JP2007152149A - Manufacturing method of design building materials - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of design building materials which enhances the durability of ink and prevents the bleeding of ink in printing on the surface of a building material using an inkjet printer. <P>SOLUTION: The manufacturing method of design building materials comprises a step (1) of applying a coating for forming the face to be printed on the building material to form the layer to be printed, a step (2) of discharging to the layer to be printed a coloring ink containing a reactive compound (A) causing to react with a reactive compound (B) by the inkjet printing system to form the colored area and a step (3) of discharging a clear ink containing the reactive compound (B) in the colored area. In these steps, the coloring ink containing the reactive compound (A) may be discharged in the clear area after discharging the clear ink containing the reactive compound (B) causing to react with the reactive compound (A) to the layer to be printed by the inkjet printing system to form the clear area. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a designable building material.

Conventionally, various methods have been taken as methods for imparting higher designability to building materials. Among these methods, a method that is usually used includes, for example, a method of coating a paint on the surface of a building material.
This method can be applied to a wide range of objects by coating the object with a pre-colored paint to a desired color and changing the coating method according to the shape of the object. Has the advantage that
However, on the other hand, the design applied by painting has the problem that it is only possible to apply a design with a single color for a certain area, and it is difficult to give a pattern with higher design properties, etc. .

On the other hand, a printing method using an ink jet printer has recently attracted attention as a method for imparting a design having a higher design property to a building material. The advantage of using an ink jet printer is that ink can be ejected in a non-contact state with respect to the object, so that it can be applied even if the surface shape of the object to be printed has irregularities, and Since patterning can be performed only on the necessary portions, it is possible to give a wide range of designs to building materials.
Various techniques have been studied as printing techniques using an ink jet printer. For example, Patent Document 1 below is representative of these techniques.

Japanese Patent No. 2636693

The technique of Patent Document 1 is an excellent technique for producing a designable building material. However, the design building material is required to have durability such as weather resistance and water resistance because it is installed outside that directly contacts sunlight or air. And in order to give durability to the colored ink used for the designable building material, a binder component such as a resin is blended with the ink, or a clear paint is applied after discharging the ink, It is necessary to form an ink protective layer.

However, when the binder component is simply blended with the ink, the ink is easily clogged with the nozzle of the ink jet printer, and there is a problem that the printer malfunctions and the production efficiency of the design base material is lowered. This is due to the fact that a binder component such as a resin blended for imparting durability to the ink reacts and cures around the ink nozzle, thereby causing clogging of the nozzle. This is particularly noticeable when a high quality design is formed. This is because, in order to form a high-quality design, it is necessary to reduce the diameter of the ink nozzle, and nozzle clogging is more likely to occur.
On the other hand, when the clear paint is applied after the ink is discharged, if the clear paint is applied after the ink containing no binder component is discharged, there is a problem that the ink in an undried state bleeds and the design properties of the building material are lowered. This problem is particularly noticeable when the ink and the clear paint are both water-based or both solvent-based.
For this reason, when manufacturing the designable building material which uses an inkjet printer, the manufacturing method of the designable building material which does not produce nozzle clogging and does not cause the bleeding of colored ink is strongly desired.

As a result of earnestly examining the means for solving the above-mentioned problems in producing a designable building material, the present inventors have found that the above-mentioned problems can be solved by the following method, and have reached the present invention. is there.
That is, this invention exists in the following invention.
1. A method for manufacturing a design building material,
(1) A process of forming a printing layer by applying a printing surface forming paint on the surface of the building material,
(2) discharging the colored ink containing the reactive compound (A) that reacts with the reactive compound (B) to the printing layer by an ink jet printing method to form a colored region;
(3) A step of discharging a clear ink containing the reactive compound (B) to the colored region,
A method characterized by comprising:
2. A method for manufacturing a design building material,
(1) A process of forming a printing layer by applying a printing surface forming paint on the surface of the building material,
(2) A step of discharging a clear ink containing a reactive compound (B) that reacts with the reactive compound (A) to the printing layer by an ink jet printing method to form a clear region;
(3) discharging colored ink containing the reactive compound (A) to the clear region;
A method characterized by comprising:

  According to the present invention, it is possible to efficiently produce a design building material while preventing the occurrence of nozzle clogging of an ink jet printer by separately ejecting reactive components that react with each other, and formed on the surface of the building material The durability and weather resistance of the designed design can be improved, and further, bleeding of the colored ink can be prevented.

The method of the present invention is applied to building materials.
A sealer may be applied to the surface of the building material in advance if necessary.
Sealers are usually used for the purpose of physical strengthening of the surface layer of building materials, prevention of permeation of moisture and alkali in building materials, prevention of inhalation of printed surface forming paints into equipment, or improvement of adhesion of printed surface forming paints to substrates. used.
The sealer is mainly composed of a binder, and may contain a solvent, a filler, other additives and the like as necessary.

As the binder, resins conventionally used for building materials can be used without any particular limitation. As such a resin, for example, an epoxy resin, a vinyl resin, an acrylic resin, a urethane resin, or the like can be used alone or in combination, or these can be used in combination with a curing agent, a curing acceleration catalyst, or the like. .
As said solvent, the solvent conventionally used by the coating material can be especially used without a restriction | limiting. Examples of such solvents include aromatic hydrocarbons such as toluene and xylene: acetates such as ethyl acetate and butyl acetate: ketones such as methyl ethyl ketone and methyl isobutyl ketone: isopropyl alcohol, butyl alcohol and the like. Alcohols: Furthermore, one kind selected from various aliphatic hydrocarbons, glycol ethers, water, etc., or a combination of two or more kinds can be used. In addition, it is preferable to mainly use water from the viewpoint of handling safety and the viewpoint of the environment.

Representative examples of the filler include, for example, titanium oxide, zinc oxide, zinc sulfide, carbon black, yellow lead, ocher, bengara, composite oxide (nickel / titanium series, chromium / titanium series, bismuth / Inorganic pigments such as vanadium) and organic pigments such as phthalocyanine blue, carmine FB, Hansa yellow, quinacridone, diketopyrrolopyrrole, benzimidazolone, isoindolinone, anthrapyramidine, selenium, dioxazine, etc. Various organic and inorganic color pigments used for paints: talc, kaolin, barium sulfate, calcium carbonate, mica, quartzite powder, diatomaceous earth, amorphous silica, allophane, imogolite, bentonite, montmorillonite, Body pigments typified by porous inorganic powders such as sepiolite And the like.
Typical examples of the additive include an antifoaming agent, a leveling agent, a film forming aid, an antibacterial agent, a crosslinking accelerator, a dispersant, and a precipitation inhibitor.

  The sealer is preferably applied on the surface of the building material so that the sealer is preferably 40 to 80 g / m 2 in terms of solid content. In addition, when applying a sealer, conventional methods for applying paint can be used without any particular restrictions, for example, air spray, airless spray, flow coater, roller, etc. It is mentioned as a thing. Moreover, after coating the sealer, it can be dried in a temperature range of 80 to 120 ° C. for a time range of 2 to 10 minutes. Furthermore, when the sealer to be used is a water-based sealer, it is possible to obtain a good sealer film by preheating the building material surface temperature to 40 to 60 ° C. before coating.

The building material is not particularly limited as long as it is a building material that has been conventionally used for construction purposes. Such building materials include, for example, plastic substrates, metal substrates such as aluminum, iron, stainless steel, galvanized plates, flexible boards, calcium silicate plates, gypsum slag bar light plates, wood chip cement plates, precast concrete Inorganic substrates such as plates, ALC plates, and gypsum boards, and wood and paper are preferable examples.
These building materials may have a smooth surface or an uneven shape.
Before the inkjet printing is performed on the building material, a printing surface forming paint is applied to form a printing layer on the surface of the building material.

Printed surface forming coating The printed surface forming coating used in the present invention improves the ink absorbency as a printed layer by providing it on the building material surface when printing a pattern or the like by the ink jet printing method. Therefore, it is used for improving the production efficiency of the design building material or preventing the ink from bleeding.
The printing surface-forming coating material is mainly composed of a binder, and a solvent, a filler, other additives, and the like can be blended as necessary. Further, the printing surface-forming coating material may be in any form such as water-based, solvent-based, and powder-based, but it is more preferable to use a water-based one from the viewpoint of handling safety and environmental problems.
The printing surface forming coating material is conventionally used for each building material, and various coating materials can be used without any particular limitation.

  As the binder used for the coating material for forming the printing surface, various resins conventionally used in building material paints can be used without particular limitation. Examples of such resins include epoxy resins, vinyl resins, polyester resins, acrylic resins, urethane resins, fluorine resins, silicone resins, acrylic silicone resins, inorganic resins such as silicone resins, and modified resins thereof. These may be used alone or in combination of two or more thereof, a curing agent, a curing catalyst, or the like.

  As the solvent used for the printing surface-forming coating material, various solvents conventionally used in coating materials can be used without particular limitation. Examples of such solvents include aromatic hydrocarbons such as toluene and xylene: acetates such as ethyl acetate and butyl acetate: ketones such as methyl ethyl ketone and methyl isobutyl ketone: isopropyl alcohol, butyl alcohol and the like. Alcohols: Further, one kind selected from various aliphatic hydrocarbons, glycol ethers, water and the like, or a combination of two or more kinds can be used. From the viewpoint of handling safety and the viewpoint of the environment, it is preferable to mainly use water.

  Typical fillers used in the coating material for printing surface formation include, for example, titanium oxide, zinc oxide, zinc sulfide, carbon black, yellow lead, ocher, petal, composite oxide (nickel Inorganic pigments such as titanium-based, chromium-titanium-based, bismuth-vanadium-based), phthalocyanine blue, carmine FB, hansa yellow, quinacridone, diketopyrrolopyrrole, benzimidazolone, isoindolinone, anthrapyramidine, selenium, Various organic and inorganic color pigments, such as organic pigments such as dioxazine, which are generally used for paints: talc, kaolin, barium sulfate, calcium carbonate, mica, quartzite powder, diatomaceous earth, amorphous Porous inorganic powders such as silica, allophane, imogolite, bentonite, montmorillonite, sepiolite And powders of polyacrylate copolymer, saponified vinyl acetate-acrylic acid ester copolymer, saponified vinyl acetate-maleic acid ester copolymer, isobutylene-maleic anhydride copolymer, polyethylene oxide crosslinked product, etc. Typical examples include organic and inorganic extender pigments such as organic resins in the form of a suspension or suspension, but are not limited thereto.

Among the fillers used in the coating surface to be printed is formed, if necessary, oil absorption of 30 to 400 ml / m ^2, preferably, 40~370ml / m ^2, more preferably, 50～350Ml / An m ² filler can be selected and blended. Hereinafter, these fillers are referred to as “water-absorbing fillers” for convenience. Than oil absorption of the filler is lower than 30 ml / m ^2, it tends to be difficult to increase the ink solvent absorbing ability of the coating. Moreover, when it exceeds 400 ml / m < ² >, when knead | mixing a coating material, a viscosity will raise large, and coating-material manufacture becomes difficult, or it exists in the tendency for durability of a building material to fall. These water-absorbing fillers can be used alone or in combination of two or more.

  Examples of such water-absorbing fillers include porous inorganic powders such as diatomaceous earth, amorphous silica, allophane, imogolite, bentonite, montmorillonite, and sepiolite, and polyacrylate-based coagulants. Polymer (including polyacrylic acid ester polymer in the core and polymer having a different phase structure of sodium acrylate polymer in the outer shell) Vinyl acetate-acrylate copolymer saponified vinyl acetate-maleic acid ester Powdered or suspended organic resins such as copolymer saponified products, isobutylene-maleic anhydride copolymers, polyethylene oxide cross-linked products, and the like can be suitably used. In the present invention, a polyacrylate copolymer having an internal cross-linked structure can be preferably used. By using such particles, when ink is ejected onto the surface to be printed, particle expansion due to absorption of the solvent of the ink can be prevented, and a high-quality image can be formed. . Typical examples of such particles include tuftic HU720, tuftic HU720P, tuftic HU720PS, etc. (toyobo Co., Ltd .: sodium polyacrylate particles).

When blending the water-absorbing filler in the coating material for forming the printing surface, the blending amount of the water-absorbing filler in the printing layer is preferably in the range of 1.5 to 70% by volume, and 5 to 50 More preferably, it is in the range of volume%. When the blending amount of the water-absorbing filler is less than 1.5% by volume, the ink absorbing ability of the printing layer is lowered, and bleeding tends to occur when a clear paint is applied. On the other hand, if it exceeds 70% by volume, the coating film strength of the printing layer is lowered, the durability of the design building material is lowered, or the ink absorbability is excessive, and the image quality is liable to be lowered. It is in.
Other additives include, for example, antifoaming agents, leveling agents, ultraviolet absorbers, film forming aids, light stabilizers, antibacterial agents, crosslinking accelerators, dispersants, suspending agents, and wetting aids for ink solvents. An agent or the like can be blended as necessary, and the type and amount of the additive can be changed depending on the binder, color pigment, extender pigment, water-absorbing filler, solvent, and the like to be used.

As the printing surface forming coating material, it is preferable to use a coating material having a liquid absorption amount of 0.5 to 15.0 g / m ² when the printing layer is dried, for example, 1.0 to 12.0 g / m ^2. It is more preferable to use a paint with m ^2, and it is even more preferable to use a paint with 2.0 to 10.0 g / m ² . If liquid absorption amount at the time of drying is lower than 0.5 g / m ² is reduced ink absorption capacity of the surface of the printing layer, production efficiency is lowered in a design building materials, a clear coating after ink printing In the case of painting, ink bleeding tends to occur. On the other hand, if the liquid absorption amount is higher than 15.0 g / m ^{2, the} ejected ink is excessively absorbed, and the image quality of the printed image tends to be lowered.
Such adjustment of the liquid absorption amount can be easily carried out by those skilled in the art, for example, by adjusting the content of the filler in the coating film, in particular, the content of the water absorbent filler. it can.

In addition, in this specification, the amount of liquid absorption refers to the numerical value measured with the following method. The following operations are all performed in a temperature-controlled room at a temperature of 23 ° C. and a humidity of 50%.
A paint for forming a printing surface is applied to a glass plate (200 × 250 × 2 mm) by spray coating. The coating amount is 40 g / m ² in terms of dry weight, and coating is performed so that the coating film surface is smooth and the film thickness is averagely oriented over the entire glass plate. When the painted surface-forming coating material is a room temperature drying type coating material, forced drying is performed at 80 ° C. for 30 minutes. When the painted surface-forming coating material is a baking-drying type coating material, forced drying is performed at 150 ° C. for 30 minutes. After finishing the forced drying, it is allowed to stand for 168 hours in a temperature-controlled room at a temperature of 23 ° C. and a humidity of 50%. After allowing to stand, coking is performed with a silicon caulking agent having no water absorption on the end face of the glass plate on which the coating film is formed.

  Silicon coking is performed in order to prevent water from penetrating and flowing out from the side of the coating film, and is performed with great care so that the caulking material does not touch the coating film surface. In addition, the silicon caulking is raised so as to have a height of 3 mm on the surface on which the coating film is formed, so that water does not spill when water is poured onto the coating film surface. After performing silicon coking and holding in a temperature-controlled room at a temperature of 23 ° C. and a humidity of 50% for 24 hours, the mass is measured, and this measured value is taken as the initial mass. Place the coked sample in a horizontal place, pour 200 g of water onto the surface of the measurement sample (the surface on which the printing surface forming coating film is formed) so that the entire surface gets wet, and pour the water. Immediately after that, tilt the measurement sample, remove the water, place it on the Kim Towel (manufactured by Crecia Co., Ltd.) with the back side down, remove the water adhering to the back side, and remove excess water adhering to the surface with the same Kim Towel. Wipe off. Immediately after the removal of excess water, measure the mass. In addition, the time from pouring water to measuring the mass should be as short as possible, and should be within 1 minute at the longest. The liquid absorption amount is calculated by the following calculation formula based on the measurement result.

(Mass immediately after wiping-initial mass) / Area of glass plate = Liquid absorption (g / m ² )

In the following, the numerical value of the liquid absorption amount refers to the numerical value measured by the above method.
As long as the coating material for printing surface formation is the coating method conventionally employ | adopted, various coating methods can be used without a restriction | limiting in particular. As such a coating method, for example, various methods such as air spray coating, airless spray coating, electrostatic coating, roll coater coating, and flow coater coating can be appropriately selected. In particular, when the surface of the building material has unevenness, airless spray coating, electrostatic coating, or the like can be suitably used from the ability to follow the uneven shape and adaptability of the coating speed. Depending on the composition of the paint for forming the printing surface, the surface temperature of the building material immediately before coating is preheated to, for example, 30 to 70 ° C., which is an effective means for forming a good printing layer. It may become.
The conditions for curing or drying the printing surface-forming coating material can be selected from any method such as room temperature drying, forced drying, or curing drying by irradiation with active energy rays, depending on the type of paint, and can be selected as appropriate depending on the paint formulation. can do.

Coating the printed face forming, to the building material surface, in terms of solid content, for example, 20 to 80 g / m ^2, preferably, the coating amount of 30 to 60 g / m ^2, it is preferable to paint.
If the coating amount is less than 20 g / m ² , the durability of the manufactured design building material may be lowered. On the other hand, if it exceeds 80 g / m ² , the time required for drying the coating material for forming the printing surface becomes longer, and the improvement in performance by applying the coating material for forming the printing surface cannot be expected, which is disadvantageous in cost. easy.
The coating material for forming the printing surface does not necessarily need to be completely cured or dried, and may be subjected to inkjet printing described later in a state where the solvent is evaporated to some extent, that is, in a semi-dry state, or may be completely cured or It may be in a dried state.
In addition, before forming a colored region to be described later, other printing means such as gravure printing, screen printing, etc. are provided on the layer to be printed in order to realize further advanced design expression or to supplement ink jet printing. You may give it.

In the first aspect, a colored region is formed on the printing layer by ejecting colored ink by an inkjet method. This colored region can be entirely colored as a single color, or partially colored with a composite color having a different hue, or patterned in a pattern. The pattern or coloring can be formed on the entire surface of the building material, or can be formed on a part of the surface of the building material. Moreover, when the building material surface has an unevenness | corrugation, a recessed part and a convex part can also be colored with a different color.

Colored ink The colored ink used in the present invention may be either solvent-based, water-based or solvent-free. From the viewpoint of safety and the environment, it is preferable to use an aqueous or solvent-free one.
The colored ink contains a coloring pigment, a solvent, a reactive compound (A) described in detail below, and a dispersant as main components, and may contain other additives such as a filler as necessary. it can.
As the color pigment, any of known color pigments generally used in paints and inks can be used. However, an inorganic pigment is mainly blended from the weather resistance or durability of the formed color and pattern. Is preferred.

Typical examples of inorganic pigments include carbon black, iron oxide, composite oxides (nickel / titanium, chromium / titanium, bismuth / vanadium), titanium oxide, and the like. It is not limited.
In addition to the above inorganic pigments, organic color pigments can also be blended. Typical examples of such organic coloring pigments include quinacridone, diketoprolope, benzimidazolone, isoindolinone, anthrapyrimidine, selenium, dioxazine and the like.

The color pigment is preferably added in an amount of, for example, 0.5 to 15.0 parts by mass, and preferably 1.0 to 10.0 parts by mass with respect to 100 parts by mass of the colored ink. When the blending amount exceeds, for example, 15.0 parts by mass, the ink viscosity rises and the ink dries too quickly, which easily causes clogging in the nozzle portion of the inkjet printer described below used for printing. In addition, the accuracy of applying ink droplets to the printing surface tends to deteriorate.
If the blending amount is less than 0.5 parts by mass, the pattern formed tends to be unclear because coloring is insufficient. In addition, when an organic pigment is used as the colorant for the ink, it is necessary to sufficiently consider light resistance and fading.

The color pigment preferably has an average particle size of, for example, 20 to 400 nm, and more preferably 25 to 300 nm.
If the average particle size is less than 20 nm, the viscosity of the ink tends to increase or the light resistance tends to decrease. If it exceeds 400 nm, clogging of the discharge nozzle of the ink jet printer tends to occur, and printing with high image quality as described above tends to be difficult.

As the solvent, various solvents conventionally used in inks can be used without particular limitation. Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, triethylene glycol monobutyl ether, and other ethylene glycols. Ethers: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene Typical examples include propylene glycol ethers such as ethylene glycol diethyl ether and dipropylene bricol diethyl ether, organic solvents such as ethylene glycol, polyhydric alcohols such as propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and glycerin, and water. Suitable examples are mentioned.
These solvents may be used alone or in combination of two or more. In the present invention, it is more preferable to use water as a main solvent from the viewpoint of safety in handling and the viewpoint of the environment.

The solvent is preferably blended in an amount of, for example, 5 to 99% by mass, and more preferably 30 to 90% by mass with respect to the colored ink. When the blending amount of the solvent is less than 5% by mass, it becomes difficult to discharge the colored ink, and clogging of the ink nozzles occurs, resulting in a decrease in the manufacturing efficiency of the design building material. On the other hand, when it is more than 99% by mass, the coloring power of the ink tends to decrease.
The reactive compound (A) is preferably blended in an amount of, for example, 0.1 to 70% by weight, more preferably 1.0 to 60% by weight, based on the colored ink. More preferably 5 to 50% by mass is blended. When the blending amount is less than 0.1% by mass, the image durability and the ink bleeding resistance as described above tend to be lowered. On the other hand, when the blending amount is more than 70% by mass, problems such as an increase in ink viscosity, a decrease in stability, and clogging of ink nozzles tend to occur.

Examples of the dispersant used in the color ink include polyester polyamide resins, fatty acid salts as carboxylic acid salts, rosin acid salts, higher alcohol sulfates as sulfates, higher alkyl ether sulfates, sulfates, and the like. Fatty acid ester salts, etc., sulfonates such as alkylbenzene sulfonate, alkylnaphthalene sulfonate, paraffin sulfonate, etc., phosphoric acid ester salts such as alkyl phosphate, ether phosphate, alkylaryl ether phosphate, etc. Dispersants, ethers such as polyoxyethylene alkyl ether, polyoxyalkyl allyl ether, polyoxyethylene polyoxypropylene glycol, etc., esters such as glycerin partial ester, sorbitan ester, etc. Glycerol ester Lupo polyoxyethylene ether as esters, sorbitan esters, polyoxyethylene ethers,

Nonionic dispersants such as fatty acid alkanolamides and polyoxyethylene fatty acid amides as nitrogen-containing compounds, or styrene-maleic anhydride copolymer salts, olefin-maleic anhydride copolymer salts, naphthalenesulfonate formalin condensates, etc. Anionic polymer dispersants, polyvinyl alcohol, polyoxyethylene ether ester copolymers, nonionic polymer dispersants such as polyacrylamide, etc., or a combination of two or more thereof can be used. . About the kind and addition amount of these dispersing agents, it can use suitably by the kind, content, the kind of diluent, content, etc. of a pigment.
As other additives used in the colored ink, for example, a conductivity adjusting agent, an antifoaming agent, a precipitation preventing agent, an ultraviolet absorber, a light stabilizer, a preservative, and the like can be added as necessary.
As the filler used for the colored ink, for example, barium sulfate, calcium carbonate and the like can be added.

The colored ink can be discharged using various ink jet printers conventionally used in ink jet printing without any limitation. As the printer type, either a continuous method or an on-demand method can be used. As a method for ejecting ink, various methods such as a valve opening / closing method, a bubble jet (registered trademark) method, and a piezo drop method can be used.
In the present invention, it is preferable to use an on-demand type piezo drop type ink jet printer for discharging colored ink from the viewpoint of manufacturing efficiency of the designable building material.

Clear Ink <br/> clear ink, water resistance and coloration regions, solvent resistance, chemical resistance, stain resistance, when improving the durability such as weather resistance, further recoated a clear paint, clear It is used to prevent bleeding of the ink in the colored area that occurs when the paint is applied.
The clear ink used in the present invention comprises a solvent and a reactive compound (B) described in detail below, and contains various additives as necessary.
As the solvent used in the clear ink, various solvents conventionally used in ink can be used without particular limitation. Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, triethylene glycol monobutyl ether, and other ethylene glycols. Ethers: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene Typical examples include propylene glycol ethers such as ethylene glycol diethyl ether and dipropylene bricol diethyl ether, organic solvents such as ethylene glycol, polyhydric alcohols such as propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and glycerin, and water. The thing is mentioned.
A solvent may be used independently and may be used in combination of 2 or more type. In the present invention, it is more preferable to use water as a main solvent from the viewpoint of safety in handling and the viewpoint of the environment.

The blending amount of the solvent is, for example, preferably 5 to 99% by mass and more preferably 30 to 90% by mass with respect to the clear ink. When the blending amount of the solvent is less than 5% by mass, it becomes difficult to discharge the clear ink, and clogging of the ink nozzles or the like occurs. As a result, the manufacturing efficiency of the design building material tends to decrease. On the other hand, if it exceeds 99% by mass, the reaction of the compound blended with the clear ink and the colored ink becomes insufficient, and the water resistance of the formed image tends to be lowered.
The reactive compound (B) is, for example, preferably blended in an amount of 0.1 to 70% by weight, more preferably 1.0 to 60% by weight, based on the clear ink. More preferably, it is blended in an amount of ˜50 mass%. When the blending amount is less than 0.1% by mass, the image durability and the ink bleeding resistance as described above tend to be lowered. On the other hand, if it exceeds 70% by mass, problems such as an increase in ink viscosity, a decrease in stability, and clogging of ink nozzles tend to occur.
As an additive compounded in the clear ink, for example, a conductivity adjusting agent, an antifoaming agent, a precipitation preventing agent, an ultraviolet absorber, a light stabilizer, a preservative, and the like can be added as necessary.

The clear ink can be ejected in the same manner as the colored ink. Of course, the ink can be ejected by an ink jet method different from that of the colored ink. For discharging the clear ink, for example, it is preferable to use an on-demand type piezo drop type ink jet printer.

After discharging the clear ink, the building material may be heated as necessary. By performing such heating, volatile components contained in the colored ink and the clear ink can be evaporated, and further the reaction between the reactive compounds (A) and (B) blended in the colored ink and the clear ink is promoted. Can be made.
The heating conditions vary depending on the types of the reactive compounds (A) and (B) to be used and the composition of the ink, but the conditions can be set in the temperature range of 40 to 150 ° C. and in the range of 10 to 1200 seconds. it can.

Regarding the reactive compound (A) in the colored ink and the reactive compound (B) in the clear ink, the reactive compound (A) blended in the colored ink used in the present invention is the It reacts with the reactive compound (B) blended in the discharged clear ink. By mixing these reactive compounds (A) and reactive compounds (B) with the colored ink and the clear ink, respectively, when the clear ink is ejected after the colored ink is ejected, both inks react. The colored ink adheres firmly on the printing surface, and the durability performance such as weather resistance and water resistance of the obtained image is improved.

  The combination of the reactive compound (A) and the reactive compound (B) can be used without particular limitation as long as it is a substance that is reactive with each other. Containing compound and amino group containing compound, epoxy group containing compound and hydroxyl group containing compound, epoxy group containing compound and carboxyl group containing compound, ethyleneimine group containing compound and carboxyl group containing compound, ethyleneimine group containing compound and hydroxyl group containing compound, ethyleneimine Group-containing compound and amino group-containing compound, oxazoline group-containing compound and carboxyl group-containing compound, carbonyl group-containing compound and hydrazide group-containing compound, isocyanate group-containing compound and hydroxyl group-containing compound, isocyanate-containing compound and carboxyl group-containing compound, isocyanate-containing compound And amino Containing compounds, combination selected from at least one silyl group-containing compound and a metal catalyst compound.

Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycidyl ethers of glycerin polyglycidyl ether, bisphenol A type epoxy resin, and bisphenol F type epoxy resin. Typical examples thereof include epoxy resins.
Examples of the amino group-containing compound include polyamides having an active hydrogen equivalent of 50 to 300, ethylenediamine, trimethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, diethylaminopropylamine, polyamide polyamine, Mensendiamine and the like are preferred as typical examples.

Representative examples of the hydroxyl group-containing compound include a resin obtained by polymerizing a monomer containing a hydroxyl group. Examples of the monomer containing a hydroxyl group include hydroxymethyl (meth) acrylate, 2-hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxyamyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) Acrylate and the like are typical examples. The resin can be obtained by using one or more of these monomers and polymerizing other monomers as required.

Examples of the carboxyl group-containing compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, monomethyl itaconate, Preferable examples include monoethyl itaconate, mono-2- (meth) acryloyloxyethyl hexahydrophthalate and the like, polymers thereof, and polymers of these with other monomers.
As said ethyleneimine group containing compound, ethyleneimine is mentioned suitably, for example.

  The oxazoline group-containing compound refers to a substance containing an oxazoline group as an essential component. Typical examples of these include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2. -Oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-4,5 -Dimethyl-2-oxazoline etc. can be raised, 1 or 2 or more of these can be used in combination, and the resin copolymerized using the monomer polymerizable with these can be used.

  Suitable examples of the carbonyl group-containing compound include a resin obtained by polymerizing a monomer containing a carbonyl group. Examples of these carbonyl group-containing monomers include diacetone acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl n-propyl ketone, vinyl i-propyl ketone, vinyl n-butyl ketone, and vinyl i. -Butyl ketone, vinyl-t-butyl ketone, vinyl phenyl ketone, vinyl benzyl ketone, divinyl ketone, diacetone acrylate, acetonitrile acrylate, 2-hydroxypropyl acrylate-acetyl acetate, and the like are preferable. When the resin is polymerized, it can be obtained by copolymerizing one or more of the carbonyl group-containing monomers together with a monomer polymerizable with these monomers.

  Examples of the hydrazide group-containing compound include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, maleic acid Itaconic acid dihydrazide, citric acid trihydrazide / nitrilolic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, ethylene-1,2-dihydrazine, propylene-1,2-dihydrazine, propylene-1,3- Typical examples include dihydrazine, butylene-1,3-dihydrazine, butylene-1,4-dihydrazine, butylene-2,3-dihydrazine and the like. .

  Examples of isocyanate group-containing compounds include tolylene diisocyanate, 1,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, tolidine diisocyanate, xylene diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and the like. A suitable example is given.

  Examples of the silyl group-containing compound include a vinyl group, an epoxy group, a styryl group, an amino group, a ureido group, a mercapto group, a sulfide group, and a functional group selected from the group consisting of an isocyanate group and a hydrolyzable silane group. Examples of the compound having vinyl trimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltri Ethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3 4-epoxycyclohexyl) ethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane ,

N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane N-β- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxy Silane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3- Ureidopropyltriethoxysilane, 3- Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (trimethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltrimethoxysilane,

Silane coupling agents such as 3-isocyanatopropyltriethoxysilane: methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i- Propyltrimethoxysilane, i-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane 3,3,3-trifluoropropyltriethoxysilane, cyclohexyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-me Lucaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxy Organosilane compounds such as silane, methylphenyldimethoxysilane, dimethyldipropoxysilane, and the like: Polymers synthesized with a silane coupling agent and / or an organosilane compound are preferred.

Typical examples of the metal catalyst compound include tetraacetyl acetate zirconium, tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxydi (ethyl acetoacetate) zirconium, and the like.

In the present invention, when the colored ink and the clear ink are water-based inks, it is more preferable to use a combination of a carbonyl group-containing compound and a hydrazide group-containing compound. In water-based inks, the advantage of using the above combination is that the reaction between the carbonyl group and the hydrazide group does not react in the presence of water, but starts when the water is removed. This is because clogging is less likely to occur.
Moreover, there is no restriction | limiting in particular which is mix | blended with a colored ink as a reactive compound (A) among the said combinations, and is mix | blended with a clear ink as a reactive compound (B).
When the colored ink and the clear ink are water-based inks, the reactive compound (A) or / and (B) is a polymer compound such as a resin. Any one can be used.

The clear ink is ejected to the colored area. However, the dot of the colored ink and the dot of the clear ink are not necessarily the same dot. Is not particularly limited. It is sufficient if the clear ink is ejected with the same or larger dots as the colored ink dots. By discharging the clear ink in this way, it is possible to avoid as much as possible that the reactive compound blended in the colored ink and the clear ink remains unreacted, and the durability of the design building material finally obtained is Can be increased. Further, from the viewpoint of efficiently producing a designable building material, it is effective to keep the colored ink in the range of 180 to 360 DPI, for example. Further, the dot of the clear ink is preferably about 100 to 360 DPI, for example.

The relationship between the discharge amount of the colored ink and the discharge amount of the clear ink is such that the equivalent ratio of the reactive compound (B) contained in the clear ink to the reactive compound (A) contained in the colored ink is 0.5-10. The discharge amount is preferably in the range of 0 equivalent, and more preferably in the range of 0.5 to 8.0 equivalent. When the equivalent ratio is lower than 0.5 equivalent, the reaction of the reactive compound A blended with the colored ink becomes insufficient, and the colored ink bleeds, whereby the design property of the building material tends to be lowered. On the other hand, when it is higher than 10.0 equivalents, due to the presence of a large amount of unreacted reactive compound B, it is easy to cause poor adhesion between the printing surface and the clear paint when the clear paint is applied repeatedly. Tend to be. Moreover, when the reactive compound B is a water-soluble substance, if it remains in an unreacted state, the water resistance performance of the design building material may be lowered. In such a case, the equivalent ratio is preferably in the range of 0.5 to 1.5 equivalents, and more preferably in the range of 0.8 to 1.2 equivalents.

In the case of using a piezo drop type ink jet printer, the piezo drop type ink jet printer may use a printer head having an ink chamber for discharging colored ink and an ink chamber for discharging clear ink. preferable. By providing such an ink chamber, it is possible to more efficiently manufacture a design building material.
In the present invention, the ink chamber that discharges the colored ink has a printer head that can individually cope with the black primary inks for lightness adjustment in addition to the three primary colors of red, blue, and yellow. It is possible to use a so-called full-color ink-jet printer having 4 to 8 groups of printer heads that can individually correspond to the intermediate colors of the four primary colors and the white ink, if necessary.

In addition, when using a piezo drop type ink jet printer having an ink chamber capable of handling colored ink and clear ink, the diameter of the discharge port for discharging the colored ink is in the range of 5 to 100 μm, more preferably 10 to 90 μm. And the diameter of the discharge port for discharging the clear ink is preferably in the range of 10 to 110 μm, more preferably in the range of 15 to 100 μm. When the diameter of the nozzle that discharges the colored ink is smaller than 5 μm, the nozzle is likely to be clogged, and the manufacturing efficiency of the design building material tends to decrease. On the other hand, if the diameter of the nozzle for discharging the colored ink is larger than 100 μm, the colored ink cannot draw clear dots with high image quality as described above, and the designability of the design building material tends to deteriorate. Further, when the diameter of the discharge port for discharging the clear ink is smaller than 5 μm, nozzle clogging is likely to occur, and the unreacted reactive compound (A) in the colored ink is likely to remain, resulting in durability of the design. Etc. tend to decrease. On the other hand, when the diameter of the discharge port for discharging the clear ink is larger than 110 μm, the supply of the clear ink becomes excessive, and depending on the components blended in the clear ink, the unreacted compound (B) remains on the building material surface. There is a tendency that performance deterioration such as durability of the design building material occurs.

The nozzle pitch of the inkjet printer is preferably 10 to 200 μm, and more preferably 15 to 150 μm. When the nozzle pitch is smaller than 10 μm, not only the required number of nozzles for the printing width becomes enormous, but also the control system has a large capacity, which tends to be disadvantageous in terms of cost. On the other hand, if it is larger than 200 μm, the distance between dots of the printed ink is excessively widened, so that the image quality tends to deteriorate.
The present invention includes a so-called line-type printer head in which the printer head is positioned above the conveyor during ink ejection and is positioned and fixed above the building material being conveyed, rather than the method of reciprocating in the width direction of the conveyor. A type of ink jet printer is preferable from the viewpoint of production speed.
10-60 m / min is preferable and, as for the speed which conveys building materials with a conveyor, 20-50 m / min is more preferable. When the conveyance speed is slower than 10 m / min, the production efficiency of the design building material is lowered, and as a result, the cost tends to increase. On the other hand, when the conveyance speed exceeds 60 m / min, the image quality of the printed pattern tends to be lowered.

  The “reaction” between the reactive compound (A) in the colored ink and the reactive compound (B) in the clear ink is generally synonymous with the curing reaction in the paint, but in the present invention, it is not necessarily completely. It need not be cured. That is, when the clear paint described below is applied after discharging the colored ink and the clear ink, it is sufficient that the paint is cured to the extent that bleeding does not occur when the clear paint is applied. There is no. On the other hand, in the case where the clear paint is not applied, it is desirable that the resin is completely cured or nearly cured from the viewpoint of ensuring the durability of the design. These cured states can be adjusted by the type of reactive compound blended in the colored ink and the clear ink, the blending amount thereof, the ejection amount of each ink, the heating conditions (temperature, time) after ink ejection, and the like.

  The clear paint is preferably applied after 10% by mass or more of the volatile components contained in the colored ink and the clear ink deposited on the printing surface are evaporated and dried. When the clear paint is applied in a state where the volatile components are dried below the above conditions, the deposited ink bleeds and the design properties of the building material tend to deteriorate.

Clear paint The clear paint used in the present invention is useful for preventing ink patterns formed by an ink jet printing method and bleeding of coloring.
Any clear paint can be used without particular limitation as long as it is conventionally applied to building materials.
The clear paint is usually composed of a binder, a pigment blended as necessary, an additive, and a solvent.
Examples of the binder used in the clear paint include one or a combination of two or more selected from acrylic resins, urethane resins, fluororesins, silicone resins, acrylic silicone resins, vinyl resins, cellulose derivatives, and the like. These and a curing agent, or a combination of these and a curing accelerating catalyst can be used.
The pigment used in the clear paint can be used to such an extent that the transparency of the clear paint is not lost. These pigments include extender pigments, coloring pigments, or colored or transparent beads such as color mica, urethane and acrylic, scaly graphite, scaly iron oxide, plated glass flakes, aluminum foil color clear Various pigments such as paint cutting products can be blended.

In the clear paint, an additive can be further blended as necessary. Examples of such additives include a dispersant, a precipitation inhibitor, a surface modifier, an ultraviolet absorber, and a surfactant. These components can be used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the solid content of the binder.
As the solvent, any of those usually used in paints can be used. For example, aromatic hydrocarbons such as toluene and xylene: acetates such as ethyl acetate and butyl acetate: methyl ethyl ketone , Ketones such as methyl isobutyl ketone: alcohols such as isopropyl alcohol and butyl alcohol: Furthermore, one kind selected from various aliphatic hydrocarbons, glycol ethers, water, or a combination of two or more kinds is used. can do. In the present invention, it is preferable to use water as a main solvent from the viewpoints of handling safety and environmental conditions.

The coating amount of the clear paint is preferably in the range of 15 to 80 g / m ^{2 in} terms of solid content, and more preferably ²⁰ to 65 g / m ² . If it exceeds 80 g / m ² , the ink tends to bleed when the ink solvent is not sufficiently evaporated, and the coating surface tends to be blocked due to poor drying. If it is less than 15 g / m ² , the durability of the design building material and the protection of the printed pattern tend to be lowered.

As the method of applying the clear paint, any of the paint methods that are usually employed when applying the paint can be used.
As such a coating method, for example, air spray coating, airless spray coating, electrostatic coating, roll coater coating, flow coater coating, or the like can be appropriately selected. In particular, in a building material having irregularities, airless spray coating or electrostatic coating can be suitably used from the followability to the shape of the building material and the coating processing speed.
After applying the clear paint, the paint is usually dried or cured. Drying conditions can be any of room temperature drying, forced drying, baking drying, or curing by irradiation with active energy rays depending on the type of coating material, and can be appropriately selected depending on the coating composition used.
In addition, when the coating material to be used is a water-based coating material, it is an effective means for forming a good clear coating film that the surface plate temperature immediately before coating is preheated to 30 to 70 ° C.

In the above embodiment, the case where the colored ink is first discharged to the printing layer to form the colored region and then the clear ink is discharged has been described as the second embodiment. On top of this, first, a clear ink may be ejected to form a clear region, and then a colored ink may be ejected thereon to form a colored region. In this aspect, compared to the first aspect in which the clear ink is ejected from above the colored ink, the bleeding of the colored ink can be further reduced.
Also in such an aspect, other conditions and the like are the same as those described in the first aspect, and can be easily understood by those skilled in the art.

  In the following, the present invention will be described in more detail with reference to examples, but these examples do not limit the scope of the present invention. In the following, unless otherwise specified, “part” or “%” means “part by mass” or “mass%”.

As the sealer sealer, V Ceranium # 300 (manufactured by Dainippon Paint Co., Ltd., acrylic resin sealer for building materials) was used.
Preparation of printing surface forming coating material A printing surface forming coating material having the following composition was prepared.
Main agent

Add the following curing agents to make 100 parts in total.
Curing agent Coronate HX (Nippon Polyurethane Industry's isocyanurate, heating residue> 99%, specific gravity 1.15) 5.3 parts

Preparation of carbonyl group-containing resin emulsion (emulsion (A))
52.3 parts by weight of water, 10.0 parts by weight of styrene, 15.0 parts by weight of butyl acrylate, 15.6 parts by weight of methyl methacrylate, 1.4 parts by weight of methacrylic acid, 3 parts by weight of diacetone acrylamide, poly as an emulsifier After emulsion polymerization was performed using 2.5 parts by mass of oxyethylene polycyclic phenyl ether sulfate (Newcol 707SF: Nippon Emulsifier Co., Ltd.) and 0.2 parts by mass of potassium persulfate, pH was adjusted with aqueous ammonia. Was adjusted to 9, and a carbonyl group-containing resin emulsion was obtained as the reactive compound (A) as the carbonyl group-containing compound A.

Preparation of colored ink
Colored ink 1 (reference)
C. I. Pigment Blue 6 parts by mass, water 62 parts by mass, BYK-190 (wet dispersant: manufactured by Big Chemie) 7 parts by mass, ethylene glycol 12 parts by mass, diethylene glycol 13 parts by mass, particle size distribution (D50) 78 nm, (D90) 135 nm Kneading was performed until a blue ink was prepared.
Colored ink 2
A colored ink 2 was prepared by blending 40 parts by mass of the carbonyl group-containing compound A with respect to 60 parts by mass of the colored ink 1.
Colored ink 3 (reference)
A colored ink 3 was prepared by adding 0.6 parts by mass of adipic acid dihydrazide (manufactured by Nippon Kasei Co., Ltd.) as reactive compound (B) to 99.4 parts by mass of colored ink 2.

Preparation of clear ink 0.6 parts by mass of adipic acid dihydrazide (manufactured by Nippon Kasei Co., Ltd.) was added and dissolved as a reactive compound (B) to 99.4 parts by mass of water to prepare a clear ink.
Clear paint V Seran # 700 (Dainippon Paint Co., Ltd., water-based acrylic silicone resin paint) was used.
Manufacture of architectural building materials

Examples 1-2
The above-mentioned sealer was applied to the surface of a gypsum slag bar light plate so as to be 60 g / m ^{2 in} terms of solid content, and was allowed to stand at room temperature overnight and dried. Next, the adjusted coating surface-forming coating material is applied to the surface of the dry sealer layer so as to be 45 g / m ^{2 in} terms of solid content, and dried under the conditions of 120 ° C. × 10 minutes. Formed. The liquid absorption amount when the printing layer was dried was 3.7 g / m ² .
On the surface of the obtained layer to be printed, each colored ink is ejected to form a colored region under the conditions shown in Table 1 below, and then a clear ink is ejected to the colored region to perform inkjet printing. It was. For ink ejection, PX-V500 (Epson Co., Ltd. piezo-type ink jet printer, nozzle diameter 20 μm) was used. After the clear ink is discharged, the clear paint is applied to a solid content of 30 g / m ² according to the conditions described in Table 1, dried at 100 ° C. × 10 minutes, and then subjected to the following criteria. Was evaluated.

Examples 3-4
The processes up to the formation of the printing layer were performed in the same manner as in Examples 1 and 2. Next, the clear ink was ejected under the conditions shown in Table 1 to form a clear region, and each colored ink was ejected and colored in that region, and ink jet printing was performed. About the apparatus used for discharge of an ink, and subsequent operation, it carried out similarly to Examples 1-2.

Comparative Examples 1-2
Except that the clear ink was not discharged, the same operation as in the example was performed based on the conditions shown in Table 1.

Appearance by visual observation ○: A good image is formed without bleeding of the colored pattern.
Δ: Although slight bleeding can be confirmed, an image having a practically no problem is formed.
X: The bleeding of the colored ink can be confirmed visually, and the disturbance of the image can be confirmed.

Observation with a laser microscope The dot diameter of the ink at the colored portion was measured with a laser microscope, and the difference between the ink dot diameters before and after the clear coating was confirmed. The laser microscope used was VK-8510 (manufactured by Keyence Corporation).

Clogging of ink nozzles After discharging the colored ink and clear ink, the ink nozzles that have been discharged are left to stand for 24 hours at room temperature, and then printed again after being left, It was determined whether clogging occurred.
○: Good printing without nozzle clogging.
Δ: Although the discharge level falls below ○, printing is possible to the extent that there is no practical problem.
X: Nozzle clogged and printing is not possible.

The results are shown in Table 1 below.
The ink droplets were measured with JetScope Pro-L (manufactured by Microjet).

From the results shown in Table 1, it can be seen that in Examples 1 and 2 that are within the scope of the present invention, there is no ink bleed and a good image is formed.
In contrast, in Comparative Example 1 in which the reactive compound (A) was not blended with the colored ink and the clear ink was not discharged, ink bleeding occurred and a good image could not be formed. It was confirmed.
Furthermore, in Comparative Example 2 in which both reactive compounds (A) and (B) are blended with the colored ink, the formed image can be formed in the same manner as the example, but the ink nozzle is clogged. As a result, continuous printing was difficult.

As the sealer sealer, V Ceranium # 300 (manufactured by Dainippon Paint Co., Ltd., acrylic resin sealer for building materials) was used.

Printed surface-forming coating material The coating surface-forming coating material used in Example 1 was used.

As the clear paint , V-Selan # 100 clear (Dainippon Paint Co., Ltd., solvent type two-component urethane paint for exterior building materials) was used.

Colored ink adjustment
Colored ink 4 (reference)
4 parts by mass of carbon black, 20 parts by mass of 2-pyrrolidone, 68 parts by mass of dipropylene glycol monomethyl ether, 8 parts by mass of a polyester polyamide resin (dispersant, Solsperse 37500, manufactured by Avicia, NV 40%), particle size distribution (D50) 80 nm (D90) Kneading was carried out until 142 nm to adjust black ink.

Colored ink 5
Reactive compound (A) is a bisphenol A type epoxy resin (Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalents 184 to 194, molecular weight 380) as reactive compound (A) with respect to 95 parts by mass of colored ink 4. As a result, 5 parts by mass were added to prepare colored ink 5.

Colored ink 6 (reference)
5 parts by mass of Epicoat 828 and 3.8 parts by mass of polyamide (Versamide 115, manufactured by Cognis Corp., active hydrogen equivalent of 135 to 155) as a reactive compound (B) are added to 4,91.2 parts by mass of the colored ink 4. As a result, a colored ink 6 was obtained.

Preparation of Clear Ink 2 70 parts by mass of xylene, 26.2 parts by mass of isobutanol, and 3.8 parts by mass of Versamide 115 as the reactive compound (B) as a reactive compound (B) were mixed to obtain a clear ink.

Examples 5-6
The processes up to the formation of the printing layer were performed in the same manner as in Examples 1 and 2. Next, under the conditions shown in Table 2 below, each colored ink was ejected to form a colored region, and then the clear ink 2 was ejected to the colored region to perform inkjet printing. About the apparatus used for discharge of an ink, and subsequent operation, it carried out similarly to Examples 1-2.

Examples 7-8
The processes up to the formation of the printing layer were performed in the same manner as in Examples 1 and 2. Next, the clear ink 2 was ejected under the conditions shown in Table 2 to form a clear region, and each colored ink was ejected and colored in that region, and ink jet printing was performed. About the apparatus used for discharge of an ink, and subsequent operation, it carried out similarly to Examples 1-2.

Comparative Examples 3-4
The same operation as in the example was performed based on the conditions in Table 2 except that the clear ink was not discharged.

Evaluation According to the above criteria, visual appearance, observation with a laser microscope, and clogging of the ink nozzle were confirmed. The base material and method used for the evaluation are as described above.
The results are shown in Table 2 below.

From the results of Table 2, it can be seen that Examples 5 to 8 which are within the scope of the present invention have no ink bleeding and are good images after being dried at 100 ° C.
On the other hand, in Comparative Example 3 in which the reactive compound (A) was not added to the colored ink and the clear ink was not discharged, ink bleeding occurred even after drying at 100 ° C. It was confirmed that a clear image could not be formed.
Furthermore, in Comparative Example 4 in which both reactive compounds (A) and (B) are blended with the colored ink, the formed image is in a state that is not inferior to the example, but the ink nozzle is clogged, The result that continuous printing becomes difficult was obtained.
In the case of the combination of the reactive compound (A) and the reactive compound (B), the reaction time is longer than that in the case of Example 1, but the initial object of the present invention is appropriately achieved. It was done.

Claims (6)

A method for manufacturing a design building material,
(1) A process of forming a printing layer by applying a printing surface forming paint on the surface of the building material,
(2) discharging the colored ink containing the reactive compound (A) that reacts with the reactive compound (B) to the printing layer by an ink jet printing method to form a colored region;
(3) A step of discharging a clear ink containing the reactive compound (B) to the colored region,
A method characterized by comprising: A method for manufacturing a design building material,
(1) A process of forming a printing layer by applying a printing surface forming paint on the surface of the building material,
(2) A step of discharging a clear ink containing a reactive compound (B) that reacts with the reactive compound (A) to the printing layer by an ink jet printing method to form a clear region;
(3) discharging colored ink containing the reactive compound (A) to the clear region;
A method characterized by comprising:   The method according to claim 1, further comprising a step of performing finish coating with a clear paint.   The discharge of the colored ink and the clear ink is performed using a piezo drop type inkjet printer having an ink chamber for discharging the clear ink together with an ink chamber for discharging the colored ink. how to.   The combination of the compound (A) and the compound (B) is an epoxy group-containing compound and an amino group-containing compound, an epoxy group-containing compound and a hydroxyl group-containing compound, an epoxy group-containing compound and a carboxyl group-containing compound, an ethyleneimine group-containing compound and a carboxyl. Group-containing compound, ethyleneimine group-containing compound and hydroxyl group-containing compound, ethyleneimine group-containing compound and amino group-containing compound, oxazoline group-containing compound and carboxyl group-containing compound, carbonyl group-containing compound and hydrazide group-containing compound, isocyanate group-containing compound and The hydroxyl group-containing compound, the isocyanate-containing compound and the carboxyl group-containing compound, the isocyanate-containing compound and the amino group-containing compound, or the group consisting of a combination of a silyl group-containing compound and a metal catalyst compound. Recorded in Method of. The printing surface is a liquid absorbing amount 0.5~15.0g / m ^2, The method according to any one of claims 1 to 5.