JP2022148346A - Manufacturing method of decorative product - Google Patents

Abstract

To provide a manufacturing method of a decorative product which can suppress glossiness of a print decorative part and achieve the excellent bending workability.SOLUTION: A manufacturing method of a decorative product includes applying processing liquid 1 and processing liquid 2 to a metal base after applying ink containing a color material to the metal base. The processing liquid 1 contains a water dispersible resin whose glass transition point is equal to or greater than 0°C. The processing liquid 2 contains a coagulant that coagulates the water dispersible resin whose glass transition point is equal to or greater than 0°C of the processing liquid 1. The processing liquid 2 and the processing liquid 1 are applied to the metal base in the order of the processing liquid 2 and the processing liquid 1.SELECTED DRAWING: None

Description

An embodiment of the present invention relates to a method for manufacturing a decorative article.

Decorated base materials are widely used for indoor and outdoor applications such as building materials, furniture, and daily necessities. Among various substrates, metal substrates are utilized in various applications due to their properties such as heat resistance, durability, and workability.

As a method of decorating a metal substrate, for example, there is a method of adding colors and patterns by printing, and examples of printing colors and patterns on metal substrates and using them for construction materials and the like are increasing. There are various printing methods such as screen printing and gravure printing. Inkjet printing using water-based pigment ink is widely used because of its high safety and easy printing.

After printing on the base material, an overcoat is often provided using a liquid containing resin or the like for the purpose of improving abrasion resistance. The texture may be impaired, and depending on the application, the appearance may be undesirable.

For the purpose of suppressing gloss, there are known paint compositions containing particles such as silica as a matting agent (Patent Documents 1 to 3).

A metal base material is often provided as a building material or the like by bending a rectangular flat plate to correspond to various shapes. In some cases, it may be necessary to bend the metal substrate after printing and applying the overcoat liquid.

JP-A-8-209029 Japanese Patent Application Laid-Open No. 2005-187701 JP-A-9-157545

As described above, there is known a coating composition containing silica particles or the like as a matting agent for the purpose of suppressing gloss. In the overcoat film formed from the overcoat liquid, micro-peeling is likely to occur at the interface between the resin and the silica particles. Therefore, when bending is performed, there is a possibility that a so-called whitening phenomenon, in which cracks are generated in the portion stretched by the bending and observed as a white discoloration, occurs.
In addition, when the bending process is performed, an indentation by the processing jig may remain at the portion where the processing jig and the printing portion contact each other.
An object of an embodiment of the present invention is to provide a method for manufacturing a decorative article that can suppress the glossiness of the printed decorative portion and achieve good bending workability.

According to one embodiment of the present invention, after applying an ink containing a coloring material to a metal substrate, the treatment liquid 1 and the treatment liquid 2 are applied to the metal substrate, and the treatment liquid 1 is The treatment liquid 2 contains a water-dispersible resin having a glass transition point of 0° C. or higher, and the treatment liquid 2 contains a flocculating agent for aggregating the water-dispersible resin having a glass transition point of 0° C. or higher in the treatment liquid 1, and the treatment liquid 1 and the treatment liquid 2 are applied to the metal substrate in the order of the treatment liquid 2 and the treatment liquid 1, thereby providing a method for manufacturing a decorative article.

ADVANTAGE OF THE INVENTION According to one Embodiment of this invention, the manufacturing method of the decoration which can suppress the glossiness of a printing decoration part, and can achieve favorable bending workability can be provided.

Hereinafter, the present invention will be described using embodiments. The examples in the following embodiments do not limit the invention.

In the method for producing a decorative article according to one embodiment, after applying an ink containing a coloring material (hereinafter sometimes simply referred to as "ink") to a metal substrate, treatment liquid 1 and treatment liquid 2 are applied to the metal substrate. The treatment liquid 1 contains a water-dispersible resin having a glass transition point of 0 ° C. or higher, and the treatment liquid 2 agglomerates the water-dispersible resin having a glass transition point of 0 ° C. or higher. In this method, the treatment liquid 1 and the treatment liquid 2 are applied to the metal substrate in the order of the treatment liquid 2 and the treatment liquid 1, respectively.

According to the manufacturing method of the decorative article of the embodiment, it is possible to suppress the glossiness of the printed decorative portion and achieve good bending workability at the same time. Some of the reasons are considered as follows, but are not bound by the following reasons.
According to the method for manufacturing a decorative article of the embodiment, after applying the ink to the metal substrate, the treatment liquid 2 containing the aggregating agent for aggregating the water-dispersible resin of the treatment liquid 1 is applied to the metal substrate, and then A treatment liquid 1 is applied to a metal substrate. Since the aggregating agent of the treatment liquid 2 spreads over the metal substrate, the water-dispersible resin of the treatment liquid 1 applied thereon quickly aggregates into micro-sized particles, making it possible to form minute unevenness. , gloss can be suppressed. As the flocculant for the treatment liquid 2, for example, an agent capable of causing a cation-anion reaction with the water-dispersible resin of the treatment liquid 1 can be used. It is believed that the cation-anion reaction between the flocculant of the treatment liquid 2 and the water-dispersible resin of the treatment liquid 1 allows the water-dispersible resin of the treatment liquid 1 to aggregate.
In addition, since the treatment liquid 1 contains a water-dispersible resin having a glass transition point of 0° C. or higher, it is possible to obtain a strong coating that is resistant to irreversible deformation due to stress. For this reason, it is difficult for an indentation due to a processing jig to be formed, and good bending workability can be obtained.

"Manufacturing method of decoration"
A metal base material can be used as the base material for the decoration. Metal substrates include metal plates such as aluminum, iron, copper, titanium, tin, chromium, cadmium, and alloys (eg, stainless steel, steel, etc.).
The metal substrate may have a plated layer, a metal oxide layer, a resin layer, or the like, or may be surface-treated using a surfactant, corona treatment, or the like.

The thickness of the metal substrate is not particularly limited, but may be, for example, 0.5 mm to 50 mm, 1 mm to 20 mm, or 1 mm to 10 mm depending on the application such as building materials.

The step of applying the ink to the metal substrate will be described below.

The method of applying the ink to the metal substrate is not particularly limited, and may be any of an inkjet recording method, an offset printing method, a screen printing method, a gravure printing method, a flexographic printing method, and the like. Among them, the ink jet recording method is preferable because it is possible to easily and freely form an image on demand without contacting the metal base material. The ink is preferably an inkjet ink suitable for an inkjet recording method.
The inkjet recording apparatus may be of any type, such as a piezo system, an electrostatic system, or a thermal system, and ejects ink from an inkjet head based on a digital signal, and adheres the ejected ink droplets to a metal substrate. can be made to

The amount of ink applied to the metal substrate is preferably 4 to 20 g/m ² , more preferably 8 to 14 g/m ² per unit area of the substrate.

The process of applying the treatment liquid 1 and the treatment liquid 2 to the metal substrate will be described.
The treatment liquid 1 and the treatment liquid 2 are preferably applied to the metal substrate after applying the ink to the metal substrate.
From the viewpoint of gloss suppression, it is preferable that the treatment liquid 1 and the treatment liquid 2 are applied to the metal substrate in the order of the treatment liquid 2 and the treatment liquid 1 .

The method of applying the treatment liquid 1 and the treatment liquid 2 to the metal substrate is not particularly limited, and can be selected independently. For example, the treatment liquid 1 may be applied by using an inkjet recording apparatus, or by applying a required amount using a roller, a spray, or the like. For example, the treatment liquid 2 may be applied by using an inkjet recording device, or by applying a required amount using a roller, a spray, or the like. The method for applying the treatment liquid 1 and the method for applying the treatment liquid 2 may be the same or different.
The application area of the treatment liquid 1 may be the entire surface of the metal substrate, or may be selectively applied only to the decorative portion. Alternatively, the treatment liquid 1 can be applied only to areas such as solid image areas where a certain amount or more of ink is applied per unit area. The application area of the treatment liquid 2 may be the entire surface of the metal substrate, or may be selectively applied only to the decorative portion. Alternatively, the treatment liquid 2 can be applied only to areas such as solid image areas where a certain amount or more of ink is applied per unit area. The treatment liquid 1 is preferably applied to the area to which the treatment liquid 2 has been applied. It is preferable that both the treatment liquid 1 and the treatment liquid 2 are applied at least to the ink-applied area.

The amount of treatment liquid 1 applied to the metal substrate may be, for example, 1 to 200 g/m ² or 10 to 100 g/m ² .

The amount of the treatment liquid 2 applied to the metal substrate may be, for example, 1 to 200 g/m ² or 10 to 100 g/m ² .

After applying the ink to the metal substrate and before applying the treatment liquid 2, a drying step may be provided in order to remove volatile matter in the ink applied to the surface of the metal substrate, and/or the ink After application of the treatment liquid 2 to the substrate and before application of the treatment liquid 2 to the substrate, a step of heating the metal substrate may be provided in order to further promote the formation of the ink film.
The temperature at which the metal substrate is heated after applying the ink and before applying the treatment liquid 2 is preferably 80 to 200.degree. C., more preferably 100 to 150.degree. Also, the heating time may be from 1 minute to 5 hours, or from 5 minutes to 1 hour.

After applying the treatment liquid 2 to the metal substrate and before applying the treatment liquid 1, a drying step may be provided, and/or after applying the treatment liquid 2 and before applying the treatment liquid 1, the metal substrate is dried. A heating step may be provided.
The temperature at which the metal substrate is heated after application of the treatment liquid 2 and before application of the treatment liquid 1 is preferably 80 to 200.degree. C., more preferably 100 to 150.degree. The heating time may be 1 minute to 5 hours, 5 minutes to 1 hour, or 10 minutes to 1 hour.

After application of the treatment liquid 1 to the metal substrate, a drying step may be provided and/or after application of the treatment liquid 1, a step of heating the metal substrate may be provided.
After applying the treatment liquid 1, the temperature for heating the metal substrate is preferably 80 to 200.degree. C., more preferably 100 to 150.degree. The heating time may be 1 minute to 5 hours, 5 minutes to 1 hour, or 10 minutes to 1 hour.

Prior to applying the ink to the metal substrate, the substrate may be surface treated using a pretreatment liquid.
The method of applying the pretreatment liquid to the metal substrate is not particularly limited. For example, an inkjet recording device may be used, or the required amount may be applied by a roller, a sprayer, or the like. The imparting region may be the entire surface of the metal substrate, or may be selectively attached only to the decorative portion. Alternatively, the pretreatment liquid can be applied only to areas such as solid image areas where a certain amount or more of ink is applied per unit area.

The amount of the pretreatment liquid applied to the metal substrate may be, for example, 1 to 200 g/m ² or 10 to 100 g/m ² .

After applying the pretreatment liquid to the metal substrate and before applying the ink, a drying step may be provided, and/or after applying the pretreatment liquid to the metal substrate and before applying the ink, the metal substrate may be dried. A step of heating the material may be provided. The temperature at which the metal substrate is heated after applying the pretreatment liquid to the metal substrate and before applying the ink is preferably 80 to 200°C, more preferably 100 to 150°C. Also, the heating time may be, for example, 1 minute to 5 hours, or 5 minutes to 1 hour.

A method for manufacturing a decorative article may include a step of bending a metal substrate.
The printed surface of the metal substrate can be bent on the outside or inside of the bent portion.

The method of bending the metal substrate is not particularly limited, but examples thereof include die bending, twisting bending, curling bending and the like. In particular, when performing V-shaped bending, L-shaped bending, Z-shaped bending, U-shaped bending, etc. in die bending using a die and a punch, whitening of the decorative object occurs because the elongation of the bent portion increases. However, this can be reduced more effectively. In particular, when bent portions such as V-shaped bends, L-shaped bends, and Z-shaped bends have sharp angles, whitening of the bent portions can be more effectively prevented.

In the bending of the metal substrate, the bending angle of the metal substrate is not particularly limited, but may be 1° or more, 10° or more, or 30° or more with an error range of 5°. good too. Also, the bending angle of the metal substrate may be 170° or less, or may be 150° or less, with an error range of 5°. The bending angle of the metal substrate may be a 90° right angle bend with an error margin of 5°. Here, the bend angle indicates the inner angle of the bent portion.

Also, the number of places where the metal substrate is bent may be one or two or more.

"ink"
The ink preferably contains a coloring material. Colorants may be pigments, dyes, or combinations thereof.
The ink preferably contains at least one of a water-dispersible resin and a water-soluble resin.
The ink can include an aqueous solvent that is water, a water-soluble organic solvent, or a combination thereof. Preferably, the ink is an aqueous ink.

The ink can include pigments, dyes, or combinations thereof as colorants. A pigment can be preferably used as the coloring material from the viewpoint of the weather resistance and water resistance of the decorative image.

The pigment can be preferably blended into the ink as a pigment dispersion.
Any pigment dispersion may be used as long as the pigment can be dispersed in a solvent and the pigment can be dispersed in the ink. For example, pigments dispersed in water with a pigment dispersant, self-dispersing pigments dispersed in water, microencapsulated pigments coated with a resin dispersed in water, and the like can be used. .

Examples of pigments that can be used include organic pigments such as azo pigments, phthalocyanine pigments, polycyclic pigments and dyed lake pigments; and inorganic pigments such as carbon black and metal oxides. Examples of azo pigments include soluble azo lake pigments, insoluble azo pigments and condensed azo pigments. Examples of phthalocyanine pigments include metal phthalocyanine pigments such as copper phthalocyanine pigments, and metal-free phthalocyanine pigments. Polycyclic pigments include quinacridone-based pigments, perylene-based pigments, perinone-based pigments, isoindoline-based pigments, isoindolinone-based pigments, dioxazine-based pigments, thioindigo-based pigments, anthraquinone-based pigments, quinophthalone-based pigments, and metal complex pigments. and diketopyrrolopyrrole (DPP). Examples of carbon black include furnace carbon black, lamp black, acetylene black, channel black and the like. Examples of metal oxides include titanium oxide and zinc oxide.
The volume-based average particle diameter of the pigment is preferably 50 nm or more from the viewpoint of color development, preferably 500 nm or less, and more preferably 200 nm or less from the viewpoint of ejection stability. For example, the volume-based average particle size of the pigment is preferably 50 to 500 nm, more preferably 50 to 200 nm.

A self-dispersible pigment may be blended as a coloring material. A self-dispersing pigment is a pigment into which a hydrophilic functional group has been introduced onto the surface of the pigment by chemical or physical treatment. As the hydrophilic functional group to be introduced into the self-dispersing pigment, those having ionic properties are preferable, and by charging the surface of the pigment anionically or cationic, the pigment particles are stably dispersed in water by electrostatic repulsion. be able to. As the anionic functional group, a sulfonic acid group, a carboxyl group, a carbonyl group, a hydroxy group, a phosphonic acid group and the like are preferable. The cationic functional group is preferably a quaternary ammonium group, a quaternary phosphonium group, or the like.

These hydrophilic functional groups may be directly bonded to the pigment surface, or may be bonded via other atomic groups. Other atomic groups include, but are not limited to, alkylene groups, phenylene groups, naphthylene groups, and the like. Examples of methods for treating the pigment surface include diazotization treatment, sulfonation treatment, hypochlorous acid treatment, humic acid treatment, and vacuum plasma treatment.

Examples of self-dispersing pigments include CAB-O-JET series manufactured by Cabot Corporation "CAB-O-JET200, CAB-O-JET300, CAB-O-JET250C, CAB-O-JET260M, CAB-O-JET270", Orient Chemical Industry Co., Ltd. BONJET series "BONJET BLACK CW-1, BONJET BLACK CW-1S, BONJET BLACK CW-2, BONJET BLACK CW-3, BONJET BLACK CW-6" can be preferably used (both Product name).

In order to stably disperse the pigment in water, the water-based ink may further contain a pigment dispersant. Examples of pigment dispersants that can be used include polymer dispersants and surfactants.
When a pigment dispersant is used, the amount of the pigment dispersant added varies depending on the type and is not particularly limited. For example, the pigment dispersant can be added in the range of 0.005 to 0.5 with respect to 1 part of the pigment in terms of mass ratio of the active ingredient.

As the dye, those commonly used in the technical field of printing can be used without particular limitation. Specific examples include basic dyes, acid dyes, direct dyes, soluble vat dyes, acid mordant dyes, mordant dyes, reactive dyes, vat dyes, sulfur dyes, etc. Among these, water-soluble dyes, reduction dyes, etc. Water-soluble substances can be used. More specific examples include azo dyes, rhodamine dyes, methine dyes, azomethine dyes, xanthene dyes, quinone dyes, triphenylmethane dyes, diphenylmethane dyes, and methylene blue.

The above coloring materials can be used alone or in combination of two or more.
The nonvolatile content of the coloring material is preferably 0.1% by mass to 30% by mass, more preferably 1% by mass to 20% by mass, and more preferably 3% by mass to 15% by mass, based on the total amount of the ink. It is even more preferable to have

The ink preferably contains a water-dispersible resin.

As the water-dispersible resin, it is preferable to use a resin that can be incorporated into the ink in the form of particles, that is, that can form an oil-in-water (O/W) resin emulsion in the ink. As the water-dispersible resin, it is preferable to use a transparent resin that forms a transparent coating film so as not to affect the color development of the ink. Moreover, it is preferable to blend as an oil-in-water resin emulsion when manufacturing the ink.
Examples of water-dispersible resins include urethane-based resins, (meth)acrylic-based resins, styrene/(meth)acrylic-based resins, polyester-based resins, olefin-based resins, vinyl chloride-based resins, vinyl acetate-based resins, and melamine-based resins. , amide resin, ethylene-vinyl chloride copolymer resin, styrene-maleic anhydride copolymer resin, vinyl acetate-(meth)acrylic copolymer resin, vinyl acetate-ethylene copolymer resin, silicone resin, etc., or These compound resins etc. are mentioned. "(Meth)acrylic resin" means an acrylic resin, a methacrylic resin, or a copolymer thereof (the same shall apply hereinafter).
An oil-in-water resin emulsion may be formed by introducing a hydrophilic functional group into these resins or surface-treating the resin with a dispersant or the like, which may be blended into the ink.

As the water-dispersible resin, it is preferable to use negatively charged anionic resin particles whose particle surfaces are negatively charged. It can form an oil-in-water resin emulsion by dispersing in particulate form without dissolving in water. As with self-emulsifying resins, the resin may have an anionic functional group present on the particle surface, or the resin particle surface may be subjected to surface treatment such as attaching an anionic dispersant. Anionic functional groups are typically carboxy groups, sulfo groups and the like, and anionic dispersants are anionic surfactants and the like.
Since an anionic component is often used in ink, the resin particle surface being anionic makes it possible to maintain good dispersibility or solubility of the colorant of the ink. For example, when carbon black is used as the colorant, an anionic water-dispersible resin can be preferably used so as to maintain the dispersion stability of carbon black in the ink.
The surface charge amount of the anionic water-dispersible resin particles is preferably −20 to −500 μeq/g. The surface charge amount of the water-dispersible resin particles can be evaluated with a particle charge meter. By measuring the amount of anions or cations required to neutralize the sample, the amount of surface charge can be calculated. As the particle charge meter, a colloidal particle charge meter "Model CAS" manufactured by Nihon Luft Co., Ltd. can be used.

Among these water-dispersible resins, urethane-based resins are preferably used from the viewpoint of fixability to the substrate and stable ejection performance from the recording head.
Examples of commercially available emulsions containing water-dispersible urethane resins include "Superflex 470, Superflex 130, Superflex 870, Superflex E-4800" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Mitsui Chemicals, Inc. "Takelac W-5661, Takelac W-6020" manufactured by the company, "Permaline UA-200" manufactured by Sanyo Chemical Industries, Ltd., "ADEKA BONDITATER HUX-350, ADEKA BONDITATER HUX-550" manufactured by Adeka Co., Ltd., "WBR-016U" manufactured by Taisei Fine Chemical Co., Ltd. and the like can be mentioned (both are trade names).

From the viewpoint of stability in ink, it is also preferable to use a (meth)acrylic resin.
Examples of commercially available emulsions containing water-dispersible (meth)acrylic resins include "NeoCryl A-1125, NeoCryl A-1127, NeoCryl A-6069" and "NeoCryl A-1092," manufactured by DSM Coating Resins. NeoCryl A-2092", "Movinyl 9780, Movinyl 727, Movinyl 745", "Movinyl 966A, Movinyl 940" manufactured by Japan Coating Resin Co., Ltd., "Joncryl 7100, Joncryl PDX-7370, Joncryl PDX" manufactured by BASF. -7341";"Boncoat EC-905EF, Boncoat 5400EF, and Boncoat CG-8400" manufactured by DIC Corporation (all are trade names).

As the water-dispersible resin, a nonionic or amphoteric water-dispersible resin may be used since it has little effect on the charge balance of the ink.

The above-described water-dispersible resin may be composed of a single resin, or may be composed of a composite resin by combining a plurality of resins, and may be a mixture of these resin emulsions. good too.
The water-dispersible resin is preferably 0.1 to 15, more preferably 0.1 to 10, and still more preferably 0.1 to 7 in terms of mass ratio of non-volatile matter to 1 part of the colorant with respect to the total amount of the ink. By setting the blending amount of the resin within this range, it is possible to sufficiently secure the fixability and image quality of the image printed on the surface of the base material. When the ratio of the resin to the coloring material 1 is 0.1 or more, the fixability of the image can be further improved. When the ratio of the resin to the coloring material is 15 or less, the on-press stability of the ink can be further improved.

The non-volatile content of the water-dispersible resin is preferably 0.1% by mass or more, more preferably 1% by mass or more, relative to the total amount of the ink.
The water-dispersible resin preferably has a non-volatile content of 20% by mass or less, more preferably 10% by mass or less, relative to the total amount of the ink.
For example, the non-volatile content of the water-dispersible resin is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total amount of the ink.

The average particle size of the water-dispersible resin particles is preferably 1 nm to 300 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 150 nm. This is the average particle size obtained by measuring the particle size of the water-dispersible resin in the state of an oil-in-water resin emulsion by a dynamic light scattering method on a volume basis.
Further, when the ink is applied to the substrate using an inkjet recording method, the average particle size of the water-dispersible resin may be any particle size suitable for the inkjet recording method, preferably 300 nm or less, more preferably 200 nm or less. It is preferably 150 nm or less, more preferably 150 nm or less.
Further, when the ink is applied to the substrate using an inkjet recording method, the average particle size of the water-dispersible resin is preferably 1 nm or more, more preferably 5 nm or more, and 10 nm or more, from the viewpoint of storage stability of the ink. is more preferred.

It is preferable that the solvent of the ink mainly contains water. Examples of water include ion-exchanged water, distilled water, ultrapure water, and deionized water. When the pigment dispersion contains water as a solvent, the ink is prepared by converting the water in the pigment dispersion into part of the water in the ink.
Water is a highly volatile solvent and can easily evaporate from the base material after being applied to the base material, thereby accelerating the drying of the decorative material. Also, since water is harmless and highly safe, and has no problems such as VOCs, the surface-treated substrate can be made environmentally friendly.
Water is preferably 30% by mass or more, more preferably 50% by mass or more, and may be 70% by mass or more, based on the total amount of ink. Water may be 95% by mass or less, or 90% by mass or less, relative to the total amount of ink. For example, water is preferably 30 to 95% by mass, more preferably 70 to 95% by mass, even more preferably 50 to 90% by mass, based on the total amount of ink.

The ink can contain a water-soluble organic solvent. As the water-soluble organic solvent, an organic compound that is liquid at room temperature and can be dissolved or miscible with water can be used, and a water-soluble organic solvent that can be uniformly mixed with the same volume of water at 1 atmosphere and 20° C. can be used. preferable. Moreover, it is preferable that the water-soluble organic solvent is capable of satisfactorily dispersing the above-described water-dispersible resin in a mixed solution with water.

Examples of water-soluble organic solvents include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 1,3-propanediol, 1,3-butanediol, and 1,2-butanediol. , 1,2-pentanediol, 1,2-hexanediol, 2-methyl-2-propanol and other lower alcohols; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, polyethylene glycol, propylene glycol , dipropylene glycol, tripropylene glycol, polypropylene glycol; glycerin; acetins such as monoacetin and diacetin; diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monobutyl ether, triethylene glycol monohexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, Glycol ethers such as tetraethylene glycol dimethyl ether and tetraethylene glycol diethyl ether; triethanolamine, 1-methyl-2-pyrrolidone, β-thiodiglycol, sulfolane and the like can be used.
These water-soluble organic solvents can be used alone or in combination of two or more.

The water-soluble organic solvent is preferably 1% by mass or more, more preferably 10% by mass or more, based on the total amount of ink from the viewpoint of viscosity adjustment and moisturizing effect. The water-soluble organic solvent is preferably 80% by mass or less, more preferably 60% by mass or less, and may be 40% by mass or less, based on the total amount of the ink. For example, the water-soluble organic solvent is preferably 1 to 80% by mass, more preferably 10 to 60% by mass, and may be 10 to 40% by mass with respect to the total amount of ink. When blending two or more water-soluble organic solvents, the total amount is preferably within this range.

The ink can further contain a surfactant.
Surfactants are broadly classified into ionic surfactants such as cationic surfactants, anionic surfactants and amphoteric surfactants, and nonionic surfactants. may be used. In addition, both low-molecular-weight surfactants and high-molecular-weight surfactants (generally refers to those having a molecular weight of about 2000 or more) may be used, but high-molecular-weight surfactants can be preferably used. . The HLB value of the surfactant is preferably 3-20.

A nonionic surfactant can be preferably used as the surfactant. Nonionic surfactants have little effect on the charge balance of the ink and can maintain good dispersibility and solubility of the coloring material.
Ionic surfactants such as cationic surfactants, anionic surfactants and amphoteric surfactants may affect the charge balance of the ink and cause the colorant to aggregate. Therefore, when using an ionic surfactant, it is preferable to use one that does not affect the charge balance of the ink. For example, when the colorant of the ink is carbon black, an anionic surfactant is preferably used because an anionic dispersant is often used.

Examples of nonionic surfactants include silicone-based surfactants, acetylene glycol-based surfactants, polyoxyethylene alkyl ether-based surfactants, polyoxypropylene alkyl ether-based surfactants, and polyoxyethylene alkylphenyl ethers. surfactant, polyoxypropylene alkylphenyl ether surfactant, polyoxyethylene fatty acid ester surfactant, polyoxypropylene fatty acid ester surfactant, sorbitan fatty acid ester surfactant, polyoxyethylene sorbitan fatty acid ester surfactants, polyoxyethylene sorbitol fatty acid ester surfactants, glycerin fatty acid ester surfactants, and the like. These may be used alone or in combination of two or more.

Among these surfactants, silicone-based surfactants, acetylene glycol-based surfactants, or combinations thereof can be preferably used, with silicone-based surfactants being more preferred.
Among silicone-based surfactants, polyether-modified silicone-based surfactants, alkyl/aralkyl-co-modified silicone-based surfactants, acrylic silicone-based surfactants, and the like can be preferably used. Examples of commercially available silicone-based surfactants include "Silface SAG503A, Sylface SAG001, Sylface SAG002, Sylface SAG003, Sylface SAG005, and Sylface SAG008" manufactured by Nissin Chemical Industry Co., Ltd. (both are product names).

The amount of active ingredients in the surfactant is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total amount of the ink. On the other hand, the amount of the surfactant is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, in terms of the active ingredient amount relative to the total amount of the ink. The surfactant is preferably 0.1 to 5% by mass, more preferably 0.1 to 4% by mass, and still more preferably 0.5 to 3% by mass in terms of active ingredient amount relative to the total amount of the ink.

In addition to the above components, optional components such as antifoaming agents, pH adjusters, antioxidants, preservatives, and ultraviolet absorbers may be further added to the ink within a range that does not impair the effects of the present invention. good.

A method for preparing the ink is not particularly limited, but a desired ink can be obtained by appropriately mixing each component. For example, it can be obtained by dispersing a water-dispersible resin in a solution in which an appropriate water-soluble organic solvent, surfactant, or the like is added to water, and mixing a coloring material component such as a pigment dispersion therein.

The viscosity of the ink is not particularly limited and can be appropriately adjusted according to the recording method. The viscosity of the ink suitable for the inkjet recording method varies depending on the nozzle diameter of the ejection head, the ejection environment, and the like. It is more preferable to have

"Processing liquid 1"
The treatment liquid 1 can contain a water-dispersible resin having a glass transition point (Tg) of 0° C. or higher.

The glass transition point of the water-dispersible resin of the treatment liquid 1 is preferably 0° C. or higher, more preferably 5° C. or higher, and even more preferably 10° C. or higher, from the viewpoint of improving bending workability. The glass transition point of the water-dispersible resin of the treatment liquid 1 is preferably 300° C. or lower, more preferably 250° C. or lower, and even more preferably 150° C. or lower. The glass transition point of the water-dispersible resin of the treatment liquid 1 is preferably 0 to 300°C, more preferably 5 to 250°C, even more preferably 10 to 150°C.

As the water-dispersible resin, it is preferable to use a resin that can be incorporated in the treatment liquid 1 in the form of particles, that is, a resin that can form an oil-in-water (O/W) type resin emulsion in the treatment liquid 1 . As the water-dispersible resin, it is preferable to use a transparent resin that forms a transparent coating film so as not to affect the color development of the ink. Further, the water-dispersible resin is preferably blended as an oil-in-water resin emulsion when the treatment liquid 1 is produced.
Examples of water-dispersible resins include urethane-based resins, (meth)acrylic-based resins, styrene/(meth)acrylic-based resins, polyester-based resins, olefin-based resins, vinyl chloride-based resins, vinyl acetate-based resins, and melamine-based resins. , amide resin, ethylene-vinyl chloride copolymer resin, styrene-maleic anhydride copolymer resin, vinyl acetate-(meth)acrylic copolymer resin, vinyl acetate-ethylene copolymer resin, silicone resin, etc., or These compound resins etc. are mentioned.
An oil-in-water resin emulsion may be formed by introducing a hydrophilic functional group into these resins or surface-treating the resin with a dispersant or the like, and this may be blended with the treatment liquid 1 .

As the water-dispersible resin having a glass transition point of 0° C. or higher contained in the treatment liquid 1, for example, anionic resin particles having a negatively charged particle surface may be used. It can form an oil-in-water resin emulsion by dispersing in particulate form without dissolving in water. As with self-emulsifying resins, the resin may have an anionic functional group present on the particle surface, or the resin particle surface may be subjected to surface treatment such as attaching an anionic dispersant. Anionic functional groups are typically carboxy groups, sulfo groups and the like, and anionic dispersants are anionic surfactants and the like.
The surface charge amount of the anionic water-dispersible resin particles is preferably −20 to −500 μeq/g.

As the anionic water-dispersible resin having a glass transition point of 0° C. or higher, a urethane-based resin, a (meth)acrylic-based resin, or a combination thereof is preferable.
Commercially available emulsions of anionic water-dispersible urethane resins having a glass transition point of 0°C or higher include, for example, "Superflex 830HS, Superflex 126, Superflex 130, and Superflex 150" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. , SUPERFLEX 150HS, SUPERFLEX 170, SUPERFLEX 210” (all are trade names).
Examples of commercially available emulsions of anionic water-dispersible (meth)acrylic resins having a glass transition point of 0° C. or higher include “NeoCryl A-1125, NeoCryl A-1127, NeoCryl A-1105” manufactured by DSM Coating Resins. (both are trade names).
The above anionic water-dispersible resins may be used alone or in combination of two or more.

As the water-dispersible resin having a glass transition point of 0° C. or higher contained in the treatment liquid 1, for example, cationic resin particles having a positively charged particle surface may be used. It can form an oil-in-water resin emulsion by dispersing in particulate form without dissolving in water. The cationic water-dispersible resin may be a self-emulsifying resin in which a cationic functional group is present on the particle surface, or may be a cationic dispersant attached to the resin particle surface. It may be surface-treated.
Cationic functional groups are typically primary, secondary or tertiary amino groups, pyridine groups, imidazole groups, benzimidazole groups, triazole groups, benzotriazole groups, pyrazole groups, benzopyrazole groups, etc. is mentioned. Cationic dispersants include primary, secondary, tertiary or quaternary amino group-containing acrylic polymers, polyethyleneimine, cationic polyvinyl alcohol resins, cationic water-soluble multi-branched polyesteramide resins, and the like.
The surface charge amount of the cationic water-dispersible resin particles is preferably 20 to 500 μeq/g.

As the cationic water-dispersible resin having a glass transition point of 0° C. or higher, a urethane-based resin, a (meth)acrylic-based resin, or a combination thereof is preferable.
Examples of commercially available emulsions of cationic water-dispersible urethane resins having a glass transition point of 0° C. or higher include “Superflex 620” (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like.
Commercially available emulsions of cationic water-dispersible (meth)acrylic resins having a glass transition point of 0° C. or higher include “Movinyl 6930” (trade name) manufactured by Japan Coating Resin Co., Ltd., and the like.
The cationic water-dispersible resins described above may be used alone or in combination of two or more.

The treatment liquid 1 can contain a surfactant.

As the surfactant, any of anionic surfactants, cationic surfactants, ionic surfactants such as amphoteric surfactants, and nonionic surfactants can be used.
From the viewpoint of the stability of the treatment liquid 1 , it is preferable that the surfactant has little effect on the charge balance of the treatment liquid 1 . From the viewpoint of the stability of the treatment liquid 1, a nonionic surfactant can be preferably used as the surfactant.
When using an ionic surfactant, it is preferable to use one that does not affect the charge balance of the treatment liquid 1 . For example, when the treatment liquid 1 contains an anionic water-dispersible resin, an anionic surfactant can be preferably used. For example, when the treatment liquid 1 contains a cationic water-dispersible resin, a cationic surfactant can be preferably used.
In addition, the surfactant may be either a low-molecular-weight surfactant or a high-molecular-weight surfactant (generally refers to those having a molecular weight of about 2000 or more). It can be preferably used.
The HLB value of the surfactant is preferably 5-20.

The surfactant can be used by appropriately selecting from, for example, the surfactants that can be blended in the aqueous ink described above.
Surfactants may be used alone or in combination of two or more.
The amount of the active ingredient of the surfactant is preferably 0.1% by mass or more relative to the total amount of the treatment liquid. The amount of active ingredients in the surfactant is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total amount of the treatment liquid. The amount of the active ingredient of the surfactant is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total amount of the treatment liquid.

The treatment liquid 1 can further contain water. For example, the treatment liquid 1 preferably contains water as a main solvent. Examples of water include, but are not particularly limited to, ion-exchanged water, distilled water, ultrapure water, and deionized water.
Water is preferably 10% by mass or more, more preferably 30% by mass, and may be 50% by mass or more, relative to the total amount of the treatment liquid 1. The water content is preferably 95% by mass or less, more preferably 90% by mass or less, and may be 80% by mass or less with respect to the total amount of the treatment liquid 1. Water is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and may be 50 to 80% by mass with respect to the total amount of the treatment liquid 1.

The treatment liquid 1 may contain a water-soluble organic solvent together with water or instead of water.
As the water-soluble organic solvent, a water-soluble organic solvent that can be blended with the water-based ink described above may be used. The water-soluble organic solvent may be used singly or in combination of two or more, and preferably forms a single phase in a mixed solvent with water.
The water-soluble organic solvent is preferably 1% by mass or more, more preferably 10% by mass or more, relative to the total amount of the treatment liquid. The water-soluble organic solvent is preferably 50% by mass or less, more preferably 40% by mass or less, relative to the total amount of the treatment liquid. The water-soluble organic solvent is preferably 1 to 50% by mass, more preferably 10 to 40% by mass, based on the total amount of the treatment liquid.

The treatment liquid 1 further contains optional components such as antifoaming agents, pH adjusters, antioxidants, preservatives, and ultraviolet absorbers, as well as the water-based inks described above, to the extent that the effects of the present invention are not impaired. It's okay.

The method for producing the treatment liquid 1 is not particularly limited, and the treatment liquid 1 can be produced as appropriate by an ordinary method. For example, the treatment liquid 1 can be prepared by putting all the components together or separately into a stirrer such as a three-one motor, mixing or dispersing them, and optionally passing them through a filter such as a membrane filter.

"Treatment liquid 2"
The treatment liquid 2 can contain an aggregating agent for aggregating the water-dispersible resin of which the glass transition point of the treatment liquid 1 is 0° C. or higher.
As the flocculant for the treatment liquid 2, those capable of causing a cation-anion reaction with the water-dispersible resin of the treatment liquid 1 can be used. It is believed that the cation-anion reaction between the flocculant of the treatment liquid 2 and the water-dispersible resin of the treatment liquid 1 allows the water-dispersible resin of the treatment liquid 1 to aggregate.
It is preferable that the coagulant of the treatment liquid 2 is appropriately selected according to the water-dispersible resin whose glass transition point of the treatment liquid 1 is 0° C. or higher. For example, when the water-dispersible resin having a glass transition point of 0° C. or higher in the treatment liquid 1 is an anionic water-dispersible resin, the flocculant in the treatment liquid 2 may be a polyvalent metal salt, a cationic resin, an organic acid, Or it is preferable to include these combinations. Further, for example, when the water-dispersible resin having a glass transition point of 0° C. or higher in the treatment liquid 1 is a cationic water-dispersible resin, the flocculant of the treatment liquid 2 may contain an anionic water-dispersible resin. preferable.
The flocculant will be described in detail below.

As the aggregating agent for the treatment liquid 2, for example, polyvalent metal salts, cationic resins, organic acids, and the like can be preferably used. The cationic resin is not particularly limited, and may be either a cationic water-soluble resin or a cationic water-dispersible resin, or may be used in combination. Among these, the cationic water-dispersible resin is more preferable as the flocculant for the treatment liquid 2 .

For example, when the treatment liquid 1 contains an anionic water-dispersible resin having a glass transition point of 0° C. or higher, the flocculant of the treatment liquid 2 contains a polyvalent metal salt, a cationic resin, an organic acid, or a combination thereof. From the viewpoint of improving good film-forming properties and film strength, and thereby improving bending workability, it is more preferable to contain a cationic water-dispersible resin.

A water-dispersible resin is preferably used as the flocculant of the treatment liquid 2 from the viewpoints of good film formability and film strength improvement, and thereby improvement of bending workability. Examples of water-dispersible resins include anionic water-dispersible resins and cationic water-dispersible resins.
For example, when the treatment liquid 1 contains an anionic water-dispersible resin having a glass transition point of 0° C. or higher, the treatment liquid is The flocculant 2 preferably contains a cationic water-dispersible resin.
For example, when the treatment liquid 1 contains a cationic water-dispersible resin having a glass transition point of 0° C. or higher, the treatment liquid is The flocculant 2 preferably contains an anionic water-dispersible resin.

Examples of polyvalent metal salts include halides, nitrates, sulfates, acetates, fatty acid salts, lactates, and chlorates of divalent or higher metals. As the halide, chloride, bromide, iodide and the like are preferable. Examples of divalent or higher metals include divalent alkaline earth metals such as Mg, Ca, Sr, and Ba; divalent metals such as Ni, Zn, Cu, and Fe(II); Examples include trivalent metals, among which alkaline earth metals are preferred.
More specific examples include calcium chloride, calcium nitrate, magnesium chloride, magnesium nitrate, magnesium sulfate, copper nitrate, calcium acetate, and magnesium acetate.
The above polyvalent metal salts may be used alone or in combination of two or more.

The cationic resin may be either a cationic water-soluble resin or a cationic water-dispersible resin, or may be used in combination.

Examples of cationic water-soluble resins include polyethyleneimine (PEI), polyvinylamine, polyallylamine and salts thereof, polyvinylpyridine, and cationic acrylamide copolymers. More specifically, for example, polydiallyldimethylammonium chloride or the like can be used.
Examples of commercially available cationic water-soluble resins include "Himax SC-700L" (trade name) manufactured by Hymo Co., Ltd., and the like.

As the cationic water-dispersible resin, it is preferable to use a transparent resin that forms a transparent coating film. Further, when manufacturing the treatment liquid 2, it is preferable to mix it as an oil-in-water resin emulsion.
Examples of cationic water-dispersible resins include urethane-based resins, (meth)acrylic-based resins, styrene/(meth)acrylic-based resins, polyester-based resins, olefin-based resins, vinyl chloride-based resins, vinyl acetate-based resins, and melamine. resins, amide resins, ethylene-vinyl chloride copolymer resins, styrene-maleic anhydride copolymer resins, vinyl acetate-(meth)acrylic copolymer resins, vinyl acetate-ethylene copolymer resins, and composites thereof In resins and the like, those obtained by introducing a cationic functional group into these resins or surface-treating them with a cationic dispersant or the like to impart a positive surface charge can be used.
Cationic functional groups are typically primary, secondary or tertiary amino groups, pyridine groups, imidazole groups, benzimidazole groups, triazole groups, benzotriazole groups, pyrazole groups, benzopyrazole groups, etc. is mentioned. Cationic dispersants include primary, secondary, tertiary or quaternary amino group-containing acrylic polymers, polyethyleneimine, cationic polyvinyl alcohol resins, cationic water-soluble multi-branched polyesteramide resins, and the like.
The surface charge amount of the cationic water-dispersible resin particles is preferably 20 to 500 μeq/g.
As the cationic water-dispersible resin, those having a glass transition point of 0° C. or higher are also preferable. may
The above cationic resins may be used alone or in combination of two or more.

Examples of organic acids include carboxylic acids such as formic acid, acetic acid and oxalic acid, hydroxycarboxylic acids such as lactic acid, glyceric acid, tartaric acid, citric acid and malic acid, ascorbic acid and sulfonic acid. These may be used alone or in combination of two or more.

The anionic water-dispersible resin is not particularly limited, and can be appropriately selected and used, for example, from anionic water-dispersible resins that can be incorporated into the ink.
The surface charge amount of the anionic water-dispersible resin particles is preferably −20 to −500 μeq/g.
Urethane-based resins, (meth)acrylic-based resins, or combinations thereof are preferred as the anionic water-dispersible resin.
In addition, as the anionic water-dispersible resin, those having a glass transition point of 0° C. or higher are also preferable. may be used.
Anionic water-dispersible resins may be used alone or in combination of two or more.

The flocculants described above may be used alone or in combination of two or more. For example, the coagulant is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 5 to 15% by mass in terms of active ingredient amount relative to the treatment liquid 1.

The treatment liquid 2 can contain a surfactant.

As the surfactant, any of anionic surfactants, cationic surfactants, ionic surfactants such as amphoteric surfactants, and nonionic surfactants can be used.
From the viewpoint of the stability of the treatment liquid 2 , the surfactant preferably has little effect on the charge balance of the treatment liquid 2 . From the viewpoint of the stability of the treatment liquid 2, a nonionic surfactant can be preferably used as the surfactant.
When using an ionic surfactant, it is preferable to use one that does not affect the charge balance of the treatment liquid 2 .
In addition, the surfactant may be either a low-molecular-weight surfactant or a high-molecular-weight surfactant (generally refers to those having a molecular weight of about 2000 or more). It can be preferably used.
The HLB value of the surfactant is preferably 5-20.

The surfactant can be used by appropriately selecting from, for example, the surfactants that can be blended in the aqueous ink described above.
Surfactants may be used alone or in combination of two or more.
The amount of the active ingredient of the surfactant is preferably 0.1% by mass or more with respect to the total amount of the treatment liquid 2 . The amount of active ingredients in the surfactant is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total amount of the treatment liquid 2 . The amount of the active ingredient of the surfactant is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total amount of the treatment liquid 2.

The treatment liquid 2 can further contain water. For example, the treatment liquid 2 preferably contains water as a main solvent. Examples of water include, but are not particularly limited to, ion-exchanged water, distilled water, ultrapure water, and deionized water.
Water is preferably 10% by mass or more, more preferably 30% by mass, and may be 50% by mass or more, based on the total amount of the treatment liquid 2 . The water content is preferably 95% by mass or less, more preferably 90% by mass or less, and may be 80% by mass or less with respect to the total amount of the treatment liquid 2 . Water is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and may be 50 to 80% by mass with respect to the total amount of the treatment liquid 2.

The treatment liquid 2 may contain a water-soluble organic solvent together with water or instead of water.
As the water-soluble organic solvent, a water-soluble organic solvent that can be blended with the water-based ink described above may be used. The water-soluble organic solvent may be used singly or in combination of two or more, and preferably forms a single phase in a mixed solvent with water.
The water-soluble organic solvent is preferably 1% by mass or more, more preferably 10% by mass or more, relative to the total amount of the treatment liquid 2 . The water-soluble organic solvent is preferably 50 mass % or less, more preferably 40 mass % or less, relative to the total amount of the treatment liquid 2 . The water-soluble organic solvent is preferably 1 to 50% by mass, more preferably 10 to 40% by mass, relative to the total amount of the treatment liquid 2.

The treatment liquid 2 further contains optional components such as antifoaming agents, pH adjusters, antioxidants, preservatives, ultraviolet absorbers, and the like, in the same manner as the water-based ink described above, within a range that does not impair the effects of the present invention. It's okay.

The method for producing the treatment liquid 2 is not particularly limited, and the treatment liquid 2 can be produced as appropriate by an ordinary method. For example, the treatment liquid 2 can be prepared by putting all the components together or separately into a stirrer such as a three-one motor, mixing or dispersing them, and optionally passing them through a filter such as a membrane filter.

"Pretreatment liquid"
The pretreatment liquid may be a pretreatment liquid that has the effect of aggregating the colorant components of the ink, a pretreatment liquid that has the effect of improving the wettability (wettability) between the ink and the substrate, or a combination of these. It is possible to use a pretreatment liquid or the like that has a

The pretreatment liquid can contain a flocculating agent. By including a flocculant in the pretreatment liquid, the coloring material component of the water-based ink agglomerates on the surface of the pretreated base material, suppressing bleeding of the image of the decoration, further increasing the image density and improving the image quality. can be further improved.
As the flocculant for the pretreatment liquid, for example, polyvalent metal salts, cationic resins, organic acids and the like can be preferably used. As the polyvalent metal salt, for example, one that can be blended with the treatment liquid 2 can be used, and one kind or two or more kinds can be used in combination. As the cationic resin, for example, one that can be blended in the treatment liquid 2 can be used, and one type or two or more types may be used in combination. As the organic acid, for example, one that can be blended in the treatment liquid 2 can be used, and one type or two or more types may be used in combination.

The flocculants described above may be used alone or in combination of two or more. For example, the flocculant is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 5 to 15% by mass in terms of active ingredient amount relative to the pretreatment liquid.

The pretreatment liquid can contain a wetting agent. By including a wetting agent in the pretreatment liquid, the wettability (wettability) between the surface of the pretreated base material and the water-based ink is enhanced, and the adhesion between the base material and the water-based ink is further enhanced, resulting in can further enhance the fixability of the toner.
As a wetting agent for the pretreatment liquid, for example, a surfactant or the like can be used.

As the surfactant, it is possible to appropriately select and use from among the above-described surfactants that can be blended in the water-based ink.
Surfactants may be used alone or in combination of two or more.
The amount of active ingredient of the surfactant is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total amount of the pretreatment liquid. When the pretreatment liquid contains a resin component or the like, from the viewpoint of the affinity between the resin component or the like and the aqueous solvent, the amount of the surfactant is 0.5% by mass or more in terms of the active ingredient amount based on the total amount of the pretreatment liquid. may be blended, and may be 1% by mass or more.

The pretreatment liquid can further contain water. For example, the pretreatment liquid preferably contains water as a main solvent. Examples of water include, but are not particularly limited to, ion-exchanged water, distilled water, ultrapure water, and deionized water.
Water is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and may be 50 to 80% by mass, based on the total amount of the pretreatment liquid.

The pretreatment liquid may contain a water-soluble organic solvent together with water or instead of water.
As the water-soluble organic solvent, a water-soluble organic solvent that can be blended with the ink described above may be used. The water-soluble organic solvent may be used singly or in combination of two or more, and preferably forms a single phase in a mixed solvent with water.
The water-soluble organic solvent is preferably 1 to 50% by mass, more preferably 10 to 40% by mass, relative to the total amount of the pretreatment liquid.

The pretreatment liquid may further contain a resin component.
By including a binder resin as a resin component, fixability of the pretreatment liquid to the substrate can be further enhanced. In addition, the fixation of the ink to the substrate can be promoted more.
As the binder resin, a nonionic resin can be preferably used so as not to affect the ionicity of the pretreatment liquid. Nonionic resins may be either water-soluble or water-dispersible. Moreover, as the nonionic resin, a nonionic resin can be selected and used from among the resin components that can be blended in the aqueous ink described above. When the pretreatment liquid contains a cationic resin as a flocculant, the cationic resin can also function as a binder resin.

As with the water-based ink described above, the pretreatment liquid further contains optional components such as antifoaming agents, pH adjusters, antioxidants, preservatives, and ultraviolet absorbers within a range that does not impair the effects of the present invention. It's okay.

The method for producing the pretreatment liquid is not particularly limited, and the pretreatment liquid can be produced as appropriate by a conventional method. For example, the pretreatment liquid can be prepared by putting all the components together or separately into a stirrer such as a three-one motor, mixing or dispersing them, and optionally passing them through a filter such as a membrane filter.

EXAMPLES The present invention will be described in detail below with reference to examples. The invention is not limited to the following examples. In the following description, the same items are used for common components.

(Example 1)
<Base material>
An aluminum plate substrate having a thickness of 0.5 mm was used as the metal substrate. The glossiness (GU) at an incident angle of 60° was 110 before decoration of this metal substrate.

<Pretreatment liquid>
For the pretreatment liquid, 1.0% by mass of "Sylface SAG002" (surfactant, manufactured by Nisshin Chemical Industry Co., Ltd., active ingredient 100% by mass), "Himax SC-700L" (manufactured by Hymo Co., Ltd., Cationic water-soluble resin, 30% by mass of active ingredient) is 6.0% by mass, "Super Flex 620" (emulsion of cationic water-dispersible urethane resin, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 30% by mass of active ingredient) 9.0% by mass, 10.0% by mass of diethylene glycol (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and the balance ion-exchanged water (100% by mass in total). For the materials containing solvents and the like among the materials of the pretreatment liquid, the above compounding amounts are indicated by the total amount of the materials including the solvent and the like.

<Ink>
For the ink, 15.0% by mass of “BONJET BLACK CW-1” (black pigment dispersion, manufactured by Orient Chemical Industry Co., Ltd., 20% by mass of active ingredient), “Superflex 470” (anionic water-dispersible urethane 5.0% by mass of "NeoCryl A-1125" (anionic water-dispersible (meth)acrylic resin emulsion, DSM Coating Resins). Co., Ltd., active ingredient 19.5% by mass) is 4.0% by mass, and "Silface SAG002" (silicone-based surfactant, manufactured by Nissin Chemical Industry Co., Ltd., active ingredient 100% by mass) is 1.0% by mass. , 20.0% by mass of diethylene glycol (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and the remainder containing ion-exchanged water (100% by mass in total). Among the ink materials described above, for the materials containing solvents and the like, the above compounding amounts are indicated by the total amount of the materials including the solvent and the like.

<Treatment solutions OC1 to OC7>
Table 1 shows the formulations of the treatment liquids OC1 to OC7. The blending amount of each raw material in Table 1 is shown in % by mass. In Table 1, for the materials containing solvents and the like among the materials, the compounding amount shown in the table is the total amount of the materials including the solvent and the like.

The raw materials listed in Table 1 are as follows.

Silface SAG002: Nissin Chemical Co., Ltd., silicone surfactant Superflex 620: Daiichi Kogyo Seiyaku Co., Ltd., water-dispersible urethane resin emulsion (cationic, Tg = 43 ° C.)
Himax SC-700L: manufactured by Hymo Co., Ltd., cationic water-soluble resin Magnesium chloride: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., magnesium chloride hexahydrate is converted to the amount of anhydrous magnesium chloride and used (the amount in the table is Amount converted to anhydrous magnesium chloride)
Superflex 830HS: Daiichi Kogyo Seiyaku Co., Ltd., water-dispersible urethane resin emulsion (anionic, Tg = 68 ° C.)
NeoCryl A-1125: manufactured by DSM Coating Resins, water-dispersible (meth)acrylic resin emulsion (anionic, Tg = 13°C)
Superflex 420: Water-dispersible urethane resin emulsion (anionic, Tg = -10°C) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
Seahoster KE-P150: manufactured by Nippon Shokubai Co., Ltd., silica particles for water dispersion 1.5 μm
Diethylene glycol: Water-soluble organic solvent manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Diethylene glycol monobutyl ether: Water-soluble organic solvent manufactured by Tokyo Chemical Industry Co., Ltd.

<Production of decoration>
After the pretreatment liquid was spray-coated on the base material, the base material was placed in a constant temperature bath and dried at 120° C. for 10 minutes. After loading the ink in an inkjet printer "MMP8130" manufactured by Mastermind Co., Ltd. and printing a 5 cm square black solid image in the area where the pretreatment liquid has been applied to the pretreated and dried base material. , the substrate was placed in a constant temperature bath and dried at 120°C for 30 minutes. After the treatment liquid 2 was spray-coated on the solid image-printed area of the base material that had been subjected to the above ink application and drying, the base material was placed in a constant temperature bath and dried at 120° C. for 10 minutes. After the treatment liquid 1 was spray-coated on the solid image-printed area of the base material to which the treatment liquid 2 was applied and dried, the base material was placed in a constant temperature bath and dried at 120° C. for 30 minutes, followed by heating. got an ornament. The amount of the pretreatment liquid applied to the substrate was 20 g/m ² per unit area of the substrate. The amount of ink applied to the substrate was 15 g/m ² per unit area of the substrate. The amount of treatment liquid 1 and treatment liquid 2 applied to the substrate was 40 g/m ² per unit area of the substrate.
In Examples 1 to 6 and Comparative Example 7, treatment liquid 1 and treatment liquid 2 shown in Tables 2 and 3 were used.
Comparative Examples 1 to 3 did not use the treatment liquid 2, and Comparative Example 4 did not use either of the treatment liquids 1 and 2.

<Glossiness at an incident angle of 60°>
The glossiness of the solid image area of the decoration obtained as described above was measured at an incident angle of 60°. The glossiness was measured according to JIS Z 8741 "Specular glossiness - measuring method" using GM-60A manufactured by Konica Minolta. The measured gloss values at an incident angle of 60° are shown in Tables 2 and 3.

In Tables 2 and 3, the 'A' and 'B' shown below the gloss value at an incident angle of 60° are as follows.
A: The glossiness at an incident angle of 60° is 30 or less B: The glossiness at an incident angle of 60° is more than 30

<Bendability>
Using a bending machine "FαBIII-5012" manufactured by Amada Co., Ltd., with a V-shaped mold of 88° and a groove width of 4 mm, the decoration is bent at an angle of 90° so that the printed surface faces outward and is bent in the solid image area. It was bent into The minimum bending radius of this bent portion is 0.47 mm on the inside, but on the outside, which is the printed surface, the value is the sum of the aluminum plate base material and the thickness of the coated and printed material, which is about 0.97 mm. become.
The bending workability was evaluated according to the following evaluation criteria. Results are shown in Tables 2 and 3.
A: Beautiful curved curved surface with no change in appearance B: Slight working indentation remained C: Working indentation remained D: Whitening was observed in the bent and stretched part

In Examples 1 to 7, the treatment liquids 2 and 1 caused an aggregation reaction, and the gloss of the overcoat layer was suppressed, resulting in a good appearance. Further, in Examples 1 to 7, the treatment liquid OC4, the treatment liquid OC5, and the treatment liquid OC1 containing a water-dispersible resin having a glass transition point of 0° C. or higher were used as the treatment liquid 1, and bending workability was also good. rice field.
In Examples 1, 2, and 7, in which a water-dispersible resin was used as a flocculating agent for the treatment liquid 2, the coating film after drying was stronger and had an appearance without any processing impressions. When the flocculant of the treatment liquid 2 is a water-dispersible resin, it is considered that the film strength after drying tends to be higher than in the case of a water-soluble resin or metal salt.

On the other hand, in Comparative Examples 1 and 2, there was no agglutination reaction due to the treatment liquid 2, and the gloss was too high, resulting in undesirable appearance.
In Comparative Example 3, the gloss was controlled by the action of the silica particles contained in the treatment liquid OC6, and the appearance was good. It is considered that delamination occurred at the interface between the silica particles added for the purpose of matting and the resin.
In Comparative Example 4, only the pretreatment liquid and the ink were applied, and although the gloss was controlled and the appearance was good, impressions from the working jig remained after bending.
In Comparative Example 5, the Tg of the water-dispersible resin contained in the treatment liquid OC7 was low, and the film strength was weak, so that bending impressions remained.

Claims (4)

After applying an ink containing a coloring material to a metal substrate, applying a treatment liquid 1 and a treatment liquid 2 to the metal substrate,
The treatment liquid 1 contains a water-dispersible resin having a glass transition point of 0° C. or higher,
The treatment liquid 2 contains an aggregating agent that aggregates the water-dispersible resin having a glass transition point of 0° C. or higher in the treatment liquid 1,
A method for manufacturing a decorative article, wherein the treatment liquid 1 and the treatment liquid 2 are applied to the metal substrate in the order of the treatment liquid 2 and the treatment liquid 1 . The method for manufacturing a decorative article according to claim 1, wherein the flocculant of the treatment liquid 2 contains a water-dispersible resin. 3. The method for producing a decorative article according to claim 1, wherein the flocculant of the treatment liquid 2 contains a cationic water-dispersible resin. The method for producing a decorative article according to any one of claims 1 to 3, wherein the water-dispersible resin having a glass transition point of 0°C or higher in the treatment liquid 1 includes an anionic water-dispersible resin.