JP6116045B2 - Painted building materials - Google Patents

Description

  The present invention relates to a painted building material that can be used as an exterior material such as an outer wall material or a corner member.

  Conventionally, a painted building material in which a pattern is formed on the surface of a base material by painting has been proposed. Moreover, in order to form a design pattern with high designability, it is performed by inkjet printing (for example, refer patent document 1). In this case, in order to improve the fixing property of the ink, a receiving layer is formed on the printing surface of the substrate, and ink jet printing is performed on the receiving layer.

JP 2010-234366 A

  However, if the ink penetrates too much into the receiving layer, the color developability of the ink may decrease.

  The present invention has been made in view of the above points, and an object of the present invention is to provide a painted building material in which the color developability of ink is unlikely to deteriorate.

The painted building material according to the present invention includes a ceramic base material, a receiving layer formed on the surface of the base material, a printed layer formed by ink jet printing on the surface of the receiving layer, and a surface side of the printed layer. A paint building material having a clear layer, an inorganic paint layer, and a functional paint layer,
The receiving layer is a cured coating material having a glass transition point after film formation of 40 to 80 ° C., a volatile component content of 9.0% or less, and crosslinked with a crosslinking agent,
The glass transition point is controlled by the amount of crosslinking agent added to the cured paint,
The content of the volatile component is controlled by the drying conditions of the receiving layer .

  In the present invention, the cross-linking agent is preferably at least one selected from the group consisting of oxazoline, aziridine, carbodiimide, isocyanate, metal chelate, and metal alkoxide.

In the present invention, the printing layer is formed of an ultraviolet curable ink, and the curing condition of the ultraviolet curable ink is an irradiation time of an ultraviolet ray having a wavelength of 300 to 390 nm and an illuminance of 0.2 to 2.0 W / cm ^2. It is preferably 0.05 to 5.00 seconds.

  In the present invention, by having the receiving layer as described above, it is difficult for the ink forming the printing layer to penetrate into the receiving layer, and the color developability of the ink does not easily decrease.

It is a schematic sectional drawing which shows an example of embodiment of this invention.

  Hereinafter, modes for carrying out the present invention will be described.

  The painted building material of the present embodiment includes a base material 1, a receiving layer 2, and a printed layer 3, and further includes a clear layer 4, an inorganic paint layer 5, and a functional paint layer 6.

  As the base material 1, a ceramic base material mainly composed of cement can be used. An undercoat layer 1 a is provided on the decorative surface (surface to be painted) of the substrate 1. The undercoat layer 1a improves the concealing property of the substrate 1, and can be formed by applying a known sealer paint.

  The receiving layer 2 is formed by laminating on the surface of the undercoat layer (decorative surface) 1a of the substrate 1. The receiving layer 2 is provided in order to improve the ink fixing property and color developing property of the printing layer 3. The receiving layer 2 can be formed by applying a coating for the receiving layer.

  The printing layer 3 is formed by being laminated on the surface of the receiving layer 2. The printed layer 3 is provided in order to improve the design by making up the painted building material with the pattern. The printing layer 3 can be formed by painting with an inkjet printer (inkjet printer). The print layer 3 can be formed of a cured product such as a water-based ink, an oil-based ink, or an ultraviolet curable ink.

  The clear layer 4 is formed by being laminated on the surface of the printing layer 3. The clear layer 4 is provided to cover and protect the surface of the printing layer 3. The clear layer 4 can be formed by applying a known clear paint.

  The inorganic paint layer 5 is formed by being laminated on the surface of the clear layer 4. The inorganic paint layer 5 is provided to improve the durability of the printing layer 3. The inorganic paint layer 5 can be formed by painting a known inorganic paint.

  The functional paint layer 6 is formed by being laminated on the surface of the inorganic paint layer 5. The functional paint layer 6 is provided to impart a hydrophilic function, a water repellent function, a photocatalytic function, a heat ray reflecting function, and the like to the outermost surface of the painted building material. The functional paint layer 6 can be formed by applying a known functional paint.

  In this Embodiment, the receiving layer 2 expresses the solvent resistance with respect to the organic solvent. Here, “solvent resistance” refers to the property that the organic solvent contained in the ink applied by ink jet printing does not easily penetrate into the receiving layer 2. Therefore, the receiving layer 2 is formed to a level that exhibits solvent resistance to the organic solvent. Examples of the index representing the film forming property (film forming level) of the receiving layer 2 include the glass transition point (Tg) or the content of volatile components.

  The glass transition point of the receiving layer 2 can indirectly grasp the film forming property of the receiving layer 2 when a high amount of heat is applied after the coating for the receiving layer is baked and cured under predetermined drying conditions. It is. The glass transition point of the receiving layer 2 can be measured by differential scanning calorimetry (DSC) after forming the receiving layer 2 from the coating for the receiving layer. Specifically, the glass transition point of the receiving layer 2 is measured by sealing a coating film cured and dried by a predetermined method in an Al cell after weighing a predetermined amount, and starting from −50 at a rate of 10 ° C./min in air. Heat to + 150 ° C. Tg can be determined by reading the endothermic change (step-like baseline shift) at that time.

  And in this Embodiment, the glass transition point of the receiving layer 2 after film forming is 40-80 degreeC. Within this range, the receiving layer 2 has high solvent resistance, and when the ink for forming the printing layer 3 is applied to the receiving layer 2, the organic solvent contained in the ink is received by the receiving layer 2. And the volatilization of the resin component contained in the ink can be reduced. Accordingly, the color developability of the ink coated on the receiving layer 2 is difficult to be lowered, and the color developability of the print layer 3 is easily exhibited to the maximum extent. If the glass transition point of the receiving layer 2 after film formation is lower than 40 ° C., the ink permeability may be increased due to softening due to the atmospheric temperature, and as a result, the color developability may be deteriorated. When the glass transition point of the receiving layer 2 after film formation exceeds 80 ° C., the color development of the ink is improved. However, the accelerated weather resistance test using a sunshine weatherometer or the like can withstand the stress of the base material and upper layer lower layer coating film stretching. There is a possibility that cracks are easily generated in the receiving layer 2 without being cut. As a result, the durability may be poor, and the high durability due to the inorganic coating and the high functionality due to the functional coating may be greatly impaired.

The content of the volatile component of the receiving layer 2 is determined by the ratio of the volatile component of the receiving layer coating remaining in the receiving layer 2 after the receiving layer coating is baked and cured under predetermined drying conditions. Can be grasped indirectly. This volatile component is measured by forming a coating film on a commercially available fluororesin tape by a predetermined coating method, and drying and curing it under predetermined baking and curing conditions. Thereafter, only the dried coating film formed on the fluororesin is peeled off and collected in a heat-resistant case (such as a glass bottle), and the initial coating film weight is measured (A). Then, after heating at 130 ° C. for 24 hours to volatilize volatile components, the weight of the coating film after drying is measured (B).
Volatile component C (%) = (A−B) / A * 100 (%)
And in this Embodiment, the content rate of the volatile component of the receiving layer 2 after film forming is 9.0% or less. Within this range, the receiving layer 2 has high solvent resistance, and when the ink for forming the printing layer 3 is applied to the receiving layer 2, the organic solvent contained in the ink is received by the receiving layer 2. And the volatilization of the resin component contained in the ink can be reduced. Accordingly, the color developability of the ink coated on the receiving layer 2 is difficult to be lowered, and the color developability of the print layer 3 is easily exhibited to the maximum extent. In addition, since it is preferable that the ratio of the volatile component remaining in the receiving layer 2 is small, the lower limit of the content of the volatile component in the receiving layer 2 is 0%.

  In the present embodiment, at least one of the glass transition point of the receiving layer 2 and the content of volatile components in the receiving layer 2, which is an index representing the film forming property of the receiving layer 2, is set to the predetermined condition. Is preferred. In order to set the index representing the film-forming property of the receiving layer 2 to the above predetermined condition, it is preferable to control the crosslinking in the film-forming process of the receiving layer 2. Specifically, it is the easiest method to control by the addition amount of a crosslinking agent that reacts with a functional group such as a carboxyl group or a hydroxyl group. For example, the compounding quantity of the crosslinking agent in 100 parts of coating materials for receiving layers can be 0.01-10 parts. As described above, the glass transition point of the receiving layer 2 can be controlled to be increased or decreased as the amount of the crosslinking agent added is increased or decreased.

  In the present embodiment, the coating for the receiving layer is prepared containing a resin component and a crosslinking agent. As this resin component, acrylic resin (acrylic resin, acrylic styrene resin, acrylic silicon resin, etc.) can be used.

  As the crosslinking agent, oxazoline and derivatives thereof, aziridine and derivatives thereof, carbodiimide compounds, isocyanate compounds, metal chelates, and metal alkoxides are preferably used. These cross-linking agents react with the functional groups of the resin in a short time at room temperature or higher. Therefore, it is possible to easily promote the crosslinking of the resin component simply by adding at the time of production at the factory, and to promote an increase in Tg.

  Here, as derivatives of oxazoline, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like can be mentioned, and selected from these groups One kind or a mixture of two or more kinds can be used. Among them, 2-isopropenyl-2-oxazoline is preferable because it is easily available industrially.

  Further, as derivatives of aziridines, 2,2′-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], ethylene glycol-bis [3- (1-aziridinyl) propionate], polyethylene glycol-bis [3 -(1-aziridinyl) propionate], propylene glycol-bis [3- (1-aziridinyl) propionate], polypropylene glycol-bis [3- (1-aziridinyl) propionate], tetramethylene glycol-bis [3- (1- Aziridinyl) propionate], polytetramethylene glycol-bis [3- (1-aziridinyl) propionate] and the like. One or more of these can be used. Such a compound has high reactivity, can efficiently increase the degree of polymerization of the polyester, and can significantly reduce the terminal carboxyl group content by using a small proportion.

  Examples of the carbodiimide compound include aqueous dicyclohexylmethane carbodiimide and aqueous tetramethylxylylene carbodiimide. One or more of these can be used.

  As the isocyanate compound, a blocked isocyanate compound is preferable from the viewpoint of reactivity. The blocked isocyanate compound used as the crosslinking agent is a compound obtained by blocking an aliphatic and / or alicyclic isocyanate compound with a blocking agent. In the case where the isocyanate compound is an isocyanate compound other than aliphatic and / or alicyclic, for example, an aromatic isocyanate compound, it is not preferable because the weather resistance of the coating film is deteriorated. Examples of the aliphatic and / or alicyclic isocyanate compounds include aliphatic and alicyclic diisocyanate compounds such as isophorone diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, and methylene diisocyanate, or dimers and 3 amounts thereof. And an excess amount of these isocyanate compounds include terminal isocyanate-containing compounds obtained by reacting low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, trimethylolpropane, hexanetriol, and castor oil. On the other hand, the blocking agent is added and blocked to the isocyanate group of the isocyanate compound, and the blocked isocyanate compound produced by the addition is stable at room temperature and when heated from about 100 ° C to 200 ° C, It is desirable to be able to dissociate and regenerate isocyanate groups. Examples of the blocking agent satisfying such conditions include lactam compounds such as ε-caprolactam and γ-caprolactam; oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime; and aromatic alkyls such as phenyl carbinol and methyl phenyl carbinol. Examples of alcohols include ether alcohol compounds such as ethylene glycol monobutyl ether.

  As the metal chelate, diisopropoxybis (triethanolaminate) titanium, titanium lactate ammonium salt, or the like can be used. As the metal alkoxide, ethyl silicate, propyl silicate, or the like can be used.

  In the present embodiment, the receiving layer 2 is prepared by diluting a receiving layer coating containing a resin component and a crosslinking agent with an appropriate solvent, and then applying the receiving layer coating to the substrate 1 by any coating means such as spraying. It is applied to the surface of the undercoat layer 1a. Then, the receiving layer 2 can be formed (film formation) by drying and baking and curing the applied coating for the receiving layer. And in the baking hardening process of the apply | coated coating for receiving layers, the resin component in the coating for receiving layers is bridge | crosslinked with a crosslinking agent.

In the present embodiment, when a printing layer is formed using an ultraviolet curable ink, the curing condition of the ultraviolet curable ink is an ultraviolet ray having a wavelength of 300 to 390 nm and an illuminance of 0.2 to 2.0 W / cm. ² and the irradiation time is preferably 0.05 to 5.00 seconds. Under these conditions, the ultraviolet curable ink can be sufficiently cured, and the volatilization of the ink and the penetration of the solvent into the receiving layer 2 can be suppressed.

  Hereinafter, the present invention will be specifically described by way of examples.

(Examples 1-4)
As the base material, a plate-shaped ceramic base material (Neolock 16 mm) mainly composed of cement is used. An undercoat layer is formed on the decorative surface of the substrate.

  As the coating for the receiving layer, resin emulsion AD77 (resin content 48.0%, acrylic-styrene emulsion, manufactured by Henkel Technologies Japan Co., Ltd.) 100 parts by weight, film-forming aid Kyowanol M (2,2,4-trimethyl) 1,3-pentanediol monoisobutyrate (produced by Kyowa Hakko Chemical Co., Ltd.) 10 parts by weight, white pigment dispersion LIOFASTWHITE H201 (pigment content 60%, produced by Toyo Ink Co., Ltd.), 10 parts by weight of water The mixture was stirred for 10 minutes, filtered through 80 mesh, and 100 parts by weight of the filtered solution was mixed with 1 part of carbodiimide (Nisshinbo Chemical Co., Ltd. Carbodilite V02) as a crosslinking agent component.

  As ink, 3 parts by weight of blue pigment Blue P-BFS (CI Pigment Blue 15: 4 copper phthalocyanine, Clariant Japan Co., Ltd.), 3 weights of dispersant Disperbyk-168 (polymer compound, manufactured by BykChemie) Parts, reactive oligomer CN985B88 (aliphatic urethane acrylate, bifunctional, manufactured by Sartomer Co., Ltd.), 20 parts by weight, reactive monomer SR238F (1,6-hexanediol diacrylate, bifunctional, manufactured by Sartomer Co., Ltd.) 68.3 parts by weight, photopolymerization initiator Darocur 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one, manufactured by Ciba Specialty Chemicals), wetting agent DOW CORNING TORAY 32 ADDITIVE (silicone wetting agent, east Dow Corning Silicone Co.) 0.7 parts by weight was added and dispersed using a bead mill disperser, and remove impurities and filtered to produce a homogeneous blue UV ink.

  As the clear paint, a clear type of V Seran # 600 manufactured by Dainippon Paint Co., Ltd. was used.

  As the inorganic coating material, a mixture of 70 parts by weight of the following component (A), 30 parts by weight of component (B), and 1 part by weight of component (C) was used. Component (A) is 100 parts of methanol-dispersed colloidal silica sol MA-ST (particle size 10-20 mμ, solid content 30%, manufactured by Nissan Chemical Industries, Ltd.) in a flask equipped with a stirrer, a heating jacket, a condenser and a thermometer. It was obtained by adding 68 parts of methyltrimethoxysilane and 10.8 parts of water and cooling the mixture by carrying out a partial hydrolysis reaction at a temperature of 65 ° C. for about 5 hours while stirring. Component (B) was prepared by measuring a mixture of 209 parts of methyltriisopropoxysilane, 11 parts of phenyltrichlorosilane and 150 parts of toluene in a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer, 150 parts of the mixture was added dropwise over 20 minutes to hydrolyze methyltriisopropoxysilane. Stirring was stopped 40 minutes after dropping, and the lower layer water / isopropyl alcohol mixed solution separated into two layers was separated to obtain a remaining toluene solution of silanol group-containing organopolysiloxane. As the component (C), N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane was used.

  As a functional paint, after mixing 100 parts by weight of methyltrimethoxysilane with 10 parts by weight of tetraethoxysilane, 90 parts by weight of IPA organosilica sol, 30 parts by weight of dimethyldimethoxysilane, 100 parts by weight of isopropyl alcohol (IPA), 90 parts by weight of water was added and stirred. The weight average molecular weight Mw was adjusted to 1500 in a constant temperature bath at 60 ° C. Then, 20 parts by weight of titanium oxide was added to the prepared coating solution and stirred and dispersed to obtain a photocatalyst-containing silicone coating agent. At this time, a titanium oxide having an average particle size of 20 nm, having no exothermic peak in the range of 400 to 500 ° C. in DTA measurement, and high anatase crystallization was used. In addition, the titanium oxide is used in the form of a titanium oxide aqueous dispersion containing 5% by weight of an acrylic dispersant, and the titanium oxide aqueous dispersion is blended in the coating liquid so that the titanium oxide is dispersed in the coating liquid. did.

Then, a receiving layer coating is applied to the surface of the undercoat layer of the substrate, and a receiving layer having a thickness of 50 μm is formed so as to be baked and cured after drying. Next, a printing layer having a thickness of 10 μm is formed by printing ink on the surface of the receiving layer using an ink jet printer. The curing conditions for the ink are ultraviolet rays emitted from a metal halide lamp having a main wavelength of 365 nm and an irradiation time of 1.00 seconds at an illuminance of 2.0 W / cm ² . Next, a clear paint is applied to the surface of the print layer, and a clear layer having a thickness of 30 μm is formed so as to be baked and cured after drying. Next, an inorganic paint is applied to the surface of the clear layer, and an inorganic paint layer having a thickness of 5 μm is formed so as to be baked and cured after drying. Next, a functional coating is applied to the surface of the inorganic coating layer, and a functional coating layer having a thickness of 1 μm is formed so as to be baked and cured after drying. In this way, a painted building material was formed.

(Example 5)
A coated building material was formed in the same manner as in Example 1 except that 1 part by weight of isocyanate (Meikanate TP-10, manufactured by Meisei Chemical Co., Ltd.) was used as a crosslinking agent instead of carbodiimide.

(Example 6)
A coated building material was formed in the same manner as in Example 1 except that 1 part by weight of a metal chelate (Orgatechs TC300 (manufactured by Matsumoto Fine Chemical Co., Ltd.)) was used as a crosslinking agent instead of carbodiimide.

(Example 7)
A coated building material was formed in the same manner as in Example 1 except that 1 part by weight of oxazoline (Nippon Shokubai Co., Ltd. Epocros WS-700) was used as a crosslinking agent instead of carbodiimide.

(Example 8)
A coated building material is formed in the same manner as in Example 1 except that 1 part by weight of a metal alkoxide (a mixed solution of 90 parts by weight of N-propyl silicate (manufactured by Colcoat) and 10 parts by weight of IPA) is used as a crosslinking agent instead of carbodiimide. did.

Example 9
A painted building material was formed in the same manner as in Example 1 except that 1 part by weight of aziridine (Nippon Shokubai Co., Ltd. Chemite DZ22E) was used as a crosslinking agent instead of carbodiimide.

(Comparative Example 1)
A painted building material was formed in the same manner as in Example 1 except that the crosslinking agent was not used.

(Comparative Example 2)
A painted building material was formed in the same manner as in Example 9 except that the baking condition at the time of forming the receiving layer was 2 minutes.

  For this painted building material, the glass transition point of the receiving layer was measured. The glass transition point of the receiving layer was measured using a DSC220 model manufactured by Seiko Instruments. Also, the penetration of the ink into the receiving layer was evaluated. Evaluation of the penetration of the ink into the receiving layer was confirmed by observing the cross section of the coating film with a laser microscope (Keyence VK8700 / 8710) 2000 times to determine whether the ink / receiving layer interface had penetrated. Further, the color developability of the printed layer was evaluated. The color development of the print layer was evaluated by printing a solid 50% blue print image and measuring the image with a spectrocolorimeter SP64: X-Rite. The saturation C * was calculated from the measured a * and b * (C * = (a * ^ 2 + b * ^ 2) ^ 0.5). The larger C *, the better the color development and the higher the evaluation. The content of the volatile component in the receiving layer can be adjusted by changing the drying conditions. When the drying condition was 130 ° C. for 5 minutes, the volatile component content could be 5.0%. Increasing the time decreases the content of volatile components, and decreasing the time increases the content of volatile components. Using a sunshine carbon arc type weather resistance tester (SWOM), surface crack observation and carbon contamination test after 5000 hours of operation time (a test in which a 5% aqueous solution of carbon pigment was sprinkled and washed with water after 60 seconds) were performed. Durability and functionality were confirmed.

  The results are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 Base material 2 Receiving layer 3 Print layer 4 Clear layer 5 Inorganic coating layer 6 Functional coating layer

Claims (3)

A ceramic base material, a receiving layer formed on the surface of the base material, a printing layer formed by ink jet printing on the surface of the receiving layer, and a clear layer and an inorganic coating layer on the surface side of the printing layer A painted building material having a functional paint layer,
The receiving layer is a cured coating material having a glass transition point after film formation of 40 to 80 ° C., a volatile component content of 9.0% or less, and crosslinked with a crosslinking agent,
The glass transition point is controlled by the amount of crosslinking agent added to the cured paint,
The painted building material, wherein the content of the volatile component is controlled by the drying condition of the receiving layer . The painted building material according to claim 1, wherein the crosslinking agent is at least one selected from the group consisting of oxazoline, aziridine, carbodiimide, isocyanate, metal chelate, and metal alkoxide . The printing layer is formed of an ultraviolet curable ink, and the curing condition of the ultraviolet curable ink is an ultraviolet ray having a wavelength of 300 to 390 nm, an illuminance of 0.2 to 2.0 W / cm ² and an irradiation time of 0.05 to 5.00. The painted building material according to claim 1 or 2 , characterized in that it is a second .

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