JP4875476B2 - Building materials - Google Patents

Description

  The present invention relates to a building material used for an exterior material or the like, and particularly relates to a high-design building material to which a water-based ink is applied.

  In recent years, as a building material used for exterior materials, etc., highly-designed building materials that have been ink-printed by inkjet coating or the like have been used, and the use of exterior wall materials, roofing materials, roofing materials, etc. has been expanded. Is expected. In order to obtain such a building material by inkjet coating, for example, a cement-based inorganic board is used as a base material, and the inkjet nozzle is synchronized with the transport speed of the base material toward the surface of the base material transported on a conveyor. It is considered to eject ink from the head. Such ink-jet coating enables local and position-controlled coating as compared with a coating roll or the like that has been generally used so far. Therefore, there is an advantage that a building material coated with a high design with a natural texture can be manufactured by expressing shades (see Patent Document 1).

As described above, when the ink is not sufficiently fixed to the base material when the ink is printed and applied to the base material, an ink receiving layer is formed on the surface of the base material in advance. This ink receiving layer has a function of fixing the ink applied during ink jet coating without bleeding and has a property of absorbing ink. For example, an ink receiving layer is formed by applying a coating material in which an inorganic powder, a water-absorbing polymer, or the like is added to an organic binder to the surface of the substrate (see Patent Document 2).
JP 2004-17007 A Japanese Patent Laid-Open No. 9-11868

  However, depending on the type of base material of the building material formed as described above, adhesion to the receiving layer cannot be obtained and peeling or cracking occurs, and the appearance of the design pattern formed by ink printing application deteriorates. May end up. In addition, if you want to make a pattern by printing using a highly transparent building material (glass plate, plastic plate, etc.) as a base material, use a colored opaque ink-receiving layer to have a transparent base material. I can not make use of the features of. For this reason, there has been a demand for a makeup technique that can be applied to various base materials and that is excellent in ink fixability. Here, conventionally, printing by a cutting sheet or transfer may be considered, but there is a problem that durability is lacking due to deterioration of a film or an ink resin.

  The present invention has been made in view of the above points, and does not select the type of base material, has high weather resistance, and does not easily peel or crack even when exposed to the outdoors, and is formed by application of ink. It aims at providing the building material which can prevent the deterioration of the external appearance of a design pattern.

  The building material according to claim 1 is characterized in that the surface of the substrate 1 is subjected to a hydrophilic treatment, and then a water-based ink is applied to form the pattern layer 2.

  The building material according to claim 2 is characterized in that, in claim 1, the hydrophilic treatment is a treatment for forming a photocatalytic coating film 3 on the surface of the substrate 1.

  The invention according to claim 3 is characterized in that, in claim 1, the hydrophilic treatment is a surface treatment with a surfactant.

  The invention according to claim 4 is characterized in that, in claim 1, the hydrophilic treatment is a treatment in which an alkoxysilane condensate coating 5 is applied to the surface of the substrate 1.

According to claim 1 invention is characterized by comprising providing by sequentially laminating a clear layer 6, inorganic coating layer 7 and the photocatalyst layer 8 with respect to pattern-like layer 2.

The invention according to claim 5 is characterized in that, in any one of claims 1 to 4 , the substrate 1 has a visible light transmittance of 80% or more.

  According to the invention according to claim 1, the water-based ink constituting the pattern layer 2 adheres to the surface of the substrate 1 without being repelled, and the water-based ink can be fixed to the surface of the substrate 1, In addition, since the water-based ink can be fixed without forming an ink receiving layer containing an organic binder on the base material 1 in this way, the transparency of the base material is prevented from being lowered even if the base material is transparent. In addition, the organic binder is not deteriorated as in the case where the ink receiving layer is provided even if the building material is irradiated with ultraviolet rays for a long period of time, and the appearance of the design pattern formed by the pattern layer 2 is improved. Deterioration can be prevented and weather resistance can be improved.

  According to the invention which concerns on Claim 2, high hydrophilicity can be provided to the base material 1 by forming the photocatalyst coating film 3. FIG.

  According to the invention which concerns on Claim 3, high hydrophilicity can be provided to the base material 1 by the surface treatment by surfactant.

  According to the invention which concerns on Claim 4, high hydrophilicity can be provided to the base material 1 by giving the alkoxysilane condensate coating 5.

According to the invention of claim 1, clear layer 6 relative to pattern-like layer 2, since the provided by sequentially laminating an inorganic coating layer 7 and the photocatalyst layer 8, the weather resistance to protect the pattern layer 2 further Even if the clear layer 6 is formed on the pattern layer 2 at this time, the water-based ink is spread and fixed on the surface of the substrate 1 subjected to the hydrophilic treatment. This water-based ink is not crushed and blotted by the clear layer 6, and therefore, a clear design pattern can be maintained.

According to the fifth aspect of the present invention, since the ink receiving layer is not formed, the transparency of the building material is not hindered by the ink receiving layer. The design pattern by the pattern layer 2 can be given to this.

  Hereinafter, the best mode for carrying out the present invention will be described. FIG. 1 shows an example of a building material obtained by the present invention.

<Base material 1>
As the base material 1 to be coated in the present invention, an appropriate one can be used. For example, a cement-based inorganic plate can be used. For the production of the inorganic board, a wet sheet (green sheet) mainly composed of cement and reinforcing fibers can be used. This wet sheet can be made by various papermaking methods such as a long-mesh type and a round-net type using a cement-based aqueous slurry as a raw material composition, but other appropriate methods such as extrusion are also adopted. be able to. Examples of the raw material composition include hydraulic cement components of 30 to 95% by mass, fillers such as silica, silica powder, and fly ash 2 to 60% by mass, and reinforcing fibers such as pulp 3 to 10% by mass. A slurry having a solid content and a ratio of about 50 to 2000 parts by weight of water with respect to 100 parts by weight of the solid content can be used. As the cement component, a composition whose composition is appropriately adjusted, such as ordinary Portland cement and blast furnace cement, can be used. As the reinforcing fiber pulp, softwood pulp, hardwood pulp, waste paper pulp, or a mixture of two or more of these can be used. The substrate 1 can be obtained by curing and curing the wet sheet.

  Curing and curing of the wet sheet can be performed by an appropriate method, but it is desirable to perform autoclave curing, and the temperature at that time is preferably 140 ° C. or higher. In practice, it is desirable that the curing is a two-stage curing of an autoclave curing and a pre-acceleration curing preceding this, that is, a pre-curing in which steam is added for heating. Thereby, the strength of the base material 1 is improved, and the structure and performance are made uniform.

  During this curing, it is desirable to apply a sealer to the surface of the wet sheet before curing. By applying this sealer, it is possible to prevent the occurrence of efflorescence during curing, and the coating film of the sealer exhibits water resistance, thereby improving the water resistance of the substrate 1. it can.

  The sealer is not particularly limited, and for example, an aqueous resin emulsion such as acrylic, vinyl acetate, epoxy, chlorinated rubber, urethane, silicon, or fluorine can be used.

  Further, in such a sealer, inorganic particles such as heavy calcium carbonate, precipitated calcium carbonate, kaolin, bentonite, sericite, dolomite, talc, clay, aluminum oxide, magnesium oxide, diatomaceous earth can be mixed. .

  And, such a sealer can be applied to the surface of the wet sheet and heated to form a film of the sealer.

  Such sealer coating is performed before curing, but when performing pre-acceleration curing as described above, it is preferable to apply the sealer after pre-acceleration curing and then perform autoclave curing. The frost damage resistance and dimensional stability of the material 1 can be improved.

  The base material 1 obtained by such curing is subjected to a drying process or a cutting process as necessary.

  In addition to the cement-based inorganic plate as described above, various substrates can be used as the substrate 1. In particular, in the present invention, the substrate 1 is formed of glass, acrylic resin, polycarbonate resin, or the like. It is preferable to use a transparent base material 1. When such a transparent substrate 1 is used, the visible light transmittance is preferably 80% or more.

<Hydrophilic treatment>
Prior to the formation of the pattern layer 2, hydrophilic treatment is performed on the surface on which the pattern layer 2 is formed.

  Although an appropriate method can be applied as the hydrophilic treatment, it is preferable that the contact angle of water on the surface of the substrate 1 subjected to the hydrophilic treatment is 40 ° or less. Preferable examples of the hydrophilic treatment include the formation of the photocatalyst coating film 3, the surfactant treatment, and the alkoxysilane condensate coating 5.

<Photocatalyst coating film 3>
The photocatalyst coating film 3 can be formed by coating an inorganic coating containing an oxide having a photocatalytic function on the surface of the substrate 1.

  Examples of the inorganic paint include those containing a silicon compound represented by the following general formula [1].

R ² _n Si (OR ¹ ) _4-n [1]
[N = 0 to 3 and R ¹ and R ^{2 each} represent a monovalent hydrocarbon group. ]

R ¹ and R ^{2 in} the formula [1] are not limited as long as they represent a monovalent hydrocarbon group, but R ² represents a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms, for example, a methyl group Alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group, 2-phenylethyl group, 3-phenylpropyl group, etc. Aryl groups such as aralkyl groups, phenyl groups, and tolyl groups; Anienyl groups such as vinyl groups and allyl groups; Halogen-substituted hydrocarbon groups such as chloromethyl groups, γ-chloropropyl groups, and 3,3,3-trifluoropropyl groups And substituted carbons such as γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group, etc. Include hydrogen group. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable because of ease of synthesis or availability.

For R ¹ in the formula [1], those having an alkyl group having 1 to 4 carbon atoms as a main raw material are used. In particular, tetramethoxysilane, tetraethoxysilane and the like are exemplified as the tetraalkoxysilane of n = 0, and methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane are exemplified as the organotrialkoxysilane of n = 1. , Phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane and the like. Further, examples of the n = 2 diorganodialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and the like, and n = 3 triorganoalkoxysilane. Examples thereof include trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, dimethylisobutylmethoxysilane and the like.

  As such an inorganic coating, for example, a silicon compound represented by the following general formula [2] and / or colloidal silica 20 to 200 parts by weight,

General formula: Si (OR ¹ ) ₄ [2]

100 parts by weight of a silicon compound represented by the following general formula [3],

General formula: R ² Si (OR ¹ ) ₃ [3]

What contains the silicon compound represented by following General formula [4] in the ratio of 0-60 weight part is mentioned.

General formula: R ² ₂ Si (OR ¹ ) ₂ [4]

R ¹ and R ² in the formulas [2] to [4] may be the same hydrocarbon group or may be different.

  In preparing the inorganic coating material, for example, the silicon compound represented by the formulas [2] to [4] is diluted with a solvent, water or a catalyst is added as a curing agent, and hydrolysis and polycondensation reactions are performed. can do. The weight average molecular weight (Mw) of these silicon compounds is calculated in terms of polystyrene. In this preparation, the weight average molecular weight (Mw) of the inorganic coating is made 900 or more in terms of polystyrene. When the weight average molecular weight (Mw) is less than 900 in terms of polystyrene, curing shrinkage increases during the polycondensation reaction, and cracks are likely to occur in the baked inorganic coating film.

  Colloidal silica used in combination with or in place of the silicon compound represented by the formula [2] is a water-dispersible colloidal silica dispersed in water or a non-aqueous organic solvent such as alcohol. Dispersed organic solvent-dispersible colloidal silica. The colloidal silica contains 20 to 50% by weight of silica as a solid content. In the preparation of the inorganic coating, the water-dispersible colloidal silica can use water existing as a component outside the solid content as a curing agent. In addition, colloidal silica dispersible in organic solvent can be easily prepared by replacing the organic solvent with water. Examples of the organic solvent in which the colloidal silica is dispersed include, for example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol, ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate. And ethylene glycol derivatives, diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether, and diacetone alcohol. One or more of these are used. Furthermore, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, etc. can be used in combination with a hydrophilic organic solvent. In addition, the said compounding quantity of the said colloidal silica is a weight also including a dispersion medium.

  Water is commonly used as a curing agent when preparing an inorganic coating, and the amount of this water is preferably 45% or less, more preferably 25% or less in the inorganic coating.

  Examples of the organic solvent used in preparing the inorganic paint include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol, ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate. And ethylene glycol derivatives, diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether, and diacetone alcohol. One or more of these are used. Furthermore, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, etc. can be used in combination with a hydrophilic organic solvent.

In preparing the inorganic paint, it is desirable that the pH of the inorganic paint is 3.8-6. If the pH is within this range, the storage stability of the inorganic paint is good, and if it is outside this pH range, the period during which the coating can be applied is limited. The method for adjusting the pH is not limited. For example, when the pH is less than 3.8 when the materials are mixed, the pH may be adjusted by adding a basic reagent such as ammonia. In this case, an acid reagent such as hydrochloric acid may be added for adjustment. Depending on the pH, if the reaction progresses slowly with a small molecular weight, the reaction may be promoted by heating, or after the reaction is advanced by lowering the pH with an acidic reagent, a basic reagent is added. It may be a predetermined pH.
In addition, as another example of the inorganic paint, a hydrolyzable organosilane represented by the following formula [5] is colloidal silica dispersed in an organic solvent or water with respect to 1 mol of the functional group (X). A silica-dispersed oligomer solution of organosilane partially hydrolyzed under conditions using 0.001 to 0.5 mol of water;

General formula: R ³ _n SiX _4-n [5]
[Wherein, R ³ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, n represents an integer of 0 to 3, and X represents a hydrolyzable group. ]

A polyorganosiloxane containing a silanol group in the molecule represented by the following formula [6]:

Average composition formula: R ⁴ _a Si (OH) _b O _{(4-ab) / 2} [6]
[Wherein, R ⁴ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and a and b are 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦, respectively. 3, a number satisfying the relationship of a + b <4. ]

The thing which consists of a catalyst is mentioned. At this time, the silica-dispersed oligomer solution contains 5 to 95% by weight of silica as a solid content, and at least 50 mol% of the hydrolyzable organosilane is an organosilane in which n in the formula [5] is 1. And the said polyorganosiloxane is contained by 99-1 weight part with respect to 1-99 weight part of said silica dispersion | distribution oligomer solutions.

  The silica-dispersed oligomer in the silica-dispersed oligomer solution is a main component of a base polymer having a hydrolyzable group as a functional group that is subjected to a curing reaction when forming a coating film. This silica-dispersed oligomer is obtained by adding one or more hydrolyzable organosilanes represented by the above formula [5] to an organic solvent or colloidal silica dispersed in water, and adding water in the colloidal silica or separately. It is obtained by partially hydrolyzing this hydrolyzable organosilane with added water.

R ^{3 in the} hydrolyzable organosilane represented by the formula [5] represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, specifically, the same hydrocarbon as R ² described above. Examples are groups.

  Examples of X representing the hydrolyzable group include an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group, and an amide group. Among these, an alkoxy group is preferable because it is easily available and a silica-dispersed oligomer solution is easily prepared.

  Such hydrolyzable organosilanes are mono-, di-, tri-, and tetra-functional alkoxysilanes in which n in the chemical formula represented by the formula [5] is an integer of 0 to 3, Examples include acetoxysilanes, oxime silanes, enoxysilanes, aminosilanes, aminoxysilanes, and amidosilanes. Among these, alkoxysilanes are preferable because they are easily available and a silica-dispersed oligomer solution is easily prepared. Examples of the tetraalkoxysilane with n = 0 include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane with n = 1 include methyltrimethoxysilane, methyltriethoxysilane, and methyltriisopropoxysilane. , Phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane and the like. Further, examples of the n = 2 diorganodialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and the like, and n = 3 triorganoalkoxysilane. Examples thereof include trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, dimethylisobutylmethoxysilane and the like. Furthermore, organosilane compounds generally called silane coupling agents are also included in the alkoxysilanes.

  The hydrolyzable organosilane must be at least 50 mol% of a trifunctional organosilane in which n in the formula [5] is represented by 1. The proportion of the trifunctional organosilane is preferably 60 mol% or more, more preferably 70 mol% or more. If this is less than 50 mol%, sufficient coating film hardness cannot be obtained, and the dry curability tends to be poor.

  Colloidal silica in which the hydrolyzable organosilane is dispersed in an organic solvent or water increases the hardness of the cured coating film of the inorganic paint. Examples of the colloidal silica include the water-dispersible colloidal silica described in the inorganic paint according to claim 1 or the organic solvent-dispersible colloidal silica.

  The colloidal silica contains silica in a range of 5 to 95% by weight as a solid content. The content is preferably 10 to 90% by weight, more preferably 20 to 85% by weight. When the content is less than 5% by weight, the hardness of the coating film of the inorganic paint cannot be obtained, and when the content exceeds 95% by weight, uniform dispersion of the silica becomes difficult and problems such as easy gelation occur. Cheap.

  The hydrolyzable organosilane represented by the formula [5] is partially hydrolyzed in an organic solvent or water-dispersed colloidal silica to obtain an organosilane silica-dispersed oligomer solution. The amount of water relative to the hydrolyzable organosilane is preferably 0.001 to 0.5 mol of water with respect to 1 mol of the hydrolyzable group (X). When the amount of water is less than 0.001 mol, sufficient partial hydrolysis cannot be obtained, and when it exceeds 0.5 mol, the stability of the partial hydrolyzate is deteriorated. The method for the partial hydrolysis is not particularly limited, and a hydrolyzable organosilane and colloidal silica may be mixed, and predetermined water may be added. At this time, the partial hydrolysis reaction proceeds at room temperature. In addition, in order to accelerate | stimulate the said partial hydrolysis reaction, you may heat at 60-100 degreeC. Furthermore, for the purpose of promoting partial hydrolysis reaction, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, Organic acids such as toluenesulfonic acid and oxalic acid and inorganic acids may be used as the catalyst.

  In order to obtain the above-mentioned silica-dispersed oligomer solution stably for a long period of time, the pH of the solution is 2.0 to 7.0, preferably 2.5 to 6.5, more preferably 3.0. It is good to set to ~ 6.0. When the pH is out of this range, the long-term performance deterioration of the silica-dispersed oligomer solution is remarkable especially when the amount of water is 0.3 mol or more per 1 mol of the hydrolyzable group (X). The method for adjusting the pH is not limited, but when the pH of the liquid deviates from the above range to the acidic side, it may be adjusted by adding a basic reagent such as ammonia or ethylenediamine. When the pH deviates from the basic side, hydrochloric acid It may be adjusted by adding an acidic reagent such as nitric acid or acetic acid.

The average composition formula of the polyorganosiloxane containing silanol groups of the inorganic coating is represented by the formula [2
R ⁴ in the formula [6] represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and specific examples thereof include the same hydrocarbon groups as those described above for R ^2. Is an alkyl group having 1 to 4 carbon atoms, phenyl group, vinyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-aminopropyl group, 3,3,3-trifluoropropyl group, etc. A substituted hydrocarbon group, more preferably a methyl group and a phenyl group. Further, a and b in the formula [6] are numbers satisfying the relations 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3, and a + b <4, respectively. When a is less than 0.2 or b is more than 3, there are disadvantages such as cracks in the cured coating film, and when a is more than 2.0 and less than 4 or when b is less than 0.0001, curing is successful. Does not progress.

  The polyorganosiloxane containing silanol groups is a large amount of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, or one or a mixture of two or more alkoxysilanes corresponding to these in a known manner. It can be obtained by hydrolysis with water. When the polyorganosiloxane containing the silanol group is obtained by hydrolysis using alkoxysilane, a trace amount of alkoxy groups that are not hydrolyzed may remain. That is, a polyorganosiloxane in which a silanol group and a trace amount of alkoxy group coexist may be obtained, but such a polyorganosiloxane may be used.

  The catalyst accelerates the condensation reaction between the silica dispersion oligomer solution and the polyorganosiloxane, and cures the coating film. Examples of the catalyst include metal salts of carboxylic acids such as alkyl titanates, tin octylate and dibutyl tin dilaurate, dioctyl tin dimaleate, amine salts such as dibutylamine-2-hexoate, dimethylamine acetate, and ethanolamine acetate. Quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate, amines such as tetraethylpentamine, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxy Amine-based silane coupling agents such as silane, acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid, aluminum compounds such as aluminum alkoxide and aluminum chelate, alkali catalysts such as sodium hydroxide, tetraisopropyl titane , Tetrabutyl titanate, titanium compounds such as titanium tetraacetyl acetonate, methyltrichlorosilane, dimethyldichlorosilane, halogenated silane such as trimethyl monochloro silane, and the like.

  The mixing ratio of the silica dispersion oligomer solution and the polyorganosiloxane is 99 to 1 part by weight of the polyorganosiloxane with respect to 1 to 99 parts by weight of the silica dispersion oligomer solution, preferably the silica dispersion oligomer solution. The polyorganosiloxane is 95 to 5 parts by weight with respect to 5 to 95 parts by weight, more preferably 90 to 10 parts by weight of the polyorganosiloxane with respect to 10 to 90 parts by weight of the silica-dispersed oligomer solution. It is. When the ratio of the silica-dispersed oligomer solution is less than the above range, it is difficult to cure at room temperature, and sufficient coating film hardness cannot be obtained. If the ratio of the silica-dispersed oligomer solution is more than the above range, the curability becomes unstable.

  The catalyst content is preferably 0.0001 to 10 parts by weight based on 100 parts by weight of the total of the silica-dispersed oligomer solution and the polyorganosiloxane. More preferably, it is 0.0005-8 weight part, Most preferably, it is 0.0007-5 weight part. If the catalyst is less than 0.0001 parts by weight, it will not be cured at room temperature, and if it exceeds 10 parts by weight, the heat resistance and weather resistance will be poor.

  The hydrolyzable group contained in the silica-dispersed oligomer and the silanol group in the polyorganosiloxane undergo a condensation reaction in the presence of a catalyst at room temperature or at a low temperature of 200 ° C. or lower to form a coating film. Therefore, the inorganic coating is cured at room temperature with almost no influence of humidity. Further, the condensation reaction can be promoted by the low temperature heating.

  The above-mentioned inorganic paint can be diluted with various organic solvents for ease of handling. The type of the organic solvent is appropriately selected depending on the type and molecular weight of the monovalent hydrocarbon group in the silica dispersion oligomer solution and the polyorganosiloxane. Examples of the organic solvent include the same organic solvents as described in the inorganic paint according to claim 1.

  Examples of the oxide having a photocatalytic function to be included in this inorganic paint include, for example, titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, Examples thereof include cadmium oxide, copper oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, rhenium oxide, and the like. These can be used alone or in combination of two or more. . The oxide having the photocatalytic function is mixed in the inorganic coating within an appropriate range, and is formulated so that the water contact angle of the substrate 1 hydrophilized by the photocatalytic coating film 3 is 40 ° or less. It is preferable to adjust the amount. Specifically, the blending amount may be adjusted in a range where the weight percentage (PWC: pigment weight concentration) of the oxide is 5 to 90% with respect to the total weight of the oxide and the resin solid content in the inorganic paint. it can.

  Further, a metal may be supported on the component having the photocatalytic function. Examples of the metal include silver, copper, iron, nickel, zinc, platinum, gold, palladium, cadmium, cobalt, rhodium, and ruthenium, or a mixture of two or more. When a metal is supported on a component having a photocatalytic function, charge separation is promoted and the photocatalytic catalyst is activated.

  Furthermore, you may contain the clay mineral which inserted the oxide which has a photocatalytic function between the layers. As the clay mineral, a smectite type mineral having swelling properties is suitable. The smectite type mineral may be either natural or synthetic. The oxides inserted into the clay mineral are titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, cadmium oxide, copper oxide, One or more of vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, rhenium oxide, and the like can be given. When an oxide is inserted between clay mineral layers, the oxide is held in fine particles and exhibits high photocatalytic activity. Further, a metal may be supported on an oxide having a photocatalytic function inserted between layers. Examples of the metal include silver, copper, iron, nickel, zinc, platinum, gold, palladium, cadmium, cobalt, rhodium, and ruthenium, or a mixture of two or more. When a metal is supported on an oxide having a photocatalytic function, charge separation is promoted and the photocatalytic catalyst is activated.

  When preparing an inorganic paint containing an oxide having a photocatalytic function, the component having the photocatalytic function is used in a state dispersed in a solvent or in a powder state. This powder is obtained by drying such as heat drying, freeze drying, and supercritical drying.

  In applying such an inorganic coating, various coating methods such as brush coating, spray coating, dipping, curtain, knife coating, etc. can be employed. In application, it may be appropriately diluted with an organic solvent as necessary.

  After the photocatalytic coating film 3 is formed, the hydrophilicity may be further improved by irradiating the photocatalytic coating film 3 with ultraviolet light.

  In addition, depending on the material of the base material 1, an appropriate primer layer may be provided on the base material 1 as necessary in order to improve adhesion and prevent cracking prior to the formation of the photocatalytic coating film 3. In addition, an inorganic paint that does not contain an oxide having a photocatalytic function may be applied to the base material 1 directly or via the primer layer.

<Surfactant treatment>
The surfactant treatment can be performed by applying an appropriate surfactant to the substrate 1. As the surfactant, an appropriate one can be used, and the hydrophilic group may be ionic or nonionic, and may be a low molecular type or a high molecular type. As such a surfactant, for example, a mixture of acrylic resin, urethane resin, fluorine resin, silicon resin, or the like in a ratio of 1 wt% or less can be applied to the substrate 1. In addition, the surfactant may be mixed with a solvent capable of dissolving the surfactant, such as water or an appropriate solvent, at a ratio of 1% by weight or less and applied to the substrate 1. The hydrophilicity of the surface of the substrate 1 after the treatment can be adjusted by adjusting the type and the coating amount of the surfactant.

<Alkoxysilane condensate coating 5>
The alkoxysilane condensate coating 5 is formed by coating an inorganic coating composition containing a silicone resin obtained by hydrolytic polycondensation of only a tetrafunctional alkoxysilane represented by the following formula [7] on a substrate 1. Can be formed.

Si (OR) ₄ [7]
[Wherein R is an alkyl group or aryl group having up to 7 carbon atoms]

  In the formula [7], R is preferably at least one selected from the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, and a phenyl group. Specific examples of the tetrafunctional alkoxysilane include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, and tetra-t-butoxysilane. Only one type of tetrafunctional alkoxysilane may be used, or two or more types may be used in combination.

  Here, when a trifunctional or lower functional alkoxysilane is added as the polymerizable component of the silicone resin, the coating film performance such as surface hydrophilicity of the formed coating film is deteriorated. The form of the silicone resin in the inorganic coating composition is not particularly limited, and may be, for example, a solution form or a dispersion liquid form.

  The silicone resin is contained as a main component in the inorganic coating composition. The main component means that the silicone resin is present in an amount of 50 to 100% by weight in the solid content of the inorganic coating composition. Preferably, the silicone resin is present in the solid content of the inorganic coating composition in an amount of 50 to 80 wt%, more preferably 50 to 70 wt%.

  Moreover, this inorganic coating composition may contain an appropriate functional component. Such functional components include curing catalysts, fillers, colorants, film forming aids, coating aids, antioxidants, and ultraviolet absorbers.

  The curing catalyst is used for the purpose of accelerating the curing of the coating layer by accelerating the condensation reaction of the silicone resin. The curing catalyst is not particularly limited. For example, alkyl titanates; metal carboxylates such as tin octylate, dibutyltin dilaurate, dioctyltin dimaleate; dibutylamine-2-hexoate, dimethylamine acetate, ethanolamine acetate Quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate; amines such as tetraethylpentamine, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ -Amine-based silane coupling agents such as aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; lithium acetate, potassium acetate and lithium formate Alkali metal salts such as sodium formate, potassium phosphate, potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate, titanium tetraacetylacetonate; halogens such as methyltrichlorosilane, dimethyldichlorosilane, trimethylmonochlorosilane Silanes and the like. However, other than these, there is no particular limitation as long as it is effective for promoting the condensation reaction of the silicone resin. When the inorganic coating composition contains a curing catalyst, the amount thereof is 10 parts by weight or less, more preferably 8 parts by weight or less based on 100 parts by weight of the silicone resin based on the solid content. If it exceeds 10 parts by weight, the storage (storage) stability of the inorganic coating composition may be impaired.

  The filler (film-forming auxiliary) is used for the purpose of increasing the hardness of the formed cured coating film and improving smoothness and crack resistance. Known silica can be used. The form of silica when introduced into the paint is not particularly limited, and may be, for example, a powder form or a colloidal silica form. Although it does not specifically limit as said colloidal silica, For example, non-aqueous organic solvent dispersible colloidal silica, such as water dispersibility or alcohol, can be used. Generally, such colloidal silica contains 20 to 50% by weight of silica as a solid content, and the amount of silica can be determined from this value.

  Silica is preferably introduced into the coating material by dispersing it in the form of colloidal silica in the reaction solvent used in the preparation of the silicone resin, from the viewpoint of film forming property and process simplification. However, this method is not limited. For example, after the silica is mixed with the silicone resin obtained without silica, the resulting mixture may be introduced into the paint, or the silica may be added to the silicone resin. May be introduced separately into the paint.

  Here, when water-dispersible colloidal silica is used, water present as a component other than solid content in the colloidal silica can be used for hydrolysis of tetrafunctional alkoxysilane which is a raw material of silicone resin. (It is added to the following amount of water used during hydrolysis) and can be used as a curing agent for inorganic coating compositions.

  Water-dispersible colloidal silica is usually made from water glass, but can be easily obtained as a commercial product. The organic solvent-dispersible colloidal silica can be easily prepared by replacing the water of the water-dispersible colloidal silica with an organic solvent. Such an organic solvent-dispersible colloidal silica can also be easily obtained as a commercial product in the same manner as the water-dispersible colloidal silica.

  In the organic solvent-dispersible colloidal silica, the type of the organic solvent in which the colloidal silica is dispersed is not particularly limited. For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene And ethylene glycol derivatives such as glycol, ethylene glycol monobutyl ether and ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. Two or more types can be used. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used.

  If the amount of silica is too large, the cured coating film becomes too hard and cracks may occur. Therefore, when using silica, the compounding quantity is 10-90 weight part with respect to 100 weight part of silicone resin on a solid content basis, Preferably it is 20-85 weight part. If the blending amount is less than 10 parts by weight, the desired film hardness tends not to be obtained. On the other hand, if it exceeds 90 parts by weight, cracks are likely to occur.

  In addition, the inorganic coating composition can be toned by further containing a colorant such as a pigment or a dye, if necessary.

  Examples of the pigment include, but are not limited to, organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and hansa yellow; inorganic pigments such as titanium oxide, barium sulfate, dials, and composite metal oxides However, one or two or more selected from these groups may be used in combination. The dispersion of the pigment is not particularly limited, and may be an ordinary method, for example, a method of directly dispersing pigment powder by dynomeal, a paint shaker or the like. At that time, it is possible to use a dispersant, a dispersion aid, a thickener, a coupling agent and the like. The amount of pigment added is not particularly limited because the concealability varies depending on the type of pigment, but is, for example, 5 to 80 parts by weight, preferably 10 to 70 parts by weight based on 100 parts by weight of the silicone resin based on the solid content . When this addition amount is less than 5 parts by weight, the concealability tends to be poor, and when it exceeds 80% by weight, the smoothness of the coating film may be deteriorated.

  Although it does not specifically limit as dye, For example, an azo type, anthraquinone type, indicoid type, sulfide type, triphenylmethane type, xanthene type, alizarin type, acridine type, quinone imine type, thiazole type, methine type, nitro type And nitroso-based dyes. One or two or more selected from these groups may be used in combination. The amount of the dye added is not particularly limited because the concealability varies depending on the type of the dye. For example, it is 5 to 80 parts by weight, preferably 10 to 70 parts by weight based on 100 parts by weight of the silicone resin based on the solid content. . When this addition amount is less than 5 parts by weight, the concealability tends to be poor, and when it exceeds 80 parts by weight, the smoothness of the coating film may be deteriorated.

  Leveling agents, metal powders, glass powders, antibacterial agents, antioxidants, ultraviolet absorbers, and the like may also be included in the inorganic coating composition within a range that does not adversely affect the effects of the present invention.

  In the inorganic coating composition, the total solid content concentration needs to be adjusted to 5% by weight or less based on the total amount of the coating. Since the total solid content concentration of the coating material is so thin, the storage stability of the coating material is improved and the coating film can be easily formed into a thin film, and the coating film can be prevented from being cracked or peeled off. In these respects, the total solid content concentration of the paint is more preferably 2% by weight or less, and further preferably 1% by weight or less. The lower limit of the total solid content concentration of the dye is preferably 0.001% by weight, more preferably 0.01% by weight. When the total solid content concentration of the paint is lower than 0.001% by weight, the function as a paint tends to be difficult to be obtained or multiple layers must be coated, which is not preferable.

  Although the dilution solvent used for the said adjustment of a density | concentration will not be specifically limited if it can mix with a silicone resin (it is an optical semiconductor material further when using an optical semiconductor material), For example, various organic solvents are mentioned. The type of the organic solvent can be appropriately selected according to the type of monovalent hydrocarbon group of each component of the silicone resin, the size of the molecular weight of each component of the silicone resin, or the like.

Such an organic solvent is not particularly limited, but examples thereof include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate. And ethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol, etc. , One or more selected from the group consisting of these can be used.
The method for producing the inorganic coating composition is not particularly limited, and each component may be mixed using a normal method and apparatus. As for the form of each component when introduced into the paint, it may be liquid in itself, a solution dissolved in a solvent, a liquid such as a dispersion dispersed in a dispersion medium, a solid such as a powder, etc. Regardless, there is no particular limitation.

  When introducing each component in the form of a solution or a dispersion, for example, water, the above-mentioned organic solvent, or a mixture of water and the above-mentioned organic solvent can be used as the solvent or dispersion medium. Each component may be added separately, or two or more components may be mixed in advance and then mixed with the remaining components, or all components may be mixed simultaneously. There is no particular limitation on the timing of mixing and the like.

  The inorganic coating composition is, for example, a hydrophilic solution of an inorganic material, in which the inorganic material contains only a tetrafunctional alkoxysilane as a polymerizable component, and the tetrafunctional in the hydrophilic solution. It may be prepared by hydrolytic polycondensation of a functional alkoxysilane. However, other non-polymerizable inorganic materials may be present in the hydrophilic solution during the hydrolysis condensation.

  Hydrolytic condensation of tetrafunctional alkoxysilane is carried out by, for example, adding water as a curing agent to the above hydrophilic solution and optionally a catalyst (for example, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid, benzoic acid, dimethyl Add necessary amount of malonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, malonic acid, toluenesulfonic acid, oxalic acid, etc. If necessary, it can be heated (for example, 40 to 100 ° C.).

  The weight average molecular weight (Mw) of the resulting silicone resin (prepolymer) is adjusted to be preferably at least 800, more preferably at least 850, and even more preferably at least 900 in terms of polystyrene. When the molecular weight distribution (weight average molecular weight (Mw)) of the silicone resin is smaller than 800, when the coating layer is cured, the silicone resin is greatly contracted, and there is a fear that the coating film may crack after curing.

  The amount of water as a curing agent is preferably 0.01 to 3.0 mol, more preferably 1.0 to 2.5 mol, per 1 mol equivalent of the alkoxy group of the tetrafunctional alkoxysilane.

  As the diluting solvent (reaction solvent) used in the hydrolysis polycondensation reaction of the tetrafunctional alkoxysilane, those described above as specific examples of the colloidal silica dispersion solvent can be used.

  The pH of the silicone resin is preferably adjusted within the range of 3.8-6. If the pH is within this range, the silicone resin can be used stably within the above molecular weight range. When the pH is outside this range, the silicone resin is not stable, and the usable period from the preparation of the paint is limited.

  The pH adjustment method is not particularly limited. For example, when the pH of the silicone resin is less than 3.8 at the time of mixing the raw materials of the silicone resin, for example, a basic reagent such as ammonia may be used. What is necessary is just to adjust to pH, and also when pH exceeds 6, it should just adjust using acidic reagents, such as hydrochloric acid, for example. Also, depending on the pH, when the reaction does not proceed conversely with a small molecular weight and it takes time to reach the molecular weight range, the reaction may be promoted by heating the silicone resin, or with an acidic reagent. After proceeding with the reaction lowered, the pH may be returned to a predetermined pH with a basic reagent.

  The method for applying the inorganic coating composition to the surface of the substrate 1 is not particularly limited. For example, brush coating, spray coating, dipping (also referred to as dipping or dip coating), roll coating, flow coating (substrate) 1), various coating methods such as curtain coating, knife coating, spin coating, and bar coating can be selected.

  The coating layer of the inorganic coating composition formed on the surface of the substrate 1 is heated at a low temperature or allowed to stand at room temperature, whereby the hydrolyzable groups of the silicone resin undergo a condensation reaction with the cured coating film. can do. Such an inorganic coating composition is hardly affected by humidity even when cured at room temperature. Moreover, if heat processing are performed, a condensation reaction can be accelerated | stimulated and a cured coating film can be formed.

  About the hardening method of an application layer, a well-known method should just be used and it does not specifically limit. Further, the temperature at the time of curing is not particularly limited, and can be in a wide range from room temperature to heating temperature depending on the desired cured coating film performance, the heat resistance of the optical semiconductor material and the substrate 1, and the like. In addition, depending on the kind of the base material 1, it is also possible to bake at about 500-700 degreeC, and it is also possible to form the silica ultrafine particle layer 4 by which the ultrafine particle of silica was arrange | positioned in the surface layer in that case.

  The thickness of the cured coating film to be formed may be about 0.01 to 0.5 μm so that cracks and peeling do not occur, but the various functions of the coating film can be exhibited more effectively or at room temperature. In order to shorten the curing time and to ensure that the cured coating film is stably adhered and held for a long time, 0.01 to 0.3 μm is preferable, and 0.01 to 0.1 μm is more preferable.

<Pattern layer 2>
After performing such hydrophilic treatment, the pattern layer 2 is formed by printing and applying water-based ink to the surface of the substrate 1 that has been subjected to the hydrophilic treatment.

  As a water-based ink, a pigment ink in which a conventionally known pigment is dispersed with a dispersant can be used. However, it is difficult to increase the pigment concentration by inkjet coating, and the amount of the binder resin is small, so that the color of the printed matter is reduced. It tends to darken, and the quality as a decorative material tends to decrease significantly. From this point of view, an aqueous pigment-type ink comprising an aqueous dispersion of colored resin particles in which pigment particles are coated with a film-forming resin having an acid group neutralized at least partially with a base has excellent weather resistance. This is preferable because the color reproduction range is wide as well as the properties and high print quality can be obtained.

  The pigment used in the above-described water-based ink is not particularly limited, and examples thereof include inorganic pigments such as carbon black, titanium black, titanium white, zinc sulfide, and bengara, azo pigments such as phthalocyanine pigments, monoazo-types, and disazo-types, and phthalocyanines. There are organic pigments such as pigments and quinacridone pigments. The amount (content) of the pigment used is not particularly limited, but is preferably an amount that is 0.5 to 10% by weight in the aqueous ink.

  An appropriate method can be used for the printing application of the water-based ink, but the printing application is preferably performed by inkjet coating.

  As a coating apparatus used for performing inkjet coating, the one shown in FIG. 2 can be exemplified. The coating apparatus controls a coating nozzle head 11 provided with an ejection nozzle 10, an ink supply tank 12 that supplies ink to the ejection nozzle 10 of the painting nozzle head 11, and ejection of ink from the ejection nozzle 10 of the painting nozzle head 11. The ink jet type coating machine 14 provided with the coating control system 13 and the like, and a conveying means 15 for conveying the substrate 1 are formed.

  The coating nozzle head 11 is provided at the lower end of the ink jet coating machine 14 and is formed as a long line head in a direction perpendicular to the feeding direction of the building board 1.

  The coating nozzle head 11 is formed of four types of coating nozzle heads 11y, 11c, 11m, and 11k that eject inks of yellow, cyan, magenta, and black, so that full-color printing can be performed. is there. The number of coating nozzle heads 11 is not limited to this, and a number corresponding to the type of ink used is provided. Similarly, the ink supply tank 12 is composed of four types. The ink supply tank 12y that supplies yellow ink is applied to the coating nozzle head 11y, and the ink supply tank 12c that supplies cyan ink is applied to the coating nozzle head 11c. The ink supply tank 12m for supplying magenta ink is connected to the coating nozzle head 11m, and the ink supply tank 12k for supplying black ink is connected to the coating nozzle head 11k. And each coating nozzle head 11y, 11c, 11m, and 11k are arranged along the conveyance direction of the base material 1. FIG.

  The painting control system 13 is composed of various CPUs, ROMs, RAMs, and the like, and includes a painting data creation unit, a painting control unit, an injection nozzle control unit, and the like. The painting data creation unit inputs and stores the color pattern data obtained by scanning the original image with a scanner, etc., and the painting control unit paints the color pattern data corresponding to the building board 1 to be painted. A control signal is output from the data creation unit to the ejection nozzle control unit based on the color pattern data. The spray nozzle control unit is connected to each spray nozzle 10 of the coating nozzle heads 11y, 1c, 11m, and 11k, and controls each spray nozzle 10 based on a control signal input from the spray nozzle control unit. . Each ejection nozzle 10 is controlled to be ejected by, for example, a piezo control system or a control system for irradiating a photothermal exchange element with laser light. By controlling each ejection nozzle 10 with an ejection nozzle controller, yellow, It is possible to perform coating by full-color printing corresponding to a color pattern by individually controlling the ejection and stop of each ink of cyan, magenta, and black.

  The conveying means 15 can be formed by a belt conveyor 15 a in which an endless belt 16 such as a timing belt is suspended between pulleys 17, and is arranged below the ink jet coating machine 14.

  In carrying out the inkjet coating, first, the substrate 1 is supplied to the conveying means 5. At this time, the plurality of base materials 1 can be sequentially conveyed at intervals.

  Thus, the base material 1 conveyed by the conveying means 5 passes below the coating nozzle head 11. At this time, ink is ejected from the coating nozzle head 11 toward the ink receiving layer 4 on the base material 1 by an ink jet method to be painted, and the building board 1 to which a design pattern is given is obtained.

  When the water-based ink is printed and applied to the base material 1 thus subjected to the hydrophilic treatment to form the pattern layer 2, the water-based ink constituting the pattern layer 2 adheres to the surface of the base material 1 without being repelled. Thus, the water-based ink can be fixed on the surface of the substrate 1.

  Further, since the water-based ink can be fixed without forming an ink receiving layer containing an organic binder on the substrate 1, the organic material as in the case where the ink receiving layer is provided even when the building material to be formed is irradiated with ultraviolet rays. The yellowing due to the deterioration of the binder does not occur, the appearance of the design pattern formed by inkjet coating is not deteriorated, and the weather resistance is improved.

  Further, since the ink receiving layer is not provided, transparency is not impaired by the ink receiving layer. For this reason, when a highly transparent material made of glass, acrylic resin, polycarbonate resin or the like is used as the base material 1, and preferably a visible light transmittance of 80% or more, a transparent building material as a whole is formed. A design pattern can be imparted to the building material. At this time, in particular, when the visible light transmittance of the substrate 1 is 80% or more, a building material having particularly excellent transparency can be obtained.

  Moreover, after performing the inkjet coating to the base material 1, the clear layer 6 (organic clear layer) for surface protection can also be formed as needed. The clear layer 6 can be formed by applying and forming an appropriate clear paint. For example, an acrylic emulsion or the like is used, and this is applied by spraying or the like, and then heated and dried at 100 to 150 ° C. for 30 seconds or more. Thus, the clear layer 6 can be formed by film formation. The thickness of the clear layer 6 is not particularly limited, but is preferably in the range of 5 to 100 μm.

  Even when the clear layer 6 is formed in this way, the water-based ink by ink-jet coating is spread and fixed on the surface of the substrate 1, so that the water-based ink is not crushed and blotted by the clear layer 6, Therefore, a clear design pattern is maintained.

  Further, an inorganic paint layer 7 (inorganic clear layer) can be further formed on the building material. The inorganic paint layer 7 can be formed by applying an inorganic paint on the surface of the clear layer 6 and thereby forming the weather resistance of the building material.

  As the inorganic coating material, an appropriate one can be used. For example, a silicon alkoxide system in which a condensation reaction catalyst such as polyorganosiloxane and alkyl titanate is added to silica dispersion oligomer solution of organosilane, or silica is further added. Paint or the like can be used.

Specifically, for example, in colloidal silica in which a hydrolyzable organosilane represented by the following formula [8] is dispersed in an organic solvent or water, 0.001 to 0.5 mol of water is used per 1 mol of X. An organosilane silica-dispersed oligomer solution (component A) formed by partial hydrolysis below, and represented by the following formula [9], wherein R ² in this formula [9] is all R ² groups The polyorganosiloxane (component B) contained in an amount of 1 to 30 mol% and a catalyst for promoting the condensation reaction between the component A and the component B are essential components, and silica is contained in the component A in an amount of 5 to 95% by weight. %, And at least 50 mol% of the hydrolyzable organosilane is an organosilane having n = 1, and an inorganic coating in which 99 to 1 part by weight of B component is blended with respect to 1 to 99 parts by weight of A component is used. In That.

R ¹ _n SiX _4-n (8)
Wherein R ¹ is the same or different, alkyl group, cycloalkyl group, alkenyl group, halogen-substituted hydrocarbon group, γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl. A monovalent hydrocarbon group having 1 to 8 carbon atoms selected from the group consisting of a group and a γ-mercaptopropyl group, n is an integer of 0 to 3, X is an alkoxy group, an acetoxy group, an oxime group, an enoxy group, It represents a hydrolyzable group selected from the group consisting of an amino group, an aminoxy group and an amide group.)

^{_{R 2 a Si (OH) b}} O (4-a-b) / 2 ... (9)
Wherein R ² is the same or different, alkyl group, cycloalkyl group, alkenyl group, halogen-substituted hydrocarbon group, γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl. A monovalent hydrocarbon group having 1 to 8 carbon atoms selected from the group consisting of a group and a γ-mercaptopropyl group, wherein a and b are 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3, a + b, respectively. <A number that satisfies the relationship of 4.

  After applying such an inorganic paint by electrostatic coating or the like, the inorganic paint layer 7 can be formed by forming a film by baking and drying at 60 to 120 ° C., for example. The thickness of the inorganic coating layer 7 is not particularly limited, but is preferably in the range of 1 to 10 μm.

  It is also preferable to form a photocatalyst layer 8 (photocatalyst-containing inorganic clear layer). The photocatalyst layer 8 can be formed by applying and forming an inorganic paint containing a photocatalyst on the surface of the inorganic paint layer 7, thereby improving the antifouling property of the building material. As the inorganic coating material containing a photocatalyst, an appropriate one can be used. For example, a coating obtained by adding a photocatalyst such as titanium oxide to the above silicon alkoxide coating material can be used. Specifically, a paint similar to the paint for forming the photocatalyst coating film 3 described above can be used. After applying such a paint by spray coating or the like, the photocatalyst layer 8 can be formed by baking and drying at 60 to 120 ° C. to form a film. The thickness of the photocatalyst layer 8 is not particularly limited, but is preferably in the range of 0.2 to 1.0 μm.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, molecular weight is the value calculated | required from the calibration curve of the standard polystyrene, using a measurement model HLC8020 (manufactured by Tosoh Corporation) by gel permeation chromatography (GPC).

Example 1
A polycarbonate resin plate ("Polyca ace ECK100L" manufactured by Tsutsunaka Plastic Industry Co., Ltd .; light transmittance 89%) is used as the base material 1, and the photocatalytic coating film 3 is applied as a hydrophilic treatment to the base material 1 as follows. Processing to form was performed.

  First, a titanium oxide powder carrying silver was prepared as follows. After dispersing titanium oxide powder (Nippon Aerosil Co., Ltd .: trade name P-25) in water to form an aqueous solution of 1% by weight (hereinafter referred to as%), the proportion of silver is 5% with respect to the titanium oxide powder. Silver nitrate was added, and ultraviolet rays were irradiated for 3 hours, so that silver was supported on the surface of titanium oxide. Then, it dried and obtained the titanium oxide powder which carry | supported silver.

  Next, 60 parts by weight of IPA organosilica sol (manufactured by Catalyst Kasei Co., Ltd .: trade name OSCAL1432) and 100 parts by weight of isopropyl alcohol (IPA) were mixed with 100 parts by weight of methyltrimethoxysilane, and then 60 parts by weight of water was added. The mixture was stirred and the weight average molecular weight was adjusted to Mw = 950 in a constant temperature bath at 60 ° C. 20 parts by weight of the titanium oxide powder supporting silver was added to the prepared liquid to obtain an inorganic paint.

  The obtained inorganic coating material was apply | coated to the base material 1, and it dried for 20 minutes at the temperature of 120 degreeC. The heating temperature was determined in consideration of the influence on the base material 1 since the base material 1 is made of polycarbonate resin. The film thickness of the photocatalyst coating film 3 after curing was 10 μm.

  The water contact angle on the surface of the substrate 1 thus subjected to hydrophilic treatment was measured and found to be 35 °.

Next, the surface of the base material 1 on which the photocatalytic coating film 3 was formed was subjected to ink jet coating using an ink jet printer “MMP13000” manufactured by Mastermind Co., Ltd., thereby producing a building material. At this time, black ink “ICMB25”, yellow ink “ICY25”, gray ink “ICGY25”, light magenta ink “ICLM25”, magenta ink “ICM25”, light cyan, which are water-based pigment inks manufactured by Seiko Epson Corporation, are used as inks. Seven inks of ink “ICLC25” and cyan ink “ICC25” were used, and then a clear layer 6 was formed. This clear layer 6 was formed by spraying an acrylic resin paint based on an acrylic emulsion and drying and baking at 120 ° C. for 5 minutes, so that the coating thickness after drying was 20 μm.

  Subsequently, the inorganic coating layer 7 was formed as follows.

  First, in a flask equipped with a stirrer, a heating jacket, a condenser and a thermometer, methanol-dispersed colloidal silica sol (“MA-ST” manufactured by Nissan Chemical Industries, Ltd .; particle diameter 10-20 mμ, solid content 30%) 100 parts by weight, methyltri 68 parts by weight of methoxysilane and 10.8 parts by weight of water were charged, and a partial hydrolysis reaction was carried out at a temperature of 65 ° C. for about 5 hours with stirring, followed by cooling to prepare an A component having a solid content of 36%.

  Also, weigh a mixed solution of 220 parts by weight of methyltriisopropoxysilane and 150 parts by weight of toluene into a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer, and mix 108 parts of 1% aqueous hydrochloric acid with the above. Methyl triisopropoxysilane was hydrolyzed by adding dropwise to the solution in 20 minutes. Stirring was stopped 40 minutes after the dropping, the lower layer water / isopropyl alcohol mixed solution containing a small amount of hydrochloric acid separated into two layers was separated, and the remaining toluene resin solution hydrochloric acid was removed by washing with water. Toluene was removed under reduced pressure, and then diluted with isopropyl alcohol to prepare a B component which was a 40% isopropyl alcohol solution of silanol group-containing organopolysiloxane having an average molecular weight of about 2000.

  Further, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane was used as the C component.

  Then, 70 parts by weight of the component A, 30 parts by weight of the component B, and 1 part of the component C are mixed and stirred, spray-coated, and cured at 120 ° C. for 30 minutes to form an inorganic coating layer 7 having a thickness of 10 μm. did.

  Furthermore, “Fressera PS1000” manufactured by Matsushita Electric Works Co., Ltd. was used as an inorganic paint containing a photocatalyst, and this was spray-coated, followed by drying and curing at room temperature to form a photocatalyst layer 8 having a thickness of 0.4 μm.

(Example 2)
What added 0.5 weight part with respect to 100 weight part of surfactant ("3M Novec FC4432" by Sumitomo 3M Co., Ltd.) and isopropyl alcohol (IPA) with respect to the same base material 1 as Example 1. A surfactant treatment was applied by applying a wet coating amount of 30 g / m ^{2 by} spraying and drying at room temperature.

  The water contact angle on the surface of the substrate 1 thus subjected to hydrophilic treatment was measured and found to be 40 °.

  Subsequently, the pattern layer 2 was formed by inkjet coating, the clear layer 6 was formed, the inorganic coating layer 7 was formed, and the photocatalyst layer 8 was formed in the same manner as in Example 1.

(Example 3)
The same substrate 1 as in Example 1 was subjected to an alkoxysilane condensation coating as a hydrophilic treatment as follows.

  Diluted to 50 parts by weight of tetraethoxysilane, 50 parts by weight of tetraisopropoxysilane, and 100 parts by weight of isopropanol-dispersed organosilica sol (trade name “OSCAL1432”, manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content 30%) which is acidic colloidal silica As a solvent, 75 parts by weight of isopropanol was mixed, and further 100 parts by weight of water was added and stirred. The obtained liquid is heated in a constant temperature bath at 60 ° C. for 5 hours to adjust the weight average molecular weight (Mw) of the hydrolysis polycondensate, which is a reaction product, to 1500 to 1800, and the alcohol of the hydrolysis polycondensation product. A solution was obtained. An inorganic coating composition was obtained by further adding and mixing 1000 parts by weight of isopropanol as a diluent solvent to this solution. In this coating material, the total solid concentration with respect to the total amount of the coating material was 4.1%.

  The newly prepared inorganic coating composition was applied to the substrate 1 washed with acetone by spray coating, and the coating film was dried and cured at room temperature for 0.5 hour, and then baked at 150 ° C. for 1 hour. As a result, an alkoxysilane condensation coating having a thickness of 0.2 μm was formed.

  The water contact angle on the surface of the substrate 1 thus subjected to hydrophilic treatment was measured and found to be 20 °.

  Subsequently, the pattern layer 2 was formed by inkjet coating, the clear layer 6 was formed, the inorganic coating layer 7 was formed, and the photocatalyst layer 8 was formed in the same manner as in Example 1.

(Comparative Example 1)
An ink receiving layer was formed on the same substrate 1 as in Example 1. The ink receiving layer contains 70 parts by weight of an acrylic emulsion resin, 30 parts by weight of polyvinyl alcohol as a hygroscopic resin (ink absorbing polymer), and 100 parts by weight of titanium oxide as a white pigment (PWC = 50%). The forming composition was applied to form a film having a thickness of 30 μm.

  Subsequently, the pattern layer 2 was formed by inkjet coating, the clear layer 6 was formed, the inorganic coating layer 7 was formed, and the photocatalyst layer 8 was formed in the same manner as in Example 1.

(Comparative Example 2)
“Scotch Cal” manufactured by Sumitomo 3M Limited was attached as a cutting sheet to the same base material 1 as in Example 1 without any treatment.

(Adhesion evaluation)
The building materials obtained in Examples 1 to 3 and Comparative Examples 1 and 2 are subjected to an accelerated weather resistance test using a xenon weatherometer specified in JIS K5600 for 3000 hours, and then crossed in accordance with JIS K5600. A peeling test using a cellophane adhesive tape with a cut (1 mm width 5 × 5 cells) was performed.

  As a result, in Examples 1 to 3, the edges of the cut were smooth, and no peeling was observed in any square. In Comparative Example 1, all the cells were peeled off regardless of the cut. In Comparative Example 2, it was not necessary to perform a peeling test, and peeling occurred on the cutting sheet. Thus, while Examples 1 to 3 have excellent adhesion, Comparative Example 1 is inferior in adhesion due to the occurrence of cracks in the coating film and delamination from the substrate. It was.

(Appearance evaluation)
Moreover, about Examples 1-3 and Comparative Examples 1-2, the building material after performing the same accelerated weather resistance test at the time of the said adhesive evaluation was observed visually, and the external appearance was evaluated.

  As a result, in Examples 1 to 3, no change was observed in the appearance, and all of the appearances were good. In Comparative Example 1, although the crack was generated, the color deterioration of printing was not observed. In Comparative Example 2, the cutting sheet peeled off.

It is sectional drawing which shows an example of the building material obtained by this invention. It is a schematic side view which shows an example of an inkjet coating apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material 2 Pattern layer 3 Photocatalyst coating film 5 Alkoxysilane condensate coating 6 Clear layer 7 Inorganic coating layer 8 Photocatalyst layer

Claims (5)

The substrate surface is subjected to a hydrophilic treatment, and then a water-based ink is applied to form a pattern layer, and a clear layer, an inorganic paint layer, and a photocatalyst layer are sequentially laminated on the pattern layer. Building materials.   The building material according to claim 1, wherein the hydrophilic treatment is a treatment of forming a photocatalytic coating film on the surface of the base material.   The building material according to claim 1, wherein the hydrophilic treatment is a surface treatment with a surfactant.   The building material according to claim 1, wherein the hydrophilic treatment is a treatment in which an alkoxysilane condensate coating is applied to the surface of the substrate. The building material according to any one of claims 1 to 4 , wherein the base material has a visible light transmittance of 80% or more.

Images