JP5189610B2 - Designable building material and method for producing the same - Google Patents

Description

  The present invention relates to a design building material such as a decorative board used in the field of building interior materials and building exterior materials, and a method for producing the same, and in particular, printing means such as an inkjet printer on the surface of a building base material. Various colored patterns and various pattern patterns such as natural stone patterns, marble patterns, tile patterns, wood grain patterns, and photographic images (hereinafter, these may be simply referred to as “patterns”) are used as image data. It is related with the designable building material which was printed based on, and was excellent in the designability, and its manufacturing method.

  Architectural decorative panels used as building materials, so-called building materials, including inorganic decorative panels used on outdoor walls of buildings, metal siding, PVC extrusion siding, ALC panels, metal plates, tiles, etc. In such a decorative board for construction, all of the base plate and the base material are formed on the surface of the base material formed into a necessary shape such as a plate shape using a material such as an inorganic material, a metal material, or an organic material. Various patterns are applied for the purpose of preventing the deterioration of the device itself and improving the design of the appearance.

  With regard to the patterning applied to the surface of such a substrate, expression of individuality, including requests based on the surrounding natural environment and landscape, as well as the surrounding environment required from consideration not to destroy the living environment Higher design properties are being demanded from the demands based on the above, etc., and in order to meet this demand, for example, a smooth surface, a relatively fine uneven surface, a relatively large uneven surface, etc. In addition to the three primary colors of yellow (Y: yellow), cyan (C: blue-green), and magenta (M: magenta) based on the predetermined image data, the surface of the base material formed of the inorganic material having as required It has been proposed that four colors of black (K: black) ink are ejected and adhered in a dot shape from nozzles, and a desired pattern is formed on the surface of the substrate by such a printing method (Patent Literature). 1 .

  And, in the decorative decorative board patterned by such a printing method, especially the decorative decorative board used outdoors, the ink is required to have water resistance, light resistance, and weather resistance. In addition, inks using pigments as colorants, especially water-based inks, are not only insufficient in print density, but also have pigment dispersion stability. Insufficient, and when an ink jet printer is used as a printing means, there is a manufacturing problem that nozzle clogging easily occurs in the head. In order to solve this problem, it has been proposed to use an aqueous pigment ink containing a binder such as a resin as an inkjet ink (Patent Document 2).

  In addition, in this type of building decorative board, the original purpose of coating the surface of the base material is to prevent the deterioration of the base material itself by blocking the building material deterioration factors such as water and oxygen from the base material surface. For this reason, there are many cases in which a base coating film for this purpose is provided on the surface of the base material before patterning. Such a base coating film inevitably has a surface state due to its necessity. For this reason, the ink dot droplets ejected onto the base coating on the substrate surface spread on the surface of the base coating without being absorbed by the base coating, resulting in a dense image. There is a problem that it becomes difficult. Therefore, in order to solve this problem, an inorganic filler such as silica fine particles having a high oil absorption amount is blended in the base coating for forming the base coating in order to improve the ink absorbability of the base coating. Has been proposed (Patent Document 2).

  Furthermore, for the purpose of performing high-quality patterning by the printing method, the surface of the base material is coated with a coating material for forming a printing surface containing hydrophilic crosslinked resin particles, and the ink receiving layer has excellent ink absorbability. By using a water-based ink that does not substantially contain a binder such as a resin as an ink, nozzle clogging is less likely to occur even if the nozzle diameter of the head of an inkjet printer is reduced, and ink bleeding Has been proposed (Patent Document 3), and similarly, the surface of the base material is covered with a method of manufacturing a designable building material that can easily print a high-quality pattern. After the printing surface forming paint is applied to form a printing layer (ink receiving layer), a colored region containing a reactive compound A is ejected in advance to form a colored region on the printing layer. A clear ink containing a reactive compound B that undergoes a curing reaction with the reactive compound A is ejected to the colored region, or, conversely, a clear ink containing the reactive compound B is ejected in advance to form a clear region. There has also been proposed a method for producing a designable building material that improves the durability of the ink and prevents bleeding by discharging colored ink containing the reactive compound A (Patent Document 4).

  By the way, in such decorative panels for buildings, as in other coating and printing industries, various paints and inks for patterning used in the manufacturing process can reduce environmental pollution and improve the working environment. The use of solvent-based paints and solvent-based inks is being discouraged for the purpose, especially for decorative boards used indoors, for the purpose of preventing the onset of sick house syndrome, and water-based paints and water-based inks may be used. It is requested.

  However, in the conventional decorative panel for building as described above, a water-based paint is used as a paint for forming a base coating film (ink receiving layer) and / or its colored pattern or pattern (printing layer). When water-based ink is used as the ink for forming the ink), the receiving layer and the printing layer of these inks are inevitably because they are formed of paint or ink using an aqueous solvent. Even if a pigment having excellent water resistance, light resistance, and weather resistance is used as a coloring material for water-based inks, for example, when exposed to wind and rain outdoors, the ink receiving layer and printing layer are It easily deteriorates and the desired pattern formed on the printed layer is destroyed. Therefore, conventionally, for the purpose of protecting the ink receiving layer and the printed layer formed on the surface of the decorative decorative board for buildings, a clear paint is applied on the printed layer to provide water resistance, light resistance, and weather resistance. A clear layer having excellent properties has been formed.

  However, when a higher degree of design is required for the colored pattern or pattern (pattern) in the printed layer, and a finer and higher quality image is formed, the clear layer is formed with the conventional water-based clear paint. In some cases, the ink that forms the pattern in the printing layer is redissolved (ink redissolving) in the aqueous solvent of the water-based clear paint applied thereon, and ink bleeding occurs in the printing layer. Peeling (delamination) occurs between the ink receiving layer and the clear layer, so that sufficient protection performance cannot be obtained in terms of water resistance and ink bleeding in the printed layer. From the viewpoint of product quality stability, the clear layer As a clear coating material for forming a layer, a solvent-based clear coating material must be used.

  Some attempts have been made to solve such problems. For example, aggregates such as acrylic resin beads, calcium carbonate fine particles, and silica fine particles are formed on a print layer formed of a water-based ink. Water-based clear paint (Patent Document 5) and water-based clear paint (Patent Document 6) containing a rheology control agent such as polyurethanes, polyamides, celluloses and clays are applied to form a clear layer, and printing is thereby performed. There has been proposed a building board that suppresses movement of water-based ink in the layer to the clear layer and prevents bleeding of the pattern formed on the printed layer. However, even when such a water-based clear paint containing an aggregate or a rheology control agent is used, sufficient protection performance is not necessarily obtained with respect to water resistance and ink bleeding in the printed layer.

Japanese Patent Laid-Open No. 07-31,929 International Publication WO2002 / 100,652 JP 2007-44,614 JP 2007-152,149 A JP 2008-073,602 JP 2008-253,942 A

  Therefore, even if the present invention uses a water-based clear paint as a clear paint, ink re-inking is performed between a print layer formed with a water-based ink and a clear layer formed with a water-based clear paint on the print layer. Surprisingly, as a result of intensive investigations on a design building material in which dissolution is substantially not observed and no delamination between the printed layer and the clear layer is observed, and an excellent design property can be expressed by the printed layer. Has found that the object can be achieved by adding a heat-sensitive gelling agent to the water-based clear coating, and has completed the present invention.

  Accordingly, an object of the present invention is to provide a printed layer composed of a colored pattern or a pattern formed by a printing method in which water-based ink is ejected in the form of dots on the surface of a substrate, and a water-based clear paint on the printed layer. And a clear layer formed on the printed layer, wherein the ink bleeding and delamination in the printed layer are improved as much as possible, whereby the durability of the entire coating film including the printed layer and the clear layer (water resistance) The object is to provide a designable building material having significantly improved properties, light resistance, and weather resistance).

  Moreover, the other objective of this invention is to provide the manufacturing method of the designable building material suitable when manufacturing such a designable building material.

  That is, the present invention provides a base material for construction, a printed layer formed by ejecting water-based ink by an ink jet printer on the surface of the base material, and a binder and a heat-sensitive gelling agent on the printed layer. It is a design building material characterized by having a clear layer formed by painting an aqueous clear paint.

  The present invention also provides a water-based clear paint containing a binder and a heat-sensitive gelling agent formed on a surface of a building substrate by discharging a water-based ink with an inkjet printer to form a printed layer. It is a manufacturing method of a designable building material characterized by forming a clear layer by painting.

  In the designable building material of the present invention, as a preferred embodiment, the water-based clear paint contains a thermosensitive gelling agent in a range of 0.1 to 12.0 parts by mass in terms of solid content with respect to 100 parts by mass of the binder. In addition, the water-based clear coating contains a glitter pigment in the range of 0.1 to 10.0 parts by mass in terms of solid content with respect to 100 parts by mass of the binder, and is further printed on the surface of the substrate. It is mentioned that the layer is provided through an undercoat layer formed by applying an undercoat paint and / or a receiving layer formed by applying a printing surface forming paint.

  In the method for producing a designable building material of the present invention, as a preferred embodiment, the water-based clear coating is applied after the formed printed layer is dried, and the temperature of the printed layer is 30 ° C. or higher and 80 ° C. Hereinafter, it is preferably performed when the temperature is in the range of 40 ° C. or more and 70, and the application of the water-based clear coating is performed by spray coating. Furthermore, the water-based clear coating is in solid content conversion, The thermosensitive gelling agent is contained in the range of 0.1 to 12.0 parts by mass with respect to 100 parts by mass of the binder, and the water-based clear coating is a glitter pigment with respect to 100 parts by mass of the binder in terms of solid content. In the range of 0.1 to 10.0 parts by mass, or on the surface of the substrate, the printed layer is an undercoat layer formed by applying an undercoat paint and / or a printing surface forming paint. Acceptance formed by painting It includes that provided via the.

  The designable building material of the present invention has a clear layer formed using a water-based clear paint containing a heat-sensitive gelling agent, and exhibits an excellent protective function for a print layer formed of water-based ink. Ink bleeding and delamination are improved as much as possible, whereby the durability (water resistance, light resistance, and weather resistance) of the entire coating film including the print layer and the clear layer is remarkably improved.

  In addition, according to the method for producing a designable building material of the present invention, there is no ink bleeding or delamination in the printed layer even though it includes a printed layer formed with a water-based ink and a clear layer formed with a water-based clear paint. Thus, the durability (water resistance, light resistance, and weather resistance) of the entire coating film is remarkably improved, and a designable building material can be produced. In particular, the water-based clear coating is applied on the printed layer by spray coating or the like when the temperature of the printed layer is in the range of 30 ° C. or higher and 80 ° C. or lower after the printing layer is dried. The heat-sensitive gelling agent in the water-based clear coating material can be rapidly gelled, and ink bleeding and delamination in the printed layer can be reliably prevented.

  Furthermore, according to the manufacturing method of the present invention, it is possible to manufacture a designable building material having a glittering appearance with less metal flow without causing ink clogging in an inkjet nozzle, and also to provide a primer coating and / or a substrate to be printed. When a surface-forming paint is applied and then patterned with an ink-jet printer using water-based ink, the surface of the base material is used even when the balance between the water absorption of the base material surface and the absorbability with respect to the pigment component is insufficient. Can solve the problem.

Hereinafter, the present invention will be described in detail.
[Measurement method of water absorption]
In the present invention, the amount of water absorption is a numerical value measured by the following method in a temperature-controlled room at a temperature of 23 ° C. and a humidity of 50% and calculated by the following formula.
First, an undercoat or a printing surface forming paint is applied to a glass plate having a size of 200 mm × 250 mm × 2 mm by spray coating, and an undercoat layer or a receiving layer (hereinafter simply referred to as “coating film” "). At this time, the coating amount of the undercoating paint or the printing surface forming paint is 40 g / m ² in terms of dry mass, the coating film surface is smooth, and the coating is applied so that the film thickness is averaged over the entire glass plate. To do. When the applied undercoat or printed surface forming paint is a room temperature drying paint, forced drying is performed under conditions of 80 ° C. × 30 minutes. When the coated undercoat paint or printed surface forming paint is a baking-drying type paint, forced drying is performed at 150 ° C. for 30 minutes. After the forced drying is completed, it is left to stand in a thermostatic chamber at a temperature of 23 ° C. and a humidity of 50% for 168 hours.

  Next, after leaving still, the end surface of the glass plate on which the coating film is formed is sealed with a silicon caulking agent having no water absorption. Silicon coking at this time is performed to prevent water from penetrating from the side of the coating film and from flowing out, and is performed with great care so that the caulking agent does not touch the surface of the coating film. Silicon caulking is raised to 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 surface of the coating film.

  The silicon caulking is performed, and after holding for 24 hours in a temperature-controlled room at a temperature of 23 ° C. and a humidity of 50%, the mass is measured, and this measured value is taken as the initial mass. Place the above caulked sample in a horizontal position, pour 200 g of water onto the surface of the measurement sample (coating surface on which the undercoat layer or receiving layer 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 paper towel [Kim Towel (made 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. Also wipe off with the above paper towel.

Immediately after 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 amount of water absorption is calculated by the following formula based on the measurement result.
Water absorption (g / m ² ) =
[Mass immediately after wiping (g) −initial mass (g)] / area of glass plate (m ² )

  The method for producing a designable building material according to the present invention can be applied on a base layer formed by applying an undercoat paint on the surface of a base material or on a surface of a base material, if necessary. Further, the undercoat layer and the receiving layer are sequentially formed on the surface of the base material on the receiving layer, and a printed layer is formed on the receiving layer by patterning with water-based ink using an inkjet printer. Forming a clear layer by coating a water-based clear paint on the printed layer.

[Substrate]
In the present invention, the base material used for producing the designable building material is not particularly limited by its material and shape as long as it can be patterned by an ink jet printer, and conventionally used for this type of building material. Various building materials that are used, such as inorganic materials such as flexible board, calcium silicate board, gypsum slag bar light board, wood chip cement board, precast concrete board, ALC board, gypsum board, aluminum From metal materials such as iron and stainless steel, and organic materials such as polyvinyl chloride, polyurethane, polyethylene terephthalate, polyethylene and polypropylene, and combinations of two or more selected from these inorganic materials, metal materials and organic materials The combination material which can be illustrated can be illustrated. These substrates may have a smooth surface, or may have a relatively fine uneven shape and / or a relatively large uneven shape.

  In the present invention, on the surface of the base material, a printing layer is formed by patterning with water-based ink, or a printing surface forming paint is applied to form an ink receiving layer. Ensuring adhesion between the printing layer and the receiving layer, improving the protection function against water and alkalis derived from base materials (especially cement base materials, etc.), and also when applying paint for forming printed surfaces For the purpose of preventing inhalation of the printing surface forming paint into the base material, the primer layer is applied to form the undercoat layer prior to the patterning with water-based ink and the coating of the printing surface forming paint. Also good.

[Undercoat layer]
As the undercoat paint for forming the undercoat layer, an undercoat paint conventionally used in the production of this kind of designable building material can be used. In particular, when the surface of the substrate used has many holes or when the distribution of these holes varies, the ink receiving layer is formed by directly applying the printing surface forming paint onto the surface of the substrate. In some cases, the water absorption amount (or the oil absorption amount) of the formed receiving layer is not uniform. In such a case, when the ink is ejected and patterning is performed, An undercoat layer having a predetermined water absorption amount (or oil absorption amount) on the surface of the base material in advance, although the pattern may be partially unclear and the quality of the manufactured architectural building material may be deteriorated. By forming the surface, the water absorption amount (or oil absorption amount) of the ink receiving layer can be kept within a certain range regardless of the type of substrate used or the surface condition, and the resulting design is produced. The quality and durability of building materials can be improved. In order to keep the water absorption amount (or oil absorption amount) of the ink receiving layer within a certain range, a double receiving layer is formed by coating the printing surface forming paint instead of the undercoat layer. It is also possible to do.

  Here, for the undercoat for forming such an undercoat layer, a solvent-based undercoat comprising a binder and a solvent mainly composed of an organic solvent (an undercoat using only a hydrophilic solvent substantially free of water) In addition, a powder undercoat without any solvent is also included), and an aqueous undercoat made of a binder and a water-based solvent (including an undercoat made of a water-soluble resin substantially free of solvent). These undercoat paints are blended with fillers and various additives as necessary. Here, as the binder, various binders can be used regardless of whether the binder is water-based or solvent-based, which has been conventionally used in undercoat paints. For example, an epoxy resin, an acrylic resin, a urethane resin, a fluororesin, an inorganic resin, an acrylic silicon resin, an alkyd resin, and the like are exemplified, but the invention is not limited thereto. Examples of the filler include inorganic color pigments such as titanium oxide, iron oxide, and carbon black: organic color pigments such as phthalocyanine blue, carmine FB, and Hansa Yellow: extender pigments such as talc, kaolin, barium sulfate, and calcium carbonate. However, it is not limited to these. As the additive, an antifoaming agent, a leveling agent, a dispersing agent, a film forming aid, a thickening agent, and the like can be blended as necessary, and are appropriately changed according to the composition and purpose of the undercoat. It is possible.

In the present invention, for environmental purposes (reducing environmental pollution, improving the working environment, preventing the onset of sick house syndrome, etc.), in order to make various paints used for the production of design building materials as water-based as possible, Alternatively, in order to make it all water-based, a water-based undercoat paint is used as the undercoat paint. In this case, the water absorption of the surface of the base material used for the production of the designable building material is not constant, and if the water absorption rate of the formed undercoat layer is too high, it becomes difficult to form a receiving layer thereon. Therefore, it is necessary to use a water-based undercoating material in which the water absorption amount of the undercoat layer is 0.1 g / m ² or more and 10.0 g / m ² or less, preferably 0.1 g / m ² or more and 2.0 g / m ² or less. preferable. When the water absorption amount of the formed undercoat layer is lower than 0.1 g / m ² , the water resistance is good, but the coating film of the undercoat layer is densely formed and the flexibility is insufficient. There is a possibility that the adhesion to the substrate may be reduced, and conversely, if it is higher than 10.0 g / m ² , it is used for forming the printing surface in the process from coating of the printing surface forming paint to the undercoat layer to the film forming process. There is a problem that the moisture of the paint is easily absorbed by the undercoat layer, the moisture necessary for the film formation is insufficient, and it becomes difficult to form the receiving layer.

In addition, as a method of applying the undercoat paint on the surface of the base material, any of the conventionally employed methods can be applied, such as air spray coating, airless spray coating, electrostatic coating, roll coater coating, flow coating. Coater coating or the like can be selected as appropriate. The coating method, the coating amount, and the like of the undercoat paint can be appropriately changed depending on the selected base material and the type of the undercoat paint. In particular, in the case of targeting inorganic materials, it is preferable to apply in the range of ²⁰ to 75 g / m ^{2 in} terms of solid content, and more preferable to apply in the range of 30 to 60 g / m ² . If it is less than 20 g / m ^2, the adhesion between the base material and the coating film and the bleed-inhibiting effect of the Efro component tend to be reduced. On the other hand, if it exceeds 75 g / m ² , it only takes a longer time to dry. However, due to the occurrence of checking or the like, formation of a smooth undercoat [coating film] layer cannot be expected, and the cost tends to be disadvantageous.

[About ink receiving layer]
In the present invention, an ink receiving layer is formed on the surface of the base material by applying a printing surface forming paint as necessary via an undercoat layer. The printing surface-forming paint used for this purpose basically forms particles such as silica fine particles and hydrophilic cross-linked resin particles that serve as ink receivers and these particles are bonded to each other to form an ink receiving layer. It consists of a binder, and if necessary, additives such as pigments for shielding, film-forming aids for improving resin film-forming properties, solvents for dilution, etc. It may be an aqueous system in which a solvent is used, a solvent system mainly composed of an organic solvent, or a powder system in which no solvent is used.

  As the binder constituting the coating material for forming the printing surface, a resin conventionally used in this kind of coating can be used. Specifically, for example, epoxy resin, vinyl resin, polyester resin, acrylic resin , Urethane resin, fluororesin, silicone resin, acrylic silicone resin, inorganic resin, and one or more selected from modified resins obtained by modifying these resins. What consists of a mixture with a hardening | curing agent, a hardening catalyst, etc. can also be used.

  Examples of the particles constituting the above-described coating material for forming a printing surface include silica fine particles having a predetermined oil absorption amount, resins such as a (meth) acrylic acid resin and a vinyl alcohol resin having a predetermined water absorption amount. Hydrophilic cross-linked resin particles can be used, but various paints used in the production of design building materials for environmental purposes can be made into water-based or all-water-based paints as much as possible. For this purpose, it is preferable to use hydrophilic crosslinked resin particles. The hydrophilic cross-linked resin particles described above need to be cross-linked. When non-cross-linked resin particles are used, the resin particles absorb water and swell when ink is absorbed. In addition to causing the quality of the pattern in the layer to deteriorate, the durability of the manufactured architectural building material is impaired.

  Here, as an acrylic resin for forming said hydrophilic crosslinked resin particle, alkali metal salts, such as sodium polyacrylate, are mentioned suitably, for example. Examples of the (meth) acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (Meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, α-chloroethyl (meth) acrylate, cyclohexyl (meth) acrylate After polymerization of (meth) acrylate monomers such as phenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxypropyl (meth) acrylate, etc. Manufactured by disassembling You can. It can also be obtained by polymerizing acrylonitrile or methacrylonitrile and then hydrolyzing it. Examples of the monomer of the vinyl alcohol resin include vinyl acetate.

  In addition, as a method of performing the above-mentioned crosslinking, a method of blending a monomer having a crosslinking property (hereinafter referred to as “crosslinking monomer”) when polymerizing monomers to produce resin particles, And a method of crosslinking resin particles formed in advance using a crosslinking agent such as hydrazine. Here, representative examples of the crosslinkable monomer used in the above crosslinkable monomer blending method include divinylbenzene, for example, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like. Monomers comprising acrylic acid derivatives having two or more polymerizable unsaturated double bonds in the molecule, such as (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropyltriethoxysilane, (meth) Reactions during emulsion polymerization of silyl group-containing ethylenically unsaturated monomers capable of hydrolytic condensation such as acryloxypropylmethyldimethoxysilane, and monomers having carboxyl groups and monomers having glycidyl groups, for example Examples thereof include monomer mixtures composed of monomers having functional groups that react with each other at temperature.

  Furthermore, the degree of cross-linking in the hydrophilic cross-linked resin particles is determined by the blending amount of the cross-linking monomer in the case of the former method of blending the cross-linking monomer. Is 0.2% by mass or more and 15.0% by mass or less, preferably 0.5% by mass or more and 12.0% by mass or less, based on the whole monomer used for polymerization. If the monomer content is less than 0.2% by mass, the produced hydrophilic crosslinked resin particles will expand more than necessary when the aqueous solvent mixed in the aqueous ink is absorbed, and the quality of the pattern in the printed layer will be increased. On the other hand, when it is more than 15.0% by mass, the uniformity of the desired particles tends to be impaired, and the water absorption tends to decrease.

  In the case of the latter method in which the previously formed resin particles are crosslinked with a crosslinking agent, the degree of crosslinking in the hydrophilic crosslinked resin particles is measured by the number of N atoms increased by the introduction of the crosslinking agent, Based on the above-obtained resin particles, the content is 0.6% by mass or more and 8.0% by mass or less, preferably 1.0% by mass or more and 5.0% by mass or less. Even in this case, if the degree of crosslinking is lower than 0.6% by mass, the pattern image may be blurred. Conversely, if the degree of crosslinking is higher than 8.0% by mass, the density of the pattern image decreases. Occurs.

For the hydrophilic crosslinked resin particles described above, an average of the water-based ink absorption performance formed in the ink receiving layer formed by using the printing surface-forming coating material containing the hydrophilic crosslinked resin particles is averaged. The particle diameter is preferably in the range of 0.3 to 130 μm, the volume expansion rate at the time of water absorption is preferably 6 to 40%, and the true specific gravity is preferably 0.7 to 2.0 g / cm. ^It should be in the range of ³ . Here, if the volume expansion coefficient at the time of water absorption is higher than 40%, the quality of the pattern in the printed layer is deteriorated, and the durability of the manufactured architectural building material is impaired. On the contrary, the volume expansion coefficient is lower than 6%. Insufficient ink adsorption causes a reduction in pattern quality in the printed layer.

  Preferable examples of the hydrophilic crosslinked resin particles include acrylonitrile, if necessary, sulfonic acid-containing monomers such as vinyl halide, vinylidene halide, (meth) acrylic acid ester and allyl sulfonic acid, and salts thereof. To produce hydrophilic resin particles by copolymerizing together with carboxylic acid-containing monomers such as acrylic acid and itaconic acid and their salts, and copolymerizable monomers such as acrylamide, styrene, and vinyl acetate. Hydrophilic resin particles obtained by adding a hydrazine-based compound as a crosslinking agent to crosslink, then acid-treating, and then hydrolyzing to the surface layer or inside of the particles using an alkali such as sodium hydroxide can be mentioned. . In this case, among the monomers to be copolymerized, acrylonitrile is preferably contained in the range of 70% by mass to 95% by mass, more preferably 75% by mass to 90% by mass, By setting the acrylonitrile content in the above range, it is possible to efficiently obtain hydrophilic crosslinked resin particles having excellent ink absorbability. Examples of the acid used here include, but are not particularly limited to, aqueous solutions of mineral acids such as nitric acid, sulfuric acid, and hydrochloric acid, and organic acids. Prior to this treatment, the hydrazine compound remaining in the crosslinking treatment is sufficiently removed. Examples of the alkali used for hydrolysis include alkali metal hydroxides, alkaline earth metal hydroxides, basic aqueous solutions such as ammonia, and the like, but are not particularly limited as long as they can be hydrolyzed.

  Specific examples of such hydrophilic crosslinked resin particles include, for example, tuftic (registered trademark of Toyobo Co., Ltd.) HU series HU720PS, HU700E, and the like, and the average particle diameter is 0.9. The moisture absorption rate (20 ° C., 65% RH) is in the range of 45 to 55% under the condition of ˜50 μm and the temperature of 20 ° C. and the humidity of 65% RH.

  Moreover, as a printing surface forming coating material, if necessary, there are a color pigment and an extender pigment, and either or both of them can be used. Examples of the color pigment include inorganic oxides such as titanium oxide, zinc oxide, zinc sulfide, carbon black, chrome lead, ocher, petal, and composite oxides (nickel / titanium, chromium / titanium, bismuth / vanadium). Various inorganic pigments commonly used for paints such as pigments and organic pigments such as phthalocyanine blue, quinacridone, diketopyrrolopyrrole, benzimidazolone, isoindolinone, anthrapyramidine, selenium, dioxazine Examples of organic pigments include talc, kaolin, barium sulfate, calcium carbonate, mica, quartzite powder, diatomaceous earth, amorphous silica, allophane, imogolite, bentonite, montmorillonite, and sepiolite. Extender pigments commonly used for paints, etc., and porous Machine powder and the like, which are not intended to be limited to those illustrated.

  In the present invention, for the purpose of improving the water absorption amount of the receiving layer formed by the coating material for forming the printing surface, preferably, as a part or all of the pigment, titanium oxide, iron oxide of a color pigment, Zinc oxide, zinc sulfide, carbon black, chrome lead, ocher, petal, etc., and extender pigments such as diatomaceous earth, calcium carbonate, and silica are preferably added. The amount of the pigment added for this purpose is, for example, in the range of 10% by mass to 20% by mass in the case of titanium oxide, preferably in the range of 15% by mass to 18% by mass, and in the case of diatomaceous earth. Is blended in the range of 1 to 10% by mass, preferably 3 to 5% by mass. By blending diatomaceous earth in this range in the coating material for forming the printing surface, the ink adsorptivity in the formed receiving layer is improved, and the quality of the pattern of the printed layer formed thereby is further improved. If the amount of titanium oxide or diatomaceous earth is too small, the significance of adding this titanium oxide or diatomaceous earth is difficult to express. On the other hand, if the amount is too large, the pigment component of the paint will increase so much that the receiving layer will be formed. There arises a problem that cracking is likely to occur.

  Furthermore, as a solvent to be added to the printing surface-forming coating material as necessary, any solvent that is usually used in coating materials can be used. For example, aromatics such as toluene and xylene can be used. Aromatic hydrocarbons, acetates such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as isopropyl alcohol and butyl alcohol, and various aliphatic hydrocarbons and glycol ethers , One or more selected from water or the like may be used in combination.

  In the present invention, as in the case of the above-mentioned undercoat paint, an aqueous printing surface is used to make various paints used for the production of a design building material for environmental purposes as water-based as possible or to make it all water-based. A forming paint is preferably used, and preferably water or an aqueous solvent containing water as a main component is used.

  The blending ratio of each of the above components in the coating composition for printing surface is in the range of 20% by mass to 80% by mass, preferably 30% by mass to 45% by mass, in terms of solid content. The hydrophilic cross-linked resin particles are in the range of 5% by mass or more and 20% by mass or less, preferably 6% by mass or more and 8% by mass or less. In the case where a solvent is used, the blending ratio thereof is 10% by mass to 80% by mass, preferably 25% by mass to 60% by mass. Here, if the blending amount of the binder is less than 20% by mass, a problem of poor film formation of the receiving layer due to insufficient binder occurs, and conversely, if it exceeds 80% by mass, the coating layer is concealed in the receiving layer. There is a possibility that the force is reduced, the intended pattern is not drawn on the printed layer, and the color of the surface of the undercoat layer or the base material is seen through. On the other hand, when the blending amount of the hydrophilic cross-linked resin particles is less than 5% by mass, the effect of adding the hydrophilic cross-linked resin particles cannot be expected, and the ink absorption capacity of the receiving layer to be formed is lowered. When the content is larger than mass%, the production efficiency of the receiving layer is lowered, and the image quality of the pattern of the printed layer formed by ejecting ink is lowered. Furthermore, if the blending amount of the pigment is less than 5% by mass, the pattern formed by ejecting the ink may become unclear, and as a result, the quality of the design building material may be deteriorated. The coating strength of the receiving layer to be formed is lowered, and the durability of the design building material is lowered. Furthermore, when the blending amount of the solvent is less than 10% by mass, the paintability is deteriorated. On the other hand, when it exceeds 80% by mass, it becomes difficult to form a smooth receiving layer.

  In the present invention, in the coating material for forming the printing surface, if necessary, other additives such as film forming aids, curing agents, antifoaming agents, leveling agents, ultraviolet absorbers, light stabilizers. , Antibacterial agents, crosslinking accelerators, dispersants, suspending agents, wetting aids for ink solvents, and the like can be blended. About the kind and addition amount of an additive mix | blended here, it selects suitably according to the binder and hydrophilic resin particle to be used, and also a color pigment, an extender pigment, a solvent, etc.

On the surface of the base material, the print surface-forming coating material is applied in order to form an ink-receiving layer directly or via an undercoat layer. in terms of usually 20 g / m ² or more 80 g / m ² or less, preferably in the range of 30 g / m ² or more 60 g / m ² or less, when the coating amount of the coating is less than 20 g / m ^2, manufactured design property On the other hand, if the durability of the building material is reduced, and if it exceeds 80 g / m ² , the time required for drying after coating the coating material for forming the printing surface will become longer, and the final designable building material will be formed. Durability cannot be expected, which is disadvantageous in cost.

  In addition, as a method of applying the coating material for forming the printing surface, any method conventionally used when applying a paint can be applied. For example, air spray coating, airless spray coating, electrostatic coating, Roll coater coating, flow coater coating, and the like can be selected as appropriate. When coating on a building material having unevenness, airless spray coating or electrostatic coating is preferred from the viewpoint of conformability to the uneven shape and adaptability of the coating speed. When the coating material to be used is a water-based coating material, it is desirable that the plate surface temperature immediately before coating is preheated to 30 to 70 ° C. in order to form a good ink receiving layer. By performing this preheating, there is an advantage that checking is difficult to occur in the receiving layer to be formed.

In the present invention, it is desirably 8.0 g / m ² or more 24.0 g / m ² or less for water absorption of the receiving layer is formed by coating the surface to be printed for forming a coating of the above, the receiving layer When the water absorption is less than 8.0 g / m ² , the ink absorption capacity of the receiving layer is lowered, the quality of the pattern in the printed layer formed on the receiving layer is lowered, or the water system is discharged after the ink is discharged. When the clear paint is applied, ink bleeding occurs. Conversely, if it is higher than 24.0 g / m ² , the discharged ink is excessively absorbed and the image quality of the printed pattern is deteriorated.

[About printed layer]
In the present invention, various colored patterns, such as natural stone patterns, marble patterns, tile patterns, and wood grain patterns, can be obtained by discharging water-based ink to the undercoat layer or the receiving layer with an inkjet printer. Etc. are printed based on the image data to form a print layer. By using this water-based ink, the durability and maintainability of the ink jet printer can be improved, the sanitary aspect of the workplace and the risk of fire can be reduced, and the load on the environment can be reduced. . In addition, by slowing down the ink evaporation rate as much as possible, it is possible to prevent clogging of nozzles of ink jet printers and occurrence of stains around the nozzles as much as possible, and the relationship with the ink receiving layer described above Can print patterns with good image quality.

  The water-based ink used in the present invention contains a color pigment, a dispersant, and a water-based aqueous solvent as a main component and does not substantially contain a binder. Here, “substantially free of a binder” means to allow a case where a binder such as a resin is inevitably mixed when a coloring pigment or a dispersant is added. The mixing ratio of the binder such as resin is desirably 10% by mass or less, preferably 5% by mass or less with respect to the whole ink. In the present invention, the required image quality accuracy is in the range of 150 to 600 DPI (dots per inch), and in order to print an unprecedented high quality pattern in the manufacture of a design building material, an ink ejection port in an ink jet printer On the other hand, a caliber that is smaller than before is inevitably required.

  As a color pigment blended in the above water-based ink, any color pigment generally used in paints and inks can be used, but it improves the weather resistance and durability of the formed color and pattern. In view of the above, it is preferable to blend mainly an inorganic coloring pigment particularly in outdoor use. Typical examples of these inorganic coloring pigments include carbon black, iron oxide, composite oxides (nickel / titanium-based, chromium / titanium-based, bismuth / vanadium-based), titanium oxide, and the like. Is not to be done. In addition to the above inorganic coloring pigments, organic coloring pigments can also be blended. Typical examples of these organic coloring pigments include quinacridone, diketoprolope, benzimidazolone, isoindolinone, anthrapyrimidine, phthalocyanine threne, dioxazine and the like.

  The color pigment has an average particle size of 20 nm to 400 nm, preferably 25 nm to 300 nm. If the average particle diameter is less than 20 nm, the ink storage stability and the print image quality are lowered due to the aggregation of the pigment, and problems such as an increase in ink viscosity and a decrease in light resistance of the printed surface are likely to occur. On the other hand, if the average particle diameter is larger than 400 nm, the discharge nozzle of the ink jet printer is likely to be clogged, and the accuracy of ink ejection to the receiving layer is likely to occur, and printing with high image quality as described above becomes difficult. .

  The blending ratio of the color pigment is preferably 0.5 to 15.0 parts by mass, more preferably 1.0 to 10.0 parts by mass in 100 parts by mass of the ink. If the amount is more than 15.0 parts by mass, the ink viscosity rises and the ink dries too quickly, and the nozzle portion of the following ink jet printer used for printing is likely to be clogged, and the ink droplets are printed. The accuracy of application to the surface is degraded. On the other hand, when the amount is less than 0.5 parts by mass, the color development becomes insufficient and the formed pattern becomes unclear. Further, when an organic pigment is used as the coloring pigment of the ink, it is necessary to select and use one that is particularly excellent in light resistance and fading.

  Examples of the dispersant added to the aqueous ink include anionic polymer dispersions such as styrene-maleic anhydride copolymer salt, olefin-maleic anhydride copolymer salt, and naphthalenesulfonate formalin condensate. And nonionic polymer dispersants such as polyvinyl alcohol, polyoxyethylene ether ester copolymer, polyacrylamide and the like, and are selected from these anionic polymer dispersants and nonionic polymer dispersants 1 Species or two or more types can be used in combination. About the kind and compounding quantity of these dispersing agents, it uses properly by the kind and compounding quantity, etc. of the color pigment to be used or the water-based aqueous solvent. As the dispersant, a dispersant having a carboxyl group or a carboxylate group that is present on the pigment surface when the printing layer is formed is preferable. When the printing layer is formed, if a carboxyl group or a carboxylate group is present in the dispersant on the pigment surface, when forming the top clear layer on the printing layer, a curing agent blended in the water-based clear coating, particularly The alkoxysilyl group of the silane coupling agent acts on the carboxyl group and carboxylate group of the dispersant present on the pigment surface, further reducing the dispersibility of the ink in the water-based clear paint and further improving the ink re-dissolvability. To do.

  Furthermore, the water-based aqueous solvent used in the above-mentioned water-based ink means water or a mixed solvent containing water as a main component and a hydrophilic solvent blended as necessary. Here, as the hydrophilic solvent, any solvent usually used in ink can be suitably used. For example, alcohols, ethylene glycol and ethylene glycol derivatives, glycerin and glycerin derivatives, propylene One or a combination of two or more selected from glycols and propylene glycol derivatives can be used.

  The amount of the aqueous solvent in the aqueous ink is in the range of 70% by mass to 92% by mass, preferably 75% by mass to 90% by mass with respect to the entire ink. Among these, the mixing ratio of water is preferably in the range of 45% by mass or more and 70% by mass or less. When the mixing ratio of water is lower than 45% by mass, the ink viscosity increases and the ink discharge performance decreases. Therefore, it becomes difficult to obtain a high quality pattern. On the other hand, when the mixing ratio of water is higher than 70% by mass, drying around the nozzle holes becomes remarkable, and nozzle clogging and ink ejection accuracy are lowered.

  In addition, also in the water-based ink used in the present invention, as other additives, for example, a conductivity adjusting agent, an antifoaming agent, a suspending agent, an ultraviolet absorber, a light stabilizer, a preservative, and the like are added as necessary. be able to.

  In the present invention, when the water-based ink is ejected to the receiving layer using an ink jet printer, and the pattern is printed to form the printed layer, the receiving layer does not necessarily need to be completely cured and dried. Printing can be performed in a state where the solvent is evaporated, or printing can be performed in a state where the solvent is completely cured and dried.

  The conditions for curing or drying the printing surface-forming paint can be selected from room temperature drying, forced drying, or curing by irradiation with active energy rays depending on the type of paint, and can be selected as appropriate according to the composition of the paint. Can be adopted. Furthermore, the entire surface or part of the printed layer printed by other printing means such as gravure printing, screen printing, etc., is further ejected with an ink jet printer to print a pattern, etc. It can also be applied in combination with printing. In addition, for printing the pattern on the receiving layer, the entire surface of the receiving layer may be printed in a single color, or it may be partially colored in a composite color having a different hue, and further, a pattern may be printed. May be. And these patterns may be formed in the whole surface of a designable building material, and may be formed only in a part. Moreover, when the surface of a base material has an unevenness | corrugation, a recessed part and a convex part can also be colored with a different color.

  In the present invention, an ink jet printer is used when ejecting ink to the receiving layer. Any type of ink jet printer used for printing can be used. In order to efficiently print a higher quality pattern, specifically, a pattern having an image quality of 100 to 600 DPI, preferably a continuous type piezo drop type ink jet printer or an on demand type piezo drop type ink jet printer. Is used. Also for the printer head, the so-called line system, in which the printer head is positioned and fixed above the substrate being conveyed, rather than the system in which the printer head is positioned above the conveyor and reciprocates in the width direction of the conveyor during ink ejection. It is preferable to use an ink jet printer of a type provided with a printer head from the viewpoint of production speed. In this case, the conveyance speed of the substrate conveyed by the conveyor is usually 10 m / min or more and 60 m / min or less, preferably 20 m / min or more and 50 m / min or less, and the conveyance speed of the substrate is 10 m / min or less. If it is slower than 5 minutes, the production efficiency of the design building material is lowered, resulting in an increase in cost. On the contrary, when the conveyance speed of the base material is faster than 60 m / min, the image quality of the printed pattern may be deteriorated. Furthermore, the printer head of the ink jet printer can individually cope with black-colored individual inks for brightness adjustment in addition to the three primary colors of red, yellow, and blue. Furthermore, if necessary, a so-called full-color ink jet printer having 4 to 8 groups of printer heads that can individually cope with the intermediate colors of the four primary colors and the white ink is used. desirable.

  When forming a 150 to 600 DPI pattern, the diameter of the discharge nozzle of the ink jet printer is preferably 10 to 45 μm, and more preferably 15 to 35 μm. If it is larger than 45 μm, it tends to be difficult to obtain a high-resolution coloring or pattern, and if it is smaller than 10 μm, nozzle clogging tends to occur frequently. Further, it is preferable from the viewpoint of production efficiency and image quality that a plurality of nozzles are provided in the width direction of the conveyor. Moreover, it is preferable that the pitch between nozzles is 10-200 micrometers, and it is more preferable that it is 15-150 micrometers. When the nozzle pitch is smaller than 10 μm, not only the number of nozzles required for the printing width is enormous, but also the capacity required for the control system is increased, which tends to be economically disadvantageous. On the other hand, if it is larger than 200 μm, the distance between dots of the printed ink is too wide, and the image quality tends to deteriorate. In the present invention, it is possible to produce a building material with high-resolution coloring or patterning of 150 to 600 DPI by taking the above-described method. In addition, when manufacturing at an appropriate production cost, it is effective to keep the resolution within the range of 180 to 360 DPI. Further, when coloring the building material surface to a single color, it is effective to keep the resolution within the range of 150 to 360 DPI. In addition, the resolution is generally the same for both the horizontal and vertical axes, but for line printers, the resolution is set to a high resolution, for example 600 DPI, in the width direction of the printer head, and the building material transport direction For example, by setting the resolution slightly lower, for example, at 300 DPI, the coloring unevenness on the straight line that occurs in the building material conveyance direction due to the specific nozzle clogging or flying droplets on the ink droplets without reducing the production speed. It is also possible to relax. The resolution can be changed as appropriate by adjusting the nozzle diameter, the frequency of the piezoelectric element, and the like. Further, the vibration frequency of the piezoelectric vibration element can be controlled by a voltage supplied to the piezoelectric vibration element.

  In the present invention, after forming a print layer by patterning with water-based ink, the volatile components in the print layer are volatilized and dried. This volatile component does not necessarily need to be completely dried, and may be dried to such an extent that ink bleeding does not occur due to the application of the water-based clear paint. Preferably, the water-based clear paint is applied. In addition, the printing layer may be maintained within a temperature range of 30 ° C. or higher and 80 ° C. or lower, preferably 40 ° C. or higher and 70 ° C. or lower. When the temperature of the printing layer is lower than 30 ° C., the gelation of the heat-sensitive gelling agent does not proceed rapidly when the water-based clear coating is applied, and ink bleeding from the printing layer may occur. When the temperature is higher than 0 ° C., there is a problem that it is difficult to form a continuous clear coating film.

[Clear layer]
In the present invention, the water-based clear paint for forming a clear layer on the printed layer is a combination of various water-based clear paints that have been conventionally applied to a substrate and a heat-sensitive gelling agent. Further, a bright pigment is further blended, and basically contains a binder and a heat-sensitive gelling agent, and further contains components such as a bright pigment, a pigment, other additives, and a solvent as necessary.

  Examples of the binder 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, etc. It is also possible to use a combination of curing accelerating catalysts.

  With respect to the heat-sensitive gelling agent added to the water-based clear coating material of the present invention, the pattern formed on the printed layer is not visually impaired when it is applied to form a clear layer. As long as it is easily gelled in the coating step, it may be an organic heat-sensitive gelling agent or an inorganic heat-sensitive gelling agent. Examples of organic heat-sensitive gelling agents include starch and derivatives thereof, nonionic activator-based organopolysiloxane alkylene oxide adducts, organopolysiloxane alkylphenol formalin condensates, and alkylphenol-formalin condensate alkylene oxide adducts. , Polyvinyl methyl ether, organopolysiloxane polyether copolymer, etc. In addition, examples of inorganic heat-sensitive gelling agents include sodium hexametaphosphate, ammonium nitrate, ammonium chloride, sodium carbonate, potassium carbonate, and sulfuric acid. Examples include sodium, potassium chloride, calcium chloride, calcium sulfate, magnesium sulfate, zinc ammonium complex, sodium nitrate, lead nitrate, sodium acetate, etc. In addition to that can be used, it can also be used in combination of two or more kinds.

  The heat-sensitive gelling agent has a cloud point of 30 ° C. or higher and 80 ° C. or lower, preferably 40 ° C. or higher and 70 ° C. or lower. By using such a heat-sensitive gelling agent within the cloud point range, the temperature of the printing layer after the drying treatment is applied when the aqueous clear coating is applied after the drying treatment of the printing layer formed by patterning with the aqueous ink. In general, the heat-sensitive gelling agent easily gels at a temperature of 30 ° C. or more and 80 ° C. or less, and when the water-based clear coating is applied on the printing layer, ink bleeding from the printing layer is effectively prevented.

  In the water-based clear coating material of the present invention, the heat-sensitive gelling agent may be any of the above organic and inorganic materials, or a combination thereof. The amount is 0.1 to 12.0 parts by mass, preferably 0.5 to 7.0 parts by mass with respect to 100 parts by mass of the binder. When the amount is less than 1 part by mass, the effect of adding the heat-sensitive gelling agent may not occur. On the other hand, when the amount exceeds 12.0 parts by mass, the viscosity may increase or the storage stability may deteriorate.

  In the present invention, examples of a preferable heat-sensitive gelling agent to be added to the water-based clear paint include nonionic surfactants described in JP-A-2001-354,847. This nonionic surfactant is composed of at least two types of nonionic surfactants, those having a cloud point of 10% to 80 ° C. and those having a temperature of 100 ° C. or higher. Here, as a component (low cloud point activator) whose cloud point of 1% aqueous solution is 10 to 80 ° C. or a component (cloud point activator) whose cloud point is 100 ° C. or higher, it is not particularly limited. For example, ethylene oxide and / or propylene oxide adduct of alcohol having 1 to 18 carbon atoms, ethylene oxide and / or propylene oxide adduct of alkylphenol, alkylene glycol and / or alkylenediamine ethylene known so far It can be appropriately selected from those showing a cloud point in the range set by oxide and / or propylene oxide adduct. Further, the ratio of the low cloud point active agent to the high cloud point active agent and the total amount of the nonionic surfactant are not particularly limited, but the ratio of the low cloud point active agent to the high cloud point active agent (low The mass ratio of cloud point activator / high cloud point activator is preferably from 0.1 to 10.

  The bright pigment added to the water-based clear paint of the present invention as necessary is referred to as normal non-leafing type aluminum pigment, aluminum powder such as aluminum paste, white mica or silver mica showing a cloudy color from white to silver. Pigments, and light interference pigments exhibiting various colors due to light interference action. The former white mica or silver mica pigment is obtained by coating the surface of scaly mica powder with titanium oxide. The coating thickness of titanium oxide is 5 to 60 μm, particularly 5 to 25 μm, the thickness is 0.25 to 1.5 μm, especially 0.5 to 1 μm, and the finish thickness is white pearl or silver pearl. Preferably, it is 90 to 160 nm based on the optical thickness and 40 to 70 nm based on the geometric thickness. On the other hand, as optical interference pigments, silica flakes, alumina flakes, mica flakes, mica flakes coated with titanium oxide, iron oxide, etc. (the coating thickness is thick in the case of the above-mentioned white mica or silver mica pigment), etc. These longitudinal directions are preferably 5 to 60 μm, particularly 5 to 25 μm, and the thickness is preferably 0.25 to 1.5 μm. Furthermore, if necessary, silver-plated glass flakes, titanium-coated graphite, metal titanium flakes, plate-like iron oxide, phthalocyanine flakes, and the like can be blended. The blending amount of the glitter pigment is not strictly limited, but usually 3 to 20 parts by weight, particularly 7 to 13 parts by weight per 100 parts by weight of the total solid content of the resin component is preferable.

  The pigment added to the water-based clear paint of the present invention as necessary is usually required to be used to the extent that the transparency of the clear layer is not lost, but depending on the desired design, it may be used as a color clear colored with a pigment or the like. May be. These pigments include extender pigments including matting agents, colored pigments, colored mica, urethane-based, acrylic-based colored or transparent beads, flaky graphite, flaky iron oxide, plated glass flakes, aluminum foil color clear paint Various pigments such as cut products may be blended. Other additives include dispersants, suspending agents, surface modifiers, UV absorbers, surfactants, etc. These components depend on the type of binder and the required performance required for the clear layer. Can be appropriately selected and added.

  The solvent used in the water-based clear coating material of the present invention is a water-based solvent mainly composed of water, and is a mixed solvent composed mainly of water or water and, if necessary, a hydrophilic solvent. Here, as the hydrophilic solvent, any of the hydrophilic solvents usually used in water-based clear paints can be suitably used. For example, alcohols, ethylene glycol and ethylene glycol derivatives, glycerin and glycerin derivatives. , One selected from propylene glycol and propylene glycol derivatives, or a combination of two or more can be used.

  In the present invention, as a method for applying the water-based clear paint, any of the methods usually employed when applying the paint can be applied. For example, air spray coating, airless spray coating, electrostatic coating, roll coater coating, Although methods such as flow coater coating can be mentioned, spray coating such as air spray coating and airless spray coating and electrostatic coating are preferable. These spray coatings and electrostatic coatings are not only excellent in the followability to the uneven surface of the substrate and the coating processing speed, but also water-based clear paints containing a heat-sensitive gelling agent are applied to the printing layer having a predetermined temperature. When this occurs, the heat-sensitive gelling agent quickly gels, and the ink bleeding of the printing layer can be more efficiently prevented.

The coating amount of the water-based clear coating composition is usually 15 g / m ² or more 80 g / m ² or less in terms of solid content, and preferably 20 g / m ² or more 65 g / m ² or less in the range of better, less than 15 g / m ^2, design However, if the amount exceeds 80 g / m ² , ink bleeding may occur when the solvent of the ink is not sufficiently evaporated. Moreover, the blocking phenomenon of the coating surface by poor drying may be caused.

  After the water-based clear paint is applied, the water-based clear paint is dried or cured to form a clear layer. Drying or curing 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 water-based clear coating, and should be appropriately selected depending on the composition of the water-based clear coating used. Can do.

Hereinafter, based on an Example and a comparative example, the designable building material of this invention and its manufacturing method are demonstrated in detail.
Here, the compositions of the undercoat paint, the printing surface forming paint, and the water-based clear paint and water-based ink used in the following Examples and Comparative Examples are as follows. The unit of composition in the following table is part by mass unless otherwise specified, and “part” in the composition of the water-based ink is shown on a mass basis.

<Undercoat paint>
Each component shown in Table 1 was blended so as to have the composition shown in Table 1, and beads were kneaded to prepare an undercoat paint.

  The main component “acrylic resin” in Table 1 is a product name “Acrydic A810-45” manufactured by Dainippon Ink Co., Ltd., having a heating residue of 45% and an OH value of 15.0, and a curing agent. “TDi-based prepolymer” is a trade name “Takenate M408” manufactured by Mitsui Takeda Chemical Co., Ltd., and has a heating residue of 50%.

<Paint for printing surface formation>
The components shown in Table 2 were blended so as to have the composition shown in Table 2, and beads were kneaded to prepare a printing surface forming coating material.

  The main agent “acrylic resin” in Table 2 is a trade name “Olestar Q164” manufactured by Mitsui Chemicals, which has a molecular weight of 23,000, a heating residue of 45%, and a specific gravity of 0.95. The “copolymer” is a trade name “Vinylite VAGH” manufactured by Union Carbide Co., which has a molecular weight of 27,000, a heating residue of more than 99% and a specific gravity of 1.39. Furthermore, the main component “acrylic resin emulsion” The trade name “Boncoat YG651” manufactured by Nippon Ink Co., Ltd., having a molecular weight of 1,500,000, a heating residue of 47% and a specific gravity of 1.05, and crosslinked hydrophilic resin particles “polysodium acrylate particles” ”Is a product name“ Toughtic HU720PS ”manufactured by Toyobo Co., Ltd., which is a powdered resin bead having an average particle diameter of 50 μm and a true specific gravity of 1.1, and crosslinked hydrophilic resin particles“ sodium polyacrylate ” grain “Aqueous dispersion” is “Toughtic HU700E” manufactured by Toyobo Co., Ltd., an acrylic polymer emulsion, an average particle size of 0.9 μm, a heating residue of 20 ± 1%, a true specific gravity of 1.1, The main agent “solvent” is a mixed solvent of butyl acetate: xylene = 1: 1, and the main agent “film-forming auxiliary” is butyl glycol ether and 2,2,4-trimethyl 1,3-pentanediol monoisobutyrate. The curing agent “isocyanurate” is a product name “Coronate HX” manufactured by Nippon Polyurethane Industry Co., Ltd. and has a heating residue exceeding 99%.

<Water-based ink>
The composition of the water-based ink of each color used in the examples and comparative examples is as follows.
[Composition of red ink]
Red-brown transparent iron oxide 7.5 parts Water 65.0 parts BYK-190 (Dispersant manufactured by Big Chemie) 8.5 parts Ethylene glycol 11.5 parts Diethylene glycol monobutyl ether 7.5 parts Viscosity (25 ° C, mPa · s): 3.81
Surface tension (25 ° C., mN / m): 33.7
Particle size distribution (D50): 65 nm, (D90): 105 nm

[Composition of yellow ink]
Yellowish brown transparent iron oxide 7.0 parts Water 65.5 parts BYK-190 8.0 parts Ethylene glycol 11.5 parts Diethylene glycol monobutyl ether 8.0 parts Viscosity (25 ° C., mPa · s): 3.90
Surface tension (25 ° C., mN / m): 34.8
Particle size distribution (D50): 70 nm, (D90): 130 nm

[Blue ink composition]
C, I, Pigment Blue 6.0 parts Water 62.0 parts BYK-190 7.0 parts Ethylene glycol 12.0 parts Diethylene glycol 13.0 parts Viscosity (25 ° C., mPa · s): 3.92
Surface tension (25 ° C., mN / m): 35.5
Particle size distribution (D50): 78 nm, (D90): 135 nm

[Composition of black ink]
C, I, pigment black 5.0 parts water 70.0 parts BYK-190 8.0 parts glycerin 5.0 parts diethylene glycol monobutyl ether 12.0 parts Viscosity (25 ° C., mPa · s): 3.75
Surface tension (25 ° C, mN / m): 34.5
Particle size distribution (D50): 115 nm, (D90): 190 nm

<Water-based clear paint>
Each component shown in Table 3 was blended so as to have the composition shown in Table 3, and a clear paint was prepared by mixing with a disper.

  The “binder” in Table 3 is an acrylic resin varnish, which is a product name “Acry Reset EX40” manufactured by Nippon Shokubai Co., Ltd., having a heating residue of 43%. “Thermosensitive gelling agent 1)” is a nonionic surfactant having a cloud point of about 30 ° C., and is a trade name “Adecoupler MPC-800” manufactured by Adeka Corporation. “2)” is a nonionic surfactant having a cloud point of about 50 ° C., and is a trade name “Adecoupler MPC-810” manufactured by Adeka. Furthermore, the “brilliant pigment” is an inorganic pearl pigment, the trade name “Iriodin 163” manufactured by Merck & Co., which is a stable inorganic pearl pigment whose surface of natural mica is coated with titanium oxide (a coating of titanium oxide). 14%). The “film-forming auxiliary” is butyl cellosolve (ethylene glycol monobutyl ether), and the “ultraviolet absorber” is a benzotriazole-based compound, trade name “Tinuvin 1130” manufactured by Ciba Specialty Chemicals. It is. Further, the “matting agent” is an acrylic resin bead having a trade name “Toughtic A-20” manufactured by Toyobo Co., Ltd. and a trade name “TS100” manufactured by Degussa. Furthermore, the “thickener” is a polymer-type special nonionic compound, and is a trade name “Adecanol UH540” manufactured by Adeka Company. Further, the “antifoaming agent” is a silicone compound emulsifier, and is a trade name “SN deformer 381” manufactured by San Nopco.

[Examples 1 to 10 and Comparative Example 1]
The viscosity of the undercoat paint composition shown in Table 1 was adjusted to 9 seconds with Ford Cup # 4, and air was applied to a gypsum slag bar light plate (base material) measuring 30 cm long × 30 cm wide × 1.6 cm thick. The coating was applied by spraying so that the dry mass was 28 g / m ² . After undercoating, drying was performed at 120 ° C. for 5 minutes to form an undercoating layer on the surface of the substrate.

For each of the printing surface forming coatings A to D prepared in the production examples shown in Table 2, the viscosity was adjusted to 13 seconds with Ford Cup # 4, and the gypsum slag bar light plate that was primed as described above was used. Then, it was coated with an airless spray so that the dry mass was 38 g / m ² . After coating each printing surface forming paint, drying was performed at 120 ° C. for 5 minutes to form a receiving layer on the undercoat layer.

  Gypsum slag bar light plate (plate temperature: 55 ° C.) coated with each of the above-mentioned printing surface forming coatings A to D using the above-mentioned aqueous ink red ink, yellow ink, blue ink and black ink. On the other hand, each ink was ejected by a piezo-type ink jet printer (full color ink jet printer: GP-604 manufactured by Mimaki Co., Ltd.) to form a pattern, and a granite pseudo-patterned printing layer was formed on the receiving layer. Then, it was dried at 100 ° C. for 30 seconds.

Using the clear paint of Examples or Comparative Examples shown in Table 3, the gypsum slag bar light plate (base material) on which the printed layer of the granite pseudo-pattern was formed as described above was dried at 32 g / m ² by airless spray. Painted to become. After coating, the coating layer was dried at 120 ° C. for 15 minutes to form a clear layer on the printed layer, and the design building materials of Examples 1 to 10 and Comparative Example 1 were obtained.

<Evaluation of design properties>
The designable building material obtained above was visually observed and the designability was evaluated according to the following criteria.
A: A clear pattern is formed without ink bleeding or repellency.
Δ: Although there is some blurring, the pattern is formed to the extent that there is no practical problem.
X: Ink bleed or repellency occurs and no clear pattern is formed.

<Evaluation of weather resistance test>
About the designable building material obtained above, the weather resistance test (cycle number 20) by a metal weather was implemented as follows.
1 cycle: L → R → shower → D → shower.
L: Wavelength 295 to 780 nm, light energy 63 mW / cm ² (temperature 65 ° C., humidity 70%),
Irradiation for 16 hours.
R: No irradiation (temperature 65 ° C., humidity 70%), 2 hours.
Shower: Sprinkled with pure water for 10 seconds.
D: No irradiation (temperature 30 ° C., humidity 98% or more), 6 hours.

The results of the weather resistance test were evaluated according to the following criteria, and the gloss retention was 60 degrees of the initial surface of the design building material measured with a digital variable gloss meter UGV-5D (manufactured by Suga Test Instruments Co., Ltd.). It was determined by the ratio of the specular gloss value to the 60 ° specular gloss value after the weather resistance test [gloss retention (%) = (gloss value after weather resistance test / initial gloss value) × 100].
○: No change was observed in the appearance of the coating film and the pattern formed, and the gloss retention was 80% or more.
Δ: A slight change was observed in the appearance of the coating film or the pattern formed, and the gloss retention was 65% or more.
X: A drastic change was observed in the appearance of the coating film or the pattern formed, and the gloss retention was less than 50%.

<Evaluation of hot water resistance>
A hot water resistance test is performed by immersing in 50 ± 1 ° C warm water for 30 days, and the subsequent state is visually observed to evaluate the hot water resistance according to the following three criteria. According to JIS K 5600-5-6 A coating film adhesion test was performed according to adhesion (cross-cut method).
○: No change in the appearance of the coating film and the pattern formed, and no delamination.
Δ: The coating film appearance or the formed pattern is slightly changed, and slight delamination is observed.
X: The appearance of the coating film or the pattern formed is drastically changed and delamination is observed.

<Ink re-solubility>
In the ink re-dissolution evaluation test, a cylindrical cup having a diameter of 10 cm is placed on the surface of the design building material, the space between the design building material and the cylindrical cup is sealed, and a high height of 3 cm is placed in the cylindrical cup. Water was poured in and left under conditions of 23 ° C. and 24 hours, and the surface state of the design building material was visually observed.

<Frost damage test B method>
In the frost damage B method test (ASTM C666-B), the evaluation was made according to the following three criteria.
○: No abnormality.
(Triangle | delta): Minute peeling is recognized in a color mixing part.
X: Peeling is observed in the mixed color part.

<Evaluation of metal flow resistance>
About each designable building material obtained above, the metal flow was observed visually and the generation | occurrence | production degree of the metal flow was evaluated with the following three steps | standards.
○: Almost no metal flow is observed.
Δ: A little metal flow is observed.
X: Many metal flows are recognized.

The above evaluation results were as shown in Table 4.

  As is clear from the evaluation results shown in Table 4, in the designable building material according to the example of the present invention, the clear layer exhibits an excellent protective function for the ink receiving layer and the printed layer formed thereon. In addition, the ink bleeding and delamination in the printed layer are improved as much as possible, and as a result, the durability (water resistance, light resistance, and weather resistance) of the entire design building material including the receiving layer, the printing layer, and the clear layer is remarkable. It can be seen that there is an improvement. Moreover, the designable building material according to the example of the present invention was excellent in metal flow resistance. On the other hand, in the comparative example using the water-based clear paint that does not contain a heat-sensitive gelling agent, the durability (water resistance, light resistance, and weather resistance) of the entire design building material including the receiving layer, the printing layer, and the clear layer. ) And the metal flow resistance was also inferior. In addition, the reason that the designability is Δ in the above-described Examples 2 and 3 is due to bleeding when patterning is performed by an ink jet printer.

Claims (14)

  A base material for construction, a printing layer formed by ejecting water-based ink with an ink jet printer on the surface of the base material, and a water-based clear paint containing a binder and a heat-sensitive gelling agent are coated on the printing layer. A designable building material comprising a clear layer formed as described above.   The design-based building material according to claim 1, wherein the water-based clear paint contains a heat-sensitive gelling agent in a range of 0.1 to 12.0 parts by mass in terms of solid content with respect to 100 parts by mass of the binder.   The designable building material according to claim 1 or 2, wherein the water-based clear paint contains a glitter pigment in a range of 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the binder in terms of solid content.   The design property according to any one of claims 1 to 3, wherein an undercoat layer is formed on the surface of the base material by applying an undercoat paint, and the printed layer is provided on the base material via the undercoat layer. Building materials.   The receiving layer is formed by applying a coating material for forming a printing surface on the surface of the substrate, and the printing layer is provided on the substrate via the receiving layer. Designed building materials described.   The surface of the substrate is provided with an undercoat layer formed by applying an undercoat paint, and a receiving layer formed by applying a printing surface forming paint on the undercoat layer. The designable building material according to any one of claims 1 to 3, which is provided on the base material via an undercoat layer and a receiving layer.   A water-based ink is ejected onto the surface of a building substrate by an ink jet printer to form a printed layer, and then a water-based clear paint containing a binder and a heat-sensitive gelling agent is applied onto the printed layer to form a clear layer. The manufacturing method of the designable building material characterized by forming.   The method for producing a designable building material according to claim 7, wherein the application of the water-based clear coating is performed after the formed printed layer is dried and when the temperature of the printed layer is in the range of 30 to 80 ° C.   The method for producing a designable building material according to claim 7 or 8, wherein the water-based clear coating is applied by spray coating. The design-based building material according to any one of claims 7 to 9 , wherein the water-based clear coating contains a heat-sensitive gelling agent in a range of 0.1 to 12.0 parts by mass in terms of solid content with respect to 100 parts by mass of the binder. Manufacturing method.   The design-based building material according to any one of claims 7 to 10, wherein the water-based clear coating contains a glitter pigment in a range of 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the binder in terms of solid content. Manufacturing method.   The method for producing a designable building material according to any one of claims 7 to 11, wherein an undercoat paint is applied to the surface of the substrate to form an undercoat layer, and a printed layer is formed on the undercoat layer.   The printed building surface coating material is applied to the surface of the substrate to form a receiving layer, and the printed layer is formed on the receiving layer. Method.   On the surface of the base material, an undercoat paint is applied to form an undercoat layer, and then a printing surface forming paint is applied onto the undercoat layer to form a receiving layer, and the printed layer is formed on the receiving layer. The manufacturing method of the designable building material in any one of Claims 7-11 which forms.