastic, foam, concrete and the like.
Adhesion to various substrates, to excellent water resistance printing ink printability.

[0002]

2. Description of the Related Art Conventionally, in the fields of printing inks, paints, adhesives, etc., from the viewpoint of resource saving and environmental pollution, aqueous coating materials containing inorganic powder particulate materials such as titanium oxide, magnetic powder, red iron oxide, aluminum, silica, etc. A composition has been used. However, the inorganic substance has a higher specific gravity than the organic pigment,
It had disadvantages such as poor pigment dispersion stability due to high surface hardness, severe plate and doctor wear.

[0003] In particular, an aqueous white coating agent using titanium oxide as an inorganic powdery particulate material has a necessity to increase the pigment concentration due to the appearance of hiding power. , A remarkable decrease in adhesion due to a decrease in the resin content, and a reduction in printability and coating suitability such as occurrence of plate fogging caused by lubricity of the aqueous coating agent.

[0004] Therefore, there has been proposed a method of compensating for the above-mentioned drawbacks by modifying the surface of the inorganic particulate material with a silane coupling agent. However, in this method, the amount of resin adsorbed on the surface of the inorganic powdery granular material was small, and disadvantages such as poor storage stability and dispersion stability were recognized.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to provide storage stability, pigment dispersibility, adhesion to various substrates, printability,
It is to provide a water printing ink which is excellent in coating suitability.

[0006]

The present invention provides a vinyl group,
(Meth) acryloyl group, epoxy group, and inorganic powder particulate material surface-modified with a silane coupling agent having at least one functional group selected from an amino group and a functional group capable of reacting with the functional group of the silane coupling agent comprise an aqueous resin containing a water-soluble printing ink according to claim.

The aqueous coating composition of the present invention is similar to the conventional one in that it contains an inorganic powdery substance surface-modified with a silane coupling agent and an aqueous resin.
Aqueous resin having a functional group capable of reacting with a silane coupling agent having at least one functional group selected from a vinyl group, a (meth) acryloyl group, an epoxy group and an amino group on the surface of the inorganic particulate material Is grafted. Therefore, not only water dispersibility, storage stability, pigment dispersibility, adhesion to polar substrates,
This makes it possible to improve printability.
If the surface-modified inorganic powdery particulate material does not react with the functional group-containing aqueous resin, storage stability and printability deteriorate. That is, the layer covering the surface of the inorganic powdery particulate material is detached, and the hard inorganic powdery particulate material comes into direct contact with the gravure-printed metal doctor blade, and the doctor blade is significantly worn. As a result, the ink is defective, and the ink adheres to the plate fogging, that is, the non-image area, thereby impairing the printing state.

[0008] The silane coupling agent in the present invention is
It has at least one functional group selected from a vinyl group, a (meth) acryloyl, an epoxy group and an amino group, and is represented by the following general formula (1). _{R-SiX 3-n Y n} (1) wherein R is a vinyl group or a terminal to (meth) acryloyl group, an alkyl group having at least one functional group selected from epoxy group and amino group, X is an alkyl group ,
Y is a hydrolyzable functional group bonded to a silicon atom, such as a methoxy group, an ethoxy group, or a chloro group, and n is an integer of 1 to 3.

Such silane coupling agents include vinyl tris (β-methoxyethoxy) silane, vinyl triethoxy silane, vinyl trimethoxy silane,
γ- (methacryloxypropyl) trimethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropyltri Methoxysilane, N-β- (aminoethyl) -γ-
Examples thereof include aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, and other various types of silane coupling agents.

[0010] Examples of the inorganic powdery particulate materials include calcium carbonate, kaolin, mica, aluminum hydroxide, titanium oxide, silica, zinc yellow, leadtan, red iron, zinc white, talc, carbon black, barium sulfate, magnesium carbonate, γ- Examples include inorganic fillers such as iron oxide, metal powder, asbestos, and glass fiber, magnetic powders, and pigments, but are not limited thereto, and substances having a hydrophilic surface are widely applied. The substance having a hydrophilic surface is a substance having a hydrophilic functional group such as a hydroxyl group on the surface or water of crystallization, or a substance having adsorbed water on the surface.

The amount of the silane coupling agent used for modifying the surface of the inorganic powdery particulate material with the silane coupling agent is 0.1 to 100 parts by weight based on 100 parts by weight of the inorganic powdery particulate material.
It is preferable to select within the range of 15 parts by weight, and if this amount is less than 0.1 part by weight, storage stability, pigment dispersibility, adhesion to various base materials, printability, coating suitability decrease, etc. occur. When the amount is more than 15 parts by weight, problems such as dispersibility of the pigment, coloration of printed matter and coated matter are apt to be lowered.

As a method of modifying the surface of the inorganic particulate material with a silane coupling agent, a mixer (V type) is used by adding the silane coupling agent to the inorganic particulate material as it is or by diluting it with an appropriate diluent. Mixing method, a Henschel mixer, etc.), a method of adding an inorganic powdery substance and a silane coupling agent to water or an organic solvent, and then removing the solvent, and a method of adding a silane coupling agent to an aqueous resin-inorganic powdery substance system. Is added directly.

The aqueous resin is a resin having at least one functional group capable of reacting with the functional group of the silane coupling agent, for example, a carboxyl group, an amino group, a hydrazine group or an epoxy group at the terminal, in the main chain or in the side chain. , An aqueous polyurethane resin, an aqueous acrylic resin, an aqueous polyester resin, and the like. Among them, aqueous polyurethane resins and aqueous acrylic resins are preferably used in view of the simplicity of the method of introducing a functional group capable of reacting with the functional group of the silane coupling agent.

The aqueous coating composition of the present invention comprises an inorganic powdery substance obtained by surface modification with a silane coupling agent having a vinyl group or a (meth) acryloyl group, and an aqueous resin having an amino group or a hydrazine group. Or an inorganic powdery substance obtained by surface modification with a silane coupling agent having an epoxy group, and an aqueous resin having an amino group, a hydrazine group or a carboxyl group, or a silane cup having an amino group A substance containing an inorganic powdery particulate material surface-modified with a ring agent and an aqueous resin having an epoxy group is preferable.

The content of the surface-modified inorganic particulate material in the aqueous coating composition of the present invention is preferably from 15 to 70% by weight based on the aqueous coating composition. When the content is less than 15% by weight, the color density of the printed matter and the coated matter tends to decrease. On the other hand, when the content exceeds 70% by weight, problems such as a decrease in pigment dispersibility and adhesion to various substrates are caused. It is easy to occur. The content of the aqueous resin is preferably from 5 to 25% by weight based on the aqueous coating composition. When the content is less than 5% by weight, the content of the surface-modified inorganic powdery particulate material in the aqueous coating composition is relatively increased, so that the pigment dispersibility and the adhesion to various substrates are reduced. When the content exceeds 25% by weight, the content of the surface-modified inorganic powdery particulate material in the aqueous coating composition is relatively reduced, so that the color density of printed matter and coated matter is reduced. It will be easier.

[0016] The method of grafting the inorganic powdery particulate material surface-modified with the silane coupling agent and the aqueous resin may be simply mixing at room temperature, and is not particularly limited. Promote the catalyst,
For example, triethylamine, N, N-dimethylbenzylamine, tributylamine, N, N-diethylaniline,
Tertiary amines such as N, N-dimethylaniline can be used. Although the grafting reaction proceeds only by mixing, the grafting reaction proceeds and is completed by forming a resin film by a conventional method such as printing, coating, impregnation, or spraying.

The aqueous coating composition of the present invention may contain, if necessary, other conventional components such as organic solvents, coloring pigments, dyes, emulsifiers, defoamers, surfactants, dispersing aids, and thickeners. ,
Heat stabilizers, leveling agents, anti-cratering agents, anti-settling agents, ultraviolet absorbers, flame retardants and the like can be added.

Further, by adding a usual crosslinking agent to the aqueous coating composition of the present invention, a cured film having excellent film strength and chemical resistance can be formed. For example, depending on the combination of the silane coupling agent and the aqueous resin, when an aqueous resin having a carboxyl group is used, a polyaziridine compound, a polyepoxy compound, a polycarbodiimide compound, a metal chelate compound, a polyoxazoline compound, a polyisocyanate , Blocked polyisocyanates, partially or fully etherified amino resins, and the like can be used as crosslinking agents. These crosslinking reactions can be carried out at room temperature, or can be promoted by heating or adding a known reaction catalyst.

The aqueous coating composition used in the present invention comprises:
Printing on any substrate including paper, wood, metal, glass, fiber, leather, plastic, foam, etc. as printing inks, paints, adhesives, fiber treatment agents, surface treatment agents, etc. containing inorganic powdery particulate materials A resin film can be formed by a conventional method such as coating, impregnation, spraying, etc., and is particularly suitable for printing ink.

[0020]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples unless it departs from the technical idea of the present invention. In the example,
“Parts” means “parts by weight” and “%” means “% by weight”.

The following compositions were mixed for 1 hour using a mixer, and dried in an air atmosphere at 100 ° C. for 12 hours to obtain 9 kinds of surface-modified inorganic powdery particulate materials. The amount of the silane coupling agent to be added in the production of the silane coupling agent-treated inorganic powdery particulate materials (A) to (G) is theoretically determined from the weight of the inorganic powdery particulate material, the specific surface area, and the minimum covering area of the silane coupling agent. The surface of the inorganic powdery particulate material is 10
The amount added was 0% coating.

(Silane Coupling Agent-Treated Inorganic Powder Particulate (A)) Rutile-type titanium oxide (Ishihara Sangyo Co., Ltd.) 100 parts γ-glycidoxypropyltrimethoxysilane 4.5 parts (Shin-Etsu Silicone Co., Ltd. “KBM403”) )

(Silane Coupling Agent-Treated Inorganic Powder Particulate (B)) Rutile-type titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.) 100 parts Vinyl trimethoxysilane 2.9 parts (“KBM1003” manufactured by Shin-Etsu Silicone Co., Ltd.)

(Silane Coupling Agent-Treated Inorganic Powder Granular Material (C)) Rutile-type titanium oxide (Ishihara Sangyo Co., Ltd.) 100 parts γ-methacryloxypropyltrimethoxysilane 4.8 parts (Shin-Etsu Silicone Co., Ltd. “KBM503”)

(Silane Coupling Agent-Treated Inorganic Powder Granular Material (D)) Rutile-type titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.) 100 parts N-β- (aminoethyl) -γ-aminopropyl 4.3 parts trimethoxysilane ( Shin-Etsu Silicone “KBM603”)

(Silane-Coupled Agent-Treated Inorganic Powder Particulate (E)) Rutile-type titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.) 100 parts Hexyltrimethoxysilane 4.0 parts (“TSL8241” manufactured by Toshiba Silicone Co., Ltd.)

(Silane Coupling Agent-Treated Inorganic Powder Particulate (F)) Bengala (red iron oxide) 100 parts γ-glycidoxypropyltrimethoxysilane 4.4 parts (“KBM403” manufactured by Shin-Etsu Silicone Co., Ltd.)

(Silane Coupling Agent-Treated Inorganic Powder Granular Material (G)) Bengala (red iron oxide) 100 parts Hexyltrimethoxysilane 4.0 parts (“TSL8241” manufactured by Toshiba Silicone Co., Ltd.)

(Silane Coupling Agent Treated Inorganic Powder Granular Material (H)) Rutile Titanium Oxide (Ishihara Sangyo Co., Ltd.) 100 parts γ-glycidoxypropyltrimethoxysilane 0.1 part (Shin-Etsu Silicone Co., Ltd. “KBM403”) )

(Silane Coupling Agent-Treated Inorganic Powder Granular Material (I)) Rutile-type titanium oxide (Ishihara Sangyo Co., Ltd.) 100 parts γ-glycidoxypropyltrimethoxysilane 15 parts (Shin-Etsu Silicone Co., Ltd. “KBM403”)

(Synthesis Example 1 of Resin) In a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 67.1 parts of polybutylene adipate glycol and polyethylene glycol were added.
7.5 parts, 14.3 parts of dimethylolpropionic acid, and 90 parts of methyl ethyl ketone are charged and heated to 80 ° C. under a nitrogen atmosphere while stirring. After the temperature was stabilized, 48.0 parts of isophorone diisocyanate was added dropwise, and 0.015 part of dibutyltin dilaurate and methyl ethyl ketone 10
Of the solution, and reacted at the same temperature for 3 hours to obtain an isocyanate group-containing polymer solution. Further, the temperature of the reaction solution was cooled to 30 ° C. or lower, and isophorone diamine 13.0 was added.
After a drop of a mixture of 25 parts of water, 200 parts of water and 200 parts of acetone was added dropwise over 1 hour, the temperature was raised to 50 ° C. to terminate the reaction. Then 2
A mixture of 7.2 parts of 5% aqueous ammonia and 320 parts of water was added dropwise to obtain an aqueous dispersion of a polyurethane resin. The resulting aqueous dispersion was desolvated at 60 ° C. under reduced pressure to obtain an aqueous dispersion (1) (solid content: 30%) of a polyurethane resin having a carboxyl group and an amino group at a terminal.

(Synthesis Example 2 of Resin) After a polymer solution containing an isocyanate group was obtained in the same manner as in Synthesis Example 1, the temperature of the reaction solution was cooled to 30 ° C. or less.
After a mixture of 1.5 parts and 150 parts of acetone was added dropwise over 1 hour, the mixture was reacted at the same temperature for 30 minutes to obtain a high molecular weight isocyanate group-containing polymer solution. Next, a mixture of 1.5 parts of adipic dihydrazide, 25 parts of water and 50 parts of acetone was added dropwise, and then the temperature was raised to 50 ° C. to terminate the reaction. Next, 7.2 parts of 25% ammonia water and water 32
0 parts of the mixture was added dropwise to obtain an aqueous dispersion of a polyurethane resin. The obtained aqueous dispersion is desolvated at 60 ° C. under reduced pressure to obtain an aqueous dispersion of a polyurethane resin having a carboxyl group and a hydrazine functional group at a terminal (2).
(Solid content 30%) was obtained.

(Synthesis example 3 of resin) 67.4 parts of polybutylene adipate glycol, polyethylene glycol
7.5 parts, 14.3 parts of dimethylolpropionic acid, and 90 parts of methyl ethyl ketone are charged into the same apparatus as in Synthesis Example 1, and heated to 80 ° C. under a nitrogen atmosphere while stirring. When the temperature was stabilized, 48.1 parts of isophorone diisocyanate was added dropwise, and then a solution of 0.015 part of dibutyltin dilaurate and 10 parts of methyl ethyl ketone was added, followed by reaction at the same temperature for 3 hours to obtain an isocyanate group-containing polymer solution. Further, the temperature of the reaction solution was cooled to 30 ° C. or lower, and 11.5 parts of isophorone diamine and 1.1 parts of dibutylamine 1.1 were added.
And a mixture of 200 parts of acetone over 1 hour, and the temperature was raised to 50 ° C. to terminate the reaction. Next, a mixture of 5.5 parts of 25% aqueous ammonia and 345 parts of water was added dropwise to obtain an aqueous dispersion of a polyurethane resin. The resulting aqueous dispersion was desolvated at 60 ° C. under reduced pressure to obtain an aqueous dispersion (3) of a polyurethane resin having a carboxyl group (solid content: 30%).

(Synthesis example 4 of resin) 24.2 parts of t-butyl methacrylate, 15.7 parts of n-butyl acrylate, 2.4 parts of 2-hydroxyethyl acrylate, 12.1 parts of polyethylene oxide acrylate, Acrylic acid 6.0
Parts, azobisisobutyronitrile 2.4 parts, water 11.
5 parts and 104 parts of isopropyl alcohol were charged into the same apparatus as in Synthesis Example 1 and stirred under a nitrogen atmosphere under a nitrogen atmosphere.
Heat to ° C. When the temperature was stabilized, 24.2 parts of t-butyl methacrylate and n-butyl acrylate were added to the dropping tube.
7 parts, 2.4 parts of 2-hydroxyethyl acrylate, 12.1 parts of polyethylene acrylate, 6.0 parts of acrylic acid, 11.5 parts of water, and 104 parts of isopropyl alcohol are added dropwise to the reaction layer over 1 hour. I do. After reacting at the same temperature for 3 hours, cool down to 60 ° C or less and 25%
6.3 parts of aqueous ammonia and 311 parts of water were added to obtain an aqueous dispersion of an acrylic resin. The resulting aqueous dispersion is desolvated at 60 ° C. under reduced pressure, and then 26.6 parts of water is added to obtain an aqueous dispersion (4) of an acrylic resin having a carboxyl group (solid content: 30%). Was.

(Synthesis Example 5 of Resin) A carboxyl group and an epoxy resin were prepared in the same manner as in Synthesis Example 4 except that 6.0 parts of glycidyl methacrylate were added to the same apparatus as in Synthesis Example 1 and the raw materials placed in the dropping tube, respectively. An aqueous dispersion (5) of an acrylic resin having a group (solid content: 30%) was obtained.

[0036]

Example 1 An aqueous dispersion (1) of a polyurethane resin having a carboxyl group and an amino group at a terminal was added to 40 parts of an inorganic powdery particulate material (A) treated with a silane coupling agent;
6 parts of water and 5 parts of isopropyl alcohol were added to obtain an aqueous printing ink by a conventional method.

[0037]

Example 2 An aqueous dispersion of a polyurethane resin having a carboxyl group and a hydrazine functional group at a terminal in 40 parts of an inorganic powdery particulate material (A) treated with a silane coupling agent (2)
49 parts, 6 parts of water and 5 parts of isopropyl alcohol were added to obtain an aqueous printing ink by a conventional method.

[0038]

Example 3 To 40 parts of a silane coupling agent-treated inorganic powdery particulate material (A), 49 parts of an aqueous dispersion of a polyurethane resin having a carboxyl group (3), 6 parts of water, and 5 parts of isopropyl alcohol were added. An aqueous printing ink was obtained by the method.

[0039]

Example 4 An aqueous dispersion (5) of an acrylic resin having a carboxyl group and an epoxy group was added to 40 parts of an inorganic powdery particulate material (D) treated with a silane coupling agent, 49 parts, and 6 parts of water.
5 parts of isopropyl alcohol was added, and an aqueous printing ink was obtained by a conventional method.

[0040]

Example 5 An aqueous dispersion (1) of a polyurethane resin having a carboxyl group and an amino group at the terminal was added to 49 parts of a silane coupling agent-treated inorganic powdery particulate material (B) (40 parts).
6 parts of water and 5 parts of isopropyl alcohol were added to obtain an aqueous printing ink by a conventional method.

[0041]

EXAMPLE 6 An aqueous dispersion (2) of a polyurethane having a carboxyl group and a hydrazine functional group at a terminal in 40 parts of an inorganic powdery particulate material (B) treated with a silane coupling agent.
Parts, 6 parts of water and 5 parts of isopropyl alcohol were added to obtain an aqueous printing ink by a conventional method.

[0042]

Example 7 49 parts of an aqueous dispersion (1) of a polyurethane resin having a carboxyl group and an amino group at a terminal was added to 40 parts of a silane coupling agent-treated inorganic powdery particulate material (C),
6 parts of water and 5 parts of isopropyl alcohol were added to obtain an aqueous printing ink by a conventional method.

[0043]

Example 8 An aqueous dispersion of a polyurethane resin having a carboxyl group and a hydrazine functional group at a terminal in 40 parts of an inorganic powdery particulate material (C) treated with a silane coupling agent (2)
49 parts, 6 parts of water and 5 parts of isopropyl alcohol were added to obtain an aqueous printing ink by a conventional method.

[0044]

Example 9 To 50 parts of an inorganic powdery particulate material (F) treated with a silane coupling agent, 45 parts of an aqueous dispersion (4) of an acrylic resin having a carboxyl group and 5 parts of water were added and kneaded with a three-roll mill. Paint was obtained.

[0045]

Example 10 An aqueous dispersion (1) of a polyurethane resin having a carboxyl group and an amino group at a terminal in 40 parts of a silane coupling agent-treated inorganic powdery particulate material (H) (49)
Parts, 6 parts of water and 5 parts of isopropyl alcohol were added to obtain an aqueous printing ink by a conventional method.

[0046]

Example 11 An aqueous dispersion (1) of a polyurethane resin having a carboxyl group and an amino group at the terminal in 40 parts of a particulate inorganic substance (I) treated with a silane coupling agent (49)
Parts, 6 parts of water and 5 parts of isopropyl alcohol were added to obtain an aqueous printing ink by a conventional method.

[0047]

Example 12 An aqueous dispersion (1) of a polyurethane resin having a carboxyl group and an amino group at the terminal in 15 parts of the inorganic powder particulate material (A) treated with a silane coupling agent (70)
, 7 parts of water and 8 parts of isopropyl alcohol were added to obtain an aqueous printing ink by a conventional method.

[0048]

Example 13 An aqueous dispersion (1) of a polyurethane resin having a carboxyl group and an amino group at the terminal in 70 parts of a silane coupling agent-treated inorganic powdery particulate material (A) (20)
Parts, 5 parts of water and 5 parts of isopropyl alcohol were added to obtain an aqueous printing ink by a conventional method.

[0049]

Example 14 An aqueous dispersion (1) of a polyurethane resin having a carboxyl group and an amino group at the terminal in 69.3 parts of an inorganic powdery particulate material (A) treated with a silane coupling agent
6.7 parts, 8 parts of water and 6 parts of isopropyl alcohol were added, and an aqueous printing ink was obtained by a conventional method.

[0050]

Example 15 An aqueous dispersion of a polyurethane resin having a carboxyl group and an amino group at a terminal in 15 parts of a granular inorganic substance (A) treated with a silane coupling agent (1)
3 parts, 1 part of water and 0.7 parts of isopropyl alcohol were added, and an aqueous printing ink was obtained by a conventional method.

[0051]

Example 16 An aqueous dispersion (1) of a polyurethane resin having a carboxyl group and an amino group at an end in 40 parts of a silane coupling agent-treated inorganic powdery particulate material (A) 49
Parts, 5.5 parts of water, 5 parts of isopropyl alcohol, and 0.5 part of triethylamine were added to obtain an aqueous printing ink by a conventional method.

[0052]

[Comparative Example 1] 40 parts of rutile type titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.) not subjected to surface modification with a silane coupling agent,
49 parts of an aqueous dispersion (3) of a polyurethane resin having a carboxyl group, 6 parts of water, and 5 parts of isopropyl alcohol were added, and an aqueous printing ink was obtained by a conventional method.

[0053]

COMPARATIVE EXAMPLE 2 To 40 parts of an inorganic powdery particulate material (E) treated with a silane coupling agent, 49 parts of an aqueous dispersion (3) of a polyurethane resin having a carboxyl group, 6 parts of water, and 5 parts of isopropyl alcohol were added. An aqueous printing ink was obtained by the method.

[0054]

Comparative Example 3 Aqueous dispersion (4) of an acrylic resin having a carboxyl group (solid content 30) was added to 50 parts of red iron oxide (red iron oxide) not subjected to surface modification with a silane coupling agent.
%) And 5 parts of water were added, and the mixture was kneaded with three rolls to obtain an aqueous coating composition.

[0055]

Comparative Example 4 45 parts of an aqueous dispersion (4) of an acrylic resin having a carboxyl group and 5 parts of water were added to 50 parts of an inorganic powdery particulate material (G) treated with a silane coupling agent, and kneaded with a three-roll mill. Paint was obtained.

Examples 1 to 8, 10 to 16 and Comparative Examples 1 to
Table 1 shows the measurement results of the 180-degree peel adhesive strength of a laminate obtained by performing gravure printing on a corona discharge-treated polyester film and a corona discharge-treated polypropylene film for the aqueous printing ink obtained in Example 2 and extrusion laminating low density polyethylene. Shown in Table 1 shows the evaluation results of the coloring properties, storage stability, printing suitability (plate fogging properties), and coating suitability of the aqueous coating composition obtained in Examples 1 to 16 and Comparative Examples 1 to 4. . The measurement was performed as follows.

(1) Peeling Adhesive Strength of the Extrusion-Laminated Laminate The obtained aqueous printing ink was applied to 45 parts of water and ethanol 40 using Zahn Cup # 3 (manufactured by Rigosha Co., Ltd.) to 18 (25 ° C.). Parts and a mixed solvent of 15 parts of isopropanol, adjusted by a corona discharge treatment polyester film (“Ester E5100” manufactured by Toyobo Co., Ltd., thickness: 12 μm),
Gravure printing at a drying temperature of 60 ° C. and a printing speed of 80 m / min using a gravure plate having a plate depth of 25 μm on a corona discharge treated surface of a corona discharge treated polypropylene film (“Pyren P2161” manufactured by Toyobo Co., Ltd., thickness: 20 μm). Was done. A polyethyleneimine-based anchor coat agent (“EL-42” manufactured by Toyo Morton Co., Ltd.)
0 ") or a polyisocyanate anchor coating agent (" EL-510A / AD RT-8 "manufactured by Toyo Morton Co., Ltd.)
0 "), and low-density polyethylene (" Yukaron LK-30 "manufactured by Mitsubishi Yuka Co., Ltd.) was extrusion-laminated on the coated surface to obtain a laminate. The laminate obtained using the polyisocyanate anchor coating agent was aged at 40 ° C. for 3 days. Next, the laminated body is 15 mm in width.
And a 180 ° peel adhesion was measured at a peel rate of 300 mm / min under conditions of 25 ° C. and 65% relative humidity.

(2) Color Development The appearance of the printed and coated products was visually evaluated comprehensively from the viewpoints of density, gloss and transparency (（: excellent, ×: poor). When the pigment dispersibility was good, the color development was good.

(3) Storage stability The appearance of the obtained aqueous coating composition after storage at 40 ° C. for 1 week was visually evaluated (（: no change, x: change).

(4) Printing suitability (plate fogging property) and coating suitability With respect to the aqueous printing ink, 45 parts of water and ethanol 40 were used using Zahn Cup # 3 (manufactured by Rigosha Co., Ltd.) to reach 18 seconds (25 ° C.). And a mixture of 15 parts of isopropanol and a gravure plate having a depth of 25 μm on a corona-discharge treated surface of a corona-discharge treated polypropylene film (“Pyrene P2161” manufactured by Toyobo Co., Ltd., thickness: 20 μm). Drying temperature 50 ° C, printing speed 50m using
/ Min for 30 minutes. Next, 10 sheets of the obtained printed matter were overlapped so that the image area and the non-image area did not overlap, and the state of the non-image area was visually evaluated (評 価: no fog on the plate, ×: fog on the plate). Regarding the water-based paint, the state of the nozzle, the bleeding of the paint, and the dripping of the paint after spray coating on 100 glass plates (area of 2500 cm2 per sheet) were evaluated using a spray gun (（: excellent;
X; poor).

[0061]

[Table 1]

[0062]

According to the present invention, an aqueous printing ink having excellent storage stability, pigment dispersibility, adhesion to various substrates, and printability is provided.
Niki can now provide. Water-based printing ink of the present invention
G is particularly excellent in adhesion to a different polarity substrate .

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C09D 11/10

Claims (2)

(57) [Claims] An inorganic powdery substance surface-modified with a silane coupling agent having at least one functional group selected from a vinyl group, a (meth) acryloyl group, an epoxy group and an amino group, and a silane coupling agent. An aqueous printing ink comprising an aqueous resin containing a functional group capable of reacting with a functional group. 2. An inorganic powdery particulate material surface-modified with a silane coupling agent having at least one functional group selected from a vinyl group, a (meth) acryloyl group, an epoxy group and an amino group, and a silane coupling agent. A method for producing an aqueous printing ink, comprising an aqueous resin containing a functional group capable of reacting with a functional group.