JP7432445B2 - Gravure offset printing ink composition for building boards, gravure offset printing method, and building boards - Google Patents

Description

The present invention relates to a gravure offset printing ink composition for building boards, a gravure offset printing method, and a building board, which can be particularly suitably used for gravure offset printing of building boards.

In recent years, building boards used as exterior wall materials for buildings are also required to have a more sophisticated design, and in addition to traditional inkjet printing, gravure offset printing is also being used to decorate boards. There is. For example, Patent Documents 1 to 5 disclose building boards printed by gravure offset printing.

JP2003-276296A Japanese Patent Application Publication No. 2003-305820 Japanese Patent Application Publication No. 2003-312117 Japanese Patent Application Publication No. 2005-28783 Japanese Patent Application Publication No. 2005-60627

In gravure offset printing, ink is deposited and retained on the surface of a gravure plate cylinder, which has small concave depressions called cells formed in correspondence with the printed image, and after scraping off the ink with a doctor blade, only the image forming area is printed. A printing method in which the remaining ink is transferred to a blanket cylinder, which is then pressed against a substrate to be printed, and the ink is transferred to the substrate, and high-definition printed matter is mass-produced on a production line. This is a printing method that can be used. However, in the case of gravure offset printing, it is generally necessary or desirable for the surface to be printed to be smooth, and although it is possible to print well on paper, resin film, etc., the base material is usually hard. It is difficult to print well on building boards that are large, have uneven surfaces, and have poor surface smoothness. Particularly when performing continuous printing, if printing is carried out over a long period of time, the substrate to be printed is usually heated in the previous process or preheated in advance, so not only the substrate to be printed but also the gravure plate cylinder and The ink composition tends to dry even on the blanket cylinder, and the ink composition may remain on the gravure plate cylinder or the blanket cylinder, causing plate fogging. The amount of ink transferred to the printing substrate may decrease, resulting in a thinner printed image and reduced color development.Also, the gravure plate cylinder and blanket cylinder may not be sufficiently cleaned, and as a result, The quality of the printed image may deteriorate.

Therefore, the present invention provides a gravure offset printing ink composition for building boards, which can be successfully printed on building boards by gravure offset printing, and can also be stably and continuously printed, and a gravure offset printing method. The purpose is to Another object of the present invention is to provide a building board printed by gravure offset printing using this gravure offset printing ink composition for building boards.

The present invention relates to the following items.
[1] A water-based ink composition used for gravure offset printing of building boards, comprising:
(A) a colorant, (B) a water-dispersible resin, (C) water, and (D) a boiling point at 1 atm of 180°C or higher, and an SP value (solubility parameter) determined by the Hoy method. an organic solvent having a molecular weight of 10.5 or more;
(D) The content of the organic solvent having a boiling point of 180° C. or higher at 1 atm and an SP value of 10.5 or higher determined by the Hoy method is 3 to 20% by mass. , a gravure offset printing ink composition for building boards.
[2] The organic solvent (D) has a boiling point of 180° C. or higher at 1 atm and an SP value of 10.5 or higher determined by the Hoy method at a rate of 1% relative to the water-dispersible resin (B). The gravure offset printing ink composition for building boards according to item [1] above, characterized in that the minimum film forming temperature (MFT) lowering ability when added by mass % is 3° C. or less.
[3] The above (D) organic solvent having a boiling point of 180° C. or higher at 1 atmosphere and an SP value of 10.5 or higher determined by the Hoy method is a diol compound having 6 or less carbon atoms. The gravure offset printing ink composition for building boards according to item [1] or [2].
[4] Any one of the above items [1] to [3], wherein the water-dispersible resin (B) is obtained by carrying out a polymerization reaction in the presence of a reactive emulsifier. The gravure offset printing ink composition for building boards as described.
[5] The gravure offset printing ink composition for building boards according to any one of items [1] to [4] above, further comprising (E) a silicone-based surface conditioner.
[6] The gravure offset printing ink composition for building boards according to any one of items [1] to [5] above, which has a surface tension of 19 to 40 mN/m at 20°C.
[7] The gravure offset printing ink composition for building boards according to any one of items [1] to [6] above, which has a viscosity at 30° C. of 10 to 50 seconds using an Iwata cup viscometer. .
[8] Gravure, characterized in that printing is performed on a printing substrate by gravure offset printing using the gravure offset printing ink composition for building boards according to any one of the above items [1] to [7]. Offset printing method.
[9] The gravure offset printing method according to item [8], wherein the gravure plate cylinder and/or the blanket cylinder used in gravure offset printing is washed with water.
[10] The temperature of the printing substrate during printing is 40 to 70°C, and
The absolute value of the difference between the temperature of the printing substrate during printing and the MFT (minimum film forming temperature) of the water-dispersible resin (B) in the gravure offset printing ink composition for building boards is 15 The gravure offset printing method according to item [8] or [9] above, characterized in that the temperature is below ℃.
[11] A method of printing on a printing substrate by gravure offset printing using an ink composition containing at least (A) a colorant, (B) a water-dispersible resin, and (C) water, the method comprising: ,
The temperature of the printing substrate during printing is 40 to 70°C, and
The absolute value of the difference between the temperature of the printing substrate during printing and the MFT (minimum film forming temperature) of the water-dispersible resin (B) in the ink composition is 15 ° C. or less. Characteristic gravure offset printing method.
[12] A building board, comprising a base material and an ink layer formed from the gravure offset printing ink composition for building boards according to any one of items [1] to [7] above.
[13] The building board according to item [12], further comprising a colored layer between the base material and the ink layer.
[14] The building board according to item [12] or [13], further comprising a clear layer on the ink layer.
[15] The building board according to item [14], further comprising an overcoat layer on the clear layer.

According to the present invention, there is provided a gravure offset printing ink composition for building boards, which can be printed satisfactorily on building boards by gravure offset printing, and capable of stable continuous printing, and a gravure offset printing method. can do. Moreover, according to the present invention, it is possible to provide a building board printed by gravure offset printing using this gravure offset printing ink composition for building boards.

<Gravure offset printing ink composition for building boards>
The gravure offset printing ink composition for building boards of the present invention (hereinafter also simply referred to as "ink composition") is an aqueous ink composition used for gravure offset printing of building boards, comprising (A) a colorant; (B) a water-dispersible resin, (C) water, and (D) an organic material having a boiling point of 180°C or higher at 1 atm and an SP value (solubility parameter) determined by the Hoy method of 10.5 or higher. The content of the high-boiling organic solvent (D) is 3 to 20% by mass.

The gravure offset printing ink composition for building boards of the present invention contains, in addition to water as a solvent, (D) a boiling point at 1 atm of 180°C or higher, and an SP value (solubility parameter) determined by the Hoy method; Contains a high boiling point organic solvent having a boiling point of 10.5 or more in a range of 3 to 20% by mass. By containing such a high boiling point organic solvent (D) in the range of 3 to 20% by mass, gravure offset can be applied even to large, hard, uneven building boards with poor surface smoothness. Printing can be performed well, even if continuous printing is performed for a long period of time, the ink composition has excellent cleaning properties and can prevent the ink composition from remaining on the gravure plate cylinder or blanket cylinder, and Decrease in color development of printed images is less likely to occur, and high-quality printed images can be stably obtained. Therefore, by using the gravure offset printing ink composition for building boards of the present invention, it is possible to stably and continuously print on building boards by gravure offset printing.

The ink composition of the present invention contains (A) a colorant. (A) The colorant may be used alone or in combination of two or more.

(A) As the colorant, any known colorant can be used. (A) Colorants include, but are not particularly limited to, carbon black, yellow iron oxide, Bengara, ultramarine blue, nickel titanium yellow, bismuth yellow, cobalt blue, cobalt aluminum blue, and nickel-titanium complex oxide. , chromium/titanium complex oxide, bismuth/vanadium complex oxide, cobalt/aluminum complex oxide, cobalt/aluminum/chromium complex oxide, iron oxide, titanium oxide, zinc oxide, zinc sulfide, magnesium oxide, etc. inorganic pigments, quinacridone pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, isoindolinone pigments, anthrapyrimidine pigments, phthalocyanine pigments, threne pigments, dioxazine pigments, azo pigments, diazo pigments. Examples include organic pigments such as perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments, and quinophthalone pigments. From the viewpoint of weather resistance, etc., it is preferable to use inorganic pigments. The inorganic pigment may be surface-treated with a known treatment agent such as a silane coupling agent, a titanium coupling agent, or a higher fatty acid metal salt. Moreover, a dye can also be used as the coloring agent (A). Note that the hue is not particularly limited and can be appropriately selected as desired.

The content of the colorant (A) in the ink composition is not particularly limited and can be selected as appropriate, but it is usually preferably 1 to 30% by mass based on the total mass of the ink composition. , more preferably 5 to 25% by mass.

The ink composition of the present invention contains (B) a water-dispersible resin. By using a water-dispersible resin, the molecular weight of the resin can be increased easily and more hydrophobic components can be added (polymerized) than when using a water-soluble resin, so an ink layer with better properties can be created. can be formed. (B) The water-dispersible resins may be used alone or in combination of two or more.

Here, the water-dispersible resin means a resin that does not substantially dissolve in water at 25°C (for example, solubility is 50% by mass or less) and exists in a dispersed state in water.

Examples of the water-dispersible resin (B) that can be used in the present invention include acrylic resins (including copolymer resins such as acrylic styrene resins, acrylic urethane resins, acrylic silicone resins, acrylic alkyd resins, and acrylic SBR resins). , silicone resin, polyester resin, polyurethane resin, fluororesin, phenol resin, melamine resin, alkyd resin, vinyl chloride resin, SBR resin, polyolefin resin, amino resin, amide resin, epoxy resin and the like.

Since the ink composition of the present invention is used for building boards, the water-dispersible resin (B) is preferably an acrylic resin, a urethane resin, a silicone resin, or a fluororesin, and more preferably an acrylic resin.

Note that the acrylic resin herein refers to a resin whose constitutional unit is one or more monomers having a (meth)acryloyl group, such as (meth)acrylic acid and (meth)acrylic acid ester, and other monomers. It may be contained as a structural unit. (Meth)acrylic acid means acrylic acid or methacrylic acid, and (meth)acryloyl group refers to acryloyl group [CH ₂ =CH-COO-] or methacryloyl group [CH ₂ =C(CH ₃ )-COO -] means.

Preferred acrylic monomers include, but are not limited to, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, sec-butyl acrylate, and t-butyl acrylate. , 2-ethylhexyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate , 2-butoxyethyl acrylate, 2-phenoxyethyl acrylate, ethyl carbitol acrylate, allyl acrylate, glycidyl acrylate, dimethylaminoethyl acrylate, sodium acrylate, trimethylolpropane acrylate, 1,4-butanediol diacrylate, 1,6 - Acrylic acid ester monomers such as hexanediol diacrylate, neopentyl glycol diacrylate, and pentaerythritol triacrylate, as well as methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, Tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, propyl methacrylate, benzyl methacrylate, isopropyl methacrylate, sec-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, allyl methacrylate, ethylene glycol methacrylate , methacrylic acid ester monomers such as triethylene glycol methacrylate, tetraethylene glycol methacrylate, 1,3-butylene glycol methacrylate, trimethylolpropane methacrylate, 2-ethoxyethyl methacrylate, 2-methoxyethyl methacrylate, acrylic acid, methacrylic acid, itacon acid, crotonic acid, maleic acid, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, etc. . Furthermore, in addition to the above acrylic monomers, α,β-ethylenic monomers having a carbonyl group such as acrolein, diacetone acrylamide, diacetone methacrylamide, formylstyrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc. Saturated monomers and vinyl monomers such as acrylamide, acrylonitrile, vinyl acetate, styrene, ethylene, propylene, isobutylene, butadiene, isoprene, and chloroprene can also be used as copolymerization components.

The number average molecular weight of the water-dispersible resin (B) used in the present invention is not particularly limited, but is usually preferably 100,000 or more, more preferably 150,000 or more. Here, the number average molecular weight is a number average molecular weight in terms of standard polystyrene measured by GPC method (gel permeation chromatography).

The method for producing (B) water-dispersible resin such as acrylic resin is not particularly limited, and may be produced by any known method, such as emulsion polymerization, forced emulsion polymerization, suspension polymerization, solution polymerization, The water-dispersible resin (B) can be produced by known methods such as bulk polymerization and miniemulsion polymerization.

As a method for producing the water-dispersible resin (B) used in the present invention, emulsion polymerization is usually preferred because a high molecular weight resin can be easily obtained. That is, as the water-dispersible resin (B) used in the present invention, emulsion resins are usually preferred. Emulsion resins also tend to have excellent dispersion stability of resin particles in water. Note that the emulsion (resin dispersion) containing the water-dispersible resin (B) obtained by emulsion polymerization can be used as it is for producing the ink composition of the present invention.

The water-dispersible resin (B) used in the present invention may be particularly preferably one obtained by carrying out a polymerization reaction in the presence of a reactive emulsifier (reactive surfactant). By using a reactive emulsifier, the dispersion stability of the resin particles in water can be further improved, and as a result, the stability of the ink composition can be further improved. In addition, the ink layer containing the water-dispersible resin (B) obtained by carrying out a polymerization reaction using a reactive emulsifier is weather-resistant even in the environment where building boards are used outdoors, where they are sometimes exposed to wind and rain. They tend to have better properties, water resistance, and hot water resistance.

Note that a reactive emulsifier is an emulsifier that has a polymerizable unsaturated bond such as a vinyl group in its molecule, and it not only has an emulsifying function but also has a polymerizable unsaturated bond such as a vinyl group in its molecule. It is also a polymerizable monomer with bonds and hydrophilic groups. At least a portion of the reactive emulsifier is incorporated into the water-dispersible resin (B) as a component of the polymer during the polymerization process.

In the present invention, it is preferable to use an anionic reactive emulsifier or a nonionic reactive emulsifier as the reactive emulsifier. An anionic reactive emulsifier and a nonionic reactive emulsifier can also be used together.

Examples of anionic reactive emulsifiers include alkyl ether type (commercially available products include Aqualon KH-05, KH-10, and KH-20 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and Adekaria Soap manufactured by ADEKA Co., Ltd.). SR-10, SR-10N, SR-20N, Latemul PD-104 manufactured by Kao Corporation), sulfosuccinic acid ester type (commercially available products include Latemul S-120, S-120A manufactured by Kao Corporation, S-180P, S-180A, Eleminol JS-2 manufactured by Sanyo Kasei Co., Ltd.), alkyl phenyl ether type or alkyl phenyl ester type (commercially available products include, for example, Aqualon H-2855A manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) , H-3855B, H-3855C, H-3856, HS-05, HS-10, HS-20, HS-30, Adekaria Soap SDX-222, SDX-223, SDX-232, SDX manufactured by ADEKA Co., Ltd. -233, SDX-259, SE-10N, SE-20N, etc.), (meth)acrylate sulfate type (commercially available products include Antox MS-60, MS-2N, manufactured by Nippon Nyukazai Co., Ltd., Sanyo Chemical Eleminol RS-30 manufactured by Kogyo Co., Ltd.), phosphate ester type (commercially available products include H-3330PL manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adekaria Soap PP-70 manufactured by ADEKA Co., Ltd.), etc. can be mentioned.

Nonionic reactive emulsifiers include, for example, alkyl ether type (commercially available products include Adekaria Soap ER-10, ER-20, ER-30, ER-40 manufactured by ADEKA Co., Ltd., and ER-40 manufactured by Kao Corporation). Latemul PD-420, PD-430, PD-450, etc.), alkylphenyl ether type or alkylphenyl ester type (commercially available products include Aqualon RN-10, RN-20, RN manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) -30, RN-50, Adekaria Soap NE-10, NE-20, NE-30, NE-40, etc. manufactured by ADEKA Co., Ltd.), (meth)acrylate sulfate ester type (commercially available products include, for example, Nippon Nyukaza) RMA-564, RMA-568, RMA-1114, etc. manufactured by Co., Ltd.).

The conditions for producing the water-dispersible resin (B) (polymerization conditions) are not particularly limited and can be appropriately selected according to known methods.

The content of the water-dispersible resin (B) in the ink composition is not particularly limited and can be selected as appropriate, but is usually 1 to 50% by mass based on the total mass of the ink composition. The content is preferably 10 to 30% by mass, and more preferably 10 to 30% by mass.

The content ratio of (A) colorant and (B) water-dispersible resin contained in the ink composition is not particularly limited, but is usually 1:0.5 to 1:50 in mass ratio. The ratio is preferably 1:1 to 1:30, more preferably 1:1 to 1:30.

The ink composition of the present invention is an environmentally preferable aqueous ink composition, and contains (C) water as a solvent (dispersion medium).

The content of (C) water in the ink composition is not particularly limited and can be selected as appropriate, but it is usually preferably 30 to 70% by mass based on the total mass of the ink composition.

The ink composition of the present invention further uses (D) an organic solvent (high boiling point organic solvent). (D) The high boiling point organic solvent may be used alone or in combination of two or more.

(D) The boiling point of the high boiling point organic solvent at 1 atm is 180°C or higher, preferably 180°C to 280°C, more preferably 190°C to 260°C. When the boiling point of the organic solvent contained is high, specifically, when the boiling point at 1 atm is 180°C or higher, the ink composition becomes difficult to dry, and as a result, the ink composition has poor scrapability and washability. Therefore, it is possible to suppress the ink composition from remaining on the gravure plate cylinder or blanket cylinder during gravure offset printing. Furthermore, even if continuous printing is performed over a long period of time, plate fogging and deterioration in color development of printed images are unlikely to occur, and high-quality printed images can be stably obtained. On the other hand, the upper limit of the boiling point of the organic solvent is not particularly limited, but is usually preferably 280° C. or lower. If the boiling point of the organic solvent is too high, the ink composition will be difficult to dry excessively, and the organic solvent will tend to remain in the formed coating film, and if a surface protective layer such as a clear layer is formed on it, the laminated film will Physical properties such as adhesion and weather resistance may deteriorate. Further, it is not preferable to lengthen the drying time of the ink composition because it increases the manufacturing cost.

(D) The SP value (solubility parameter) of the high boiling point organic solvent determined by the Hoy method is 10.5 or more, preferably 10.5 to 18, more preferably 11 to 18, 11 More preferably, it is between .5 and 18. When the SP value of the organic solvent contained is close to that of (B) water-dispersible resin, the organic solvent easily swells or dissolves the resin and functions as a film-forming aid, resulting in the ink composition being absorbed into the gravure plate cylinder during gravure offset printing. A film is formed and hardened on the blanket cylinder, which not only reduces cleaning performance but also leads to a decrease in the color development of printed images and deterioration of printed images. Generally, the SP value of the water-dispersible resin (B) is 10.2 or less, for example 8.0 to 10.2, and if the SP value of the organic solvent is 10.5 or more, the organic solvent may be present in the ink composition. It is difficult to swell or dissolve water-dispersible resins used in products, and it suppresses the film formation and hardening of the ink composition on the gravure plate cylinder and blanket cylinder during gravure offset printing. Decrease in color development and deterioration of printed images can be suppressed. On the other hand, the upper limit of the SP value of the organic solvent is not particularly limited, but is usually preferably 18 or less. When the SP value of the organic solvent exceeds 18, the compatibility with the water-dispersible resin deteriorates, and the dispersion stability of the ink composition decreases during the printing or drying process, resulting in poor drying and poor image quality. may decrease.

In the present invention, the SP value (solubility parameter) means the SP value determined by the Hoy method, and is described in the literature [K. L. Hoy, J. Paint Technology, 42, [541], 76 (1970)].

In the present invention, the content of the high boiling point organic solvent (D) as described above is also important. The content of the high boiling point organic solvent (D) in the ink composition is 3 to 20% by mass, preferably 4 to 17% by mass, and 5 to 15% by mass, based on the total mass of the ink composition. % is more preferable. (D) If the content of the high boiling point organic solvent is less than 3% by mass, sufficient cleaning performance cannot be obtained, and the decrease in color development of printed images and the deterioration of printed images cannot be sufficiently suppressed. . On the other hand, if the content of (D) high-boiling organic solvent exceeds 20% by mass, the organic solvent tends to remain in the formed coating film, and if a surface protective layer such as a clear layer is formed on it, the lamination Physical properties such as film adhesion and weather resistance deteriorate.

In the present invention, by keeping the boiling point and SP value of the high-boiling organic solvent (D) used, as well as the content thereof, all within the above ranges, it is possible to print well even on building boards by gravure offset printing. It becomes possible to obtain a gravure offset printing ink composition for building boards that can be stably and continuously printed.

The high boiling point organic solvent (D) used in the present invention is preferably one that does not significantly lower the minimum film forming temperature (MFT) of the water-dispersible resin (B). Specifically, it is preferable that (D) the high boiling point organic solvent has a minimum film forming temperature (MFT) lowering ability of 3° C. or less when 1% by mass is added to (B) the water-dispersible resin; It is more preferable that the temperature is below ℃. Here, the minimum film forming temperature (MFT) lowering ability of the high boiling point organic solvent (D) when 1% by mass is added to the water-dispersible resin (B) is determined by the following method.

<How to determine the minimum film forming temperature (MFT)>
The minimum film forming temperature (MFT) is determined according to JIS K 6828-2:2003. Apply the sample uniformly to a thickness of 0.2 mm, dry the sample by flowing dry air at room temperature to form a film, and determine the boundary position of the part where a uniform film with no cracks is formed. is visually confirmed, and the temperature is determined to be MFT.
<How to determine minimum film forming temperature (MFT) lowering ability>
First, an emulsion in which the solvent (dispersion medium) is water and the content (solid content) of (B) water-dispersible resin is 40% by mass (provided that the water-dispersible resin (B) is The MFT is determined as described above for the emulsifier (surfactant), polymerization initiator, etc.), and is defined as the MFT of (B) the water-dispersible resin.
Next, in the emulsion used to determine the MFT of (B) water-dispersible resin, the content of (D) organic solvent is equivalent to 1/100 (mass ratio) of the content of (B) water-dispersible resin. For an emulsion prepared by adding and mixing (D) an organic solvent [an emulsion in which 1% by mass of (D) an organic solvent is added to (B) water-dispersible resin], (D) MFT when 1% by mass of organic solvent is added.
Then, the difference between the MFT of (B) the water-dispersible resin and the MFT when 1% by mass of the (D) organic solvent is added is calculated by 1% by mass of the (D) organic solvent with respect to the (B) water-dispersible resin. It is defined as the MFT decreasing ability upon addition.
However, if the MFT reduction ability when 1% by mass of organic solvent is added is low and cannot be measured satisfactorily, the MFT reduction ability when 5% or 10% by mass of organic solvent is added to the water-dispersible resin is measured. The MFT reduction ability when 1% by mass of organic solvent was added was calculated by dividing it by the amount of organic solvent added.

Examples of the high-boiling organic solvent (D) that can be used in the present invention include ethylene glycol (1,2-ethanediol) (boiling point at 1 atm: 197.3°C; SP value: 17.19), propylene glycol (1,2-propanediol) (boiling point at 1 atm: 188.2°C; SP value: 14.9), 1,3-propylene glycol (1,3-propanediol) (boiling point at 1 atm: 214.4 °C; SP value: 15.31), 1,3-butanediol (boiling point at 1 atmosphere: 204 °C; SP value: 13.8), 1,4-butanediol (boiling point at 1 atmosphere: 230 °C; SP value : 14.15), diethylene glycol (boiling point at 1 atm: 245°C; SP value: 14.45), diethylene glycol monobutyl ether (boiling point at 1 atm: 230.6°C; SP value: 10.88), triethylene glycol ( Boiling point at 1 atm: 287.4°C; SP value: 13.31), triethylene glycol monobutyl ether (boiling point at 1 atm: 271.2°C; SP value: 10.8).

Among the high-boiling organic solvents (D), diol compounds having 6 or less carbon atoms, more preferably 4 or less carbon atoms are preferred. As the diol compound, compounds containing -O- such as diethylene glycol and triethylene glycol are also preferable, but alkanediols are more preferable. As the high-boiling organic solvent (D), particularly preferred are glycerol, 1,3-propanediol, 1,3-butanediol, and 1,4-butanediol.

The ink composition of the present invention may contain (D) an organic solvent other than a high boiling point organic solvent, that is, a boiling point at 1 atm of less than 180°C or an SP determined by the Hoy method, to the extent that the effects of the present invention are not impaired. It is also possible to further include an organic solvent having a value (solubility parameter) of less than 10.5. (D) Organic solvents other than the high boiling point organic solvent may be used alone or in combination of two or more.

The content of organic solvents other than (D) high-boiling organic solvent in the ink composition is usually preferably 80% by mass or less based on the mass of (D) high-boiling organic solvent; It is preferably 45% by mass or less, more preferably 40% by mass or less, based on the total mass of organic solvents contained in the product.

It is preferable that the ink composition of the present invention further includes (E) a silicone-based surface conditioner. Addition of a silicone surface conditioner may further improve cleaning performance. (E) The silicone surface conditioner may be used alone or in combination of two or more.

The silicone surface conditioner (E) that can be used in the present invention is not particularly limited, but examples include organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylalkylpolysiloxane, and modified organopolysiloxanes. For example, polyether-modified polysiloxanes such as polyether-modified dimethylpolysiloxane, polyester-modified polysiloxanes such as polyester-modified dimethylpolysiloxane, polyester-modified methylalkylpolysiloxane, and aralkyl-modified polysiloxanes such as aralkyl-modified methylalkylpolysiloxane. Examples include polysiloxane. Also included are dimethylpolysiloxane alkylene oxide and the like.

(E) Commercially available silicone surface conditioners can also be used. Commercially available products include, for example, DC11PA, ST80PA, DC3074, DC3037, SR2402 manufactured by Dow Corning Toray; KP-321, KP-324, KP-327, KR-9218, X-40- manufactured by Shin-Etsu Chemical Co., Ltd. 9220; manufactured by Toshiba Silicone Corporation TSR165, , BYK-323, BYK-300, BYK-302, BYK-330, BYK-333, BYK-335, BYK-370, BYK-SILCLEAN3700; DISPARLON1711, 1751N, 1761, LS-001, LS- manufactured by Kusumoto Kasei Co., Ltd. 050; Examples include Polyflow KL-400HF, KL-401, KL-402, KL-403, and KL-404 manufactured by Kyoeisha Kagaku Co., Ltd. Shin-Etsu Chemical Co., Ltd. KF-6011, KF-6012, KF-6013, KF-6015, KF-6016, KF-6017, KF-6028, KF-6038, KF-6043; TEGO WET240 manufactured by Evonik Japan Co., Ltd. TEGO WET270 etc. are also mentioned.

The weight average molecular weight of the silicone surface conditioner (E) used in the present invention is not particularly limited, but is usually preferably from 1,000 to 120,000, more preferably from 8,000 to 15,000. preferable. Here, the weight average molecular weight is a weight average molecular weight in terms of standard polystyrene measured by GPC method (gel permeation chromatography).

The content of the (E) silicone surface conditioner in the ink composition is not particularly limited and can be selected as appropriate, but is usually 0.1 to 10% by mass based on the total mass of the ink composition. It is preferably 1 to 5% by mass, and more preferably 1 to 5% by mass.

In addition to or in place of (E) the silicone-based surface conditioner, the ink composition of the present invention may contain other surface conditioners, such as acrylic surface conditioners, silicone, etc. It may also contain a modified acrylic surface conditioner, a fluorine surface conditioner, a vinyl surface conditioner, and the like.

The ink composition of the present invention may contain various other additives, such as viscosity modifiers, antifoaming agents, dispersants, surfactants, antioxidants, light stabilizers, ultraviolet absorbers, and preservatives, as necessary. , antibacterial agents, algaecides, fungicides, rodent repellents, slip agents, metal pigments, pearl pigments, extender pigments, and the like.

The ink composition of the present invention can be prepared by stirring and mixing each component until uniform by a known method.

Although the ink composition of the present invention is not particularly limited, the surface tension at 20° C. is preferably 19 to 40 mN/m, more preferably 25 to 35 mN/m. Note that details of the method for measuring the surface tension of the ink composition will be explained in Examples below.

Although the ink composition of the present invention is not particularly limited, the viscosity at 30° C. is preferably 10 to 50 seconds, more preferably 15 to 40 seconds, as measured by an Iwata cup viscometer. Note that details of the method for measuring the viscosity of the ink composition will be explained in Examples below.

<Gravure offset printing method>
The gravure offset printing method of the present invention is to print on a printing substrate by gravure offset printing using the ink composition of the present invention (gravure offset printing ink composition for building boards) as described above.

Gravure offset printing can be performed by a conventional method. Printing conditions are also not particularly limited and can be selected as appropriate.

In the present invention, it is preferable that the gravure plate cylinder and/or blanket cylinder used in gravure offset printing be washed with water.

Further, in the present invention, the temperature of the printing substrate during printing is 40 to 70°C, and the temperature of the printing substrate during printing and (B) in the ink composition are It is preferable that the absolute value of the difference from the MFT (minimum film forming temperature) of the water-dispersible resin is 15° C. or less. It is more preferable that the absolute value of the difference between the temperature of the printing substrate during printing and the MFT (minimum film forming temperature) of the water-dispersible resin (B) in the ink composition is less than 13°C. , it is particularly preferable that the temperature is 10°C or less. If the temperature of the printing substrate during printing is more than 15°C higher than the MFT (minimum film forming temperature) of the water-dispersible resin (B) in the ink composition, the ink composition will easily dry. As a result, the cleaning performance is reduced, and the color development of the printed image is likely to be reduced and the printed image is likely to be deteriorated. On the other hand, if the temperature of the printing substrate during printing is more than 15°C lower than the MFT (minimum film forming temperature) of the water-dispersible resin (B) in the ink composition, the ink layer can be formed well. This may cause fine defects within the layer, resulting in a decline in physical properties such as weather resistance. Note that here, the temperature of the substrate to be printed upon printing means the surface temperature of the substrate to be printed.

Even when using an ink composition other than the ink composition of the present invention, the temperature of the printing substrate during printing is 40 to 70°C, and the temperature of the printing substrate during printing is The absolute value of the difference between the temperature and the MFT (minimum film forming temperature) of the water-dispersible resin in the ink composition is preferably 15° C. or less. The gravure offset printing method according to the second embodiment of the present invention uses an ink composition containing at least (A) a colorant, (B) a water-dispersible resin, and (C) water, and uses a gravure offset printing method to print on a printed material. A method of printing on a substrate, the temperature of the substrate to be printed at the time of printing is 40 to 70 ° C., and the temperature of the substrate to be printed at the time of printing and the ink composition. (B) The absolute value of the difference from the MFT (minimum film forming temperature) of the water-dispersible resin is 15° C. or less.

In the present invention, the substrate to be printed is a building board. The substrate to be printed may be only the building board (building board base material), but as described below, one or more layers are usually formed on the building board base material. Those listed above are preferably used.

<Architectural board>
The building board of the present invention has a base material (building board base material) and an ink layer formed from the ink composition of the present invention (gravure offset printing ink composition for building boards) as described above. . The building board of the present invention may further have one or more colored layers between the base material and the ink layer, and may further have one or more clear layers on the ink layer. It may also have one or more overcoat layers on the clear layer. Furthermore, in the building board of the present invention, a solvent-based or water-based sealer may be applied to the building board base material to impregnate it before forming the ink layer, colored layer, or the like.

The building board base material used in the present invention is not particularly limited, and can be appropriately selected depending on the application and the like. Examples of building board base materials include ceramic siding boards, flexible boards, calcium silicate boards, gypsum slag barlite boards, wood chip cement boards, asbestos cement boards, pulp cement boards, wood fiber reinforced cement boards, fiber reinforced cement boards, Fiber-reinforced cement/calcium silicate board, slate board, precast concrete board, lightweight aerated concrete (ALC) board, ceramic building board such as gypsum board, aluminum, aluminum alloy, iron, iron alloy, magnesium alloy, stainless steel, galvanized Examples include metal building boards such as steel and tin-plated steel, and wooden building boards. The metal building board may be subjected to surface treatment, such as oxidation treatment, and the building board base material may be subjected to cutting, polishing, etc., as necessary. good. Among these, the present invention can be particularly suitably applied to ceramic building boards. Note that the shape of the building board base material is usually plate-like, but is not particularly limited and can be appropriately selected depending on the purpose and the like.

The building board base material may be subjected to a primer treatment or the like, if necessary.

In particular, in the case of ceramic building boards, it is usually preferable to apply and impregnate the board with a sealer. The sealer is not particularly limited, and any known sealer may be used, and may be in either an organic solvent-based or water-based form, and may be appropriately selected and used as desired. Inorganic sealers can also be used. The amount of sealer applied is also not particularly limited and can be selected as appropriate.

The sealer can be applied by a known method, for example, a spray method, a roll coating method, a dipping method, a screen printing method, a brush coating method, or the like. After applying a sealer to a building board base material (ceramic building board), the base material is usually dried. The drying method and drying conditions are also not particularly limited and can be selected as appropriate.

After optional application and impregnation of a sealer, it is usually preferred to form one or more colored layers over the building board substrate.

The colored layer usually contains at least a colorant and a resin.

The colorant contained in the colored layer is not particularly limited, and any known colorant can be used. Examples of the coloring agent contained in the colored layer include those similar to the coloring agent (A) contained in the ink composition of the present invention described above. One type of colorant may be used alone, or two or more types may be used in combination.

The hue of the colored layer is not particularly limited, and can be appropriately selected as desired. The ink layer and the colored layer formed from the ink composition of the present invention may have similar colors or may have non-similar colors (colors that are not similar colors). When two or more colored layers are formed, they may be of similar colors or may be of non-similar colors.

The resin contained in the colored layer is not particularly limited, and any resin commonly used as a binder resin for the undercoat layer (base layer) or ink-receiving layer of building boards can be used. Examples of the resin contained in the colored layer include acrylic resin (including copolymer resins such as acrylic styrene resin, acrylic urethane resin, and acrylic silicone resin), silicone resin, polyester resin, polyurethane resin, fluororesin, rosin resin, Petroleum resin, coumaron resin, phenolic resin, melamine resin, urea resin, epoxy resin, cellulose resin, xylene resin, alkyd resin, aliphatic hydrocarbon resin, butyral resin, maleic acid resin, fumaric acid resin, vinyl resin, amine resin, Examples include ketimine resin. Among these, acrylic resins, polyurethane resins, and vinyl resins are preferred, and acrylic resins are more preferred. One type of resin may be used alone, or two or more types may be used in combination.

In particular, the resin contained in the colored layer directly laminated on the ink layer formed from the ink composition of the present invention is the resin contained in the ink layer, that is, the (B) water dispersion contained in the ink composition of the present invention. It is preferable that the resin is the same type as the synthetic resin. By using the same type of resin, better adhesion between the colored layer and the ink layer and other properties tend to be obtained.

The content of the colorant in the colored layer is not particularly limited and can be selected as appropriate, for example, from 1 to 70% by mass.

The content of the resin (binder resin) in the colored layer is also not particularly limited, and can be appropriately selected, for example, from 30 to 99% by mass.

The colored layer can also further contain an extender pigment.

The extender pigment contained in the colored layer is not particularly limited, and any known extender pigment can be used. Extender pigments contained in the colored layer include, for example, talc, kaolin, clay, diatomaceous earth, barium sulfate, calcium carbonate, mica, silica powder, silica, allophane, imogolite, bentonite, montmorillonite, sepiolite, glass beads, and the like. Extender pigments may be used singly or in combination of two or more.

When an extender pigment is used, the content of the extender pigment in the colored layer is not particularly limited and can be appropriately selected, for example, from 1 to 20% by mass. The content ratio of the colorant and extender pigment contained in the colored layer is also not particularly limited, and can be appropriately selected.

The colored layer can also further include resin beads. Here, the resin beads are particulate resin whose particle shape is maintained even in the colored layer.

The resin beads contained in the colored layer are not particularly limited, and any known resin beads can be used. Examples of resin beads included in the colored layer include acrylic resin particles, polyurethane resin particles, polyamide resin particles, urea/formaldehyde resin particles, silicone resin particles, fluororesin particles, phenolic resin particles, and melamine. / formaldehyde resin particles, acrylonitrile resin particles, styrene resin particles, etc. One type of resin beads may be used alone, or two or more types may be used in combination.

When using resin beads, the content of the resin beads in the colored layer is not particularly limited and can be selected as appropriate, for example, from 1 to 20% by mass. The content ratio of the coloring agent and resin beads contained in the colored layer is also not particularly limited, and can be appropriately selected.

The average thickness of the colored layer (when two or more colored layers are formed, the total thickness of all colored layers) is not particularly limited and can be selected as appropriate, for example, from 1 to 200 μm. be able to.

When two or more colored layers are formed, a decoration such as a pattern may be formed between the colored layers using, for example, silica sand, glass beads, resin beads, or the like.

The colored layer can be formed by a known method. For example, if necessary, a sealer is applied and the impregnated building board base is coated with the above-mentioned coloring agent, resin, and solvent (water or organic It can be formed by applying a coating composition for forming a colored layer, which further contains an extender pigment and/or resin beads as required, and forming a film by drying or curing.

The coating composition for forming a colored layer can be prepared by stirring and mixing the respective components until they become uniform by a known method. The content of the solvent in the coating composition for forming a colored layer is not particularly limited, and can be appropriately selected. In addition, the coating composition for forming a colored layer may contain various additives, such as film-forming aids, wetting agents, viscosity modifiers, antifoaming agents, dispersants, surfactants, emulsifiers, and anti-settling agents, as necessary. , an anti-skinning agent, an anti-sagging agent, a leveling agent, a plasticizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a preservative, a curing accelerator, and the like.

The coating composition for forming a colored layer can be applied by a known method, such as a spray method, an air spray method, an airless spray method, a roll coating method, a bar coating method, a blade coating method, a knife coating method, and dipping. It can be carried out by a method such as a dipping method, a flow coating method, or an electrostatic coating method. The coating conditions, drying method and drying conditions, curing method and curing conditions of the coating composition for forming a colored layer are not particularly limited, and can be appropriately selected.

The building board of the present invention has the above-mentioned book on the building board base material coated and impregnated with a sealer as needed, preferably on the colored layer formed on the building board base material. It has an ink layer formed from the ink composition of the invention (gravure offset printing ink composition for building boards).

The ink layer of the building board of the present invention is formed by applying the ink layer of the building board, which is the substrate to be printed, using the ink composition of the present invention, as in the gravure offset printing method of the present invention as described above. , preferably by performing gravure offset printing on a colored layer formed on a building board base material. The ink compositions of the present invention may be used alone or as an ink set in which two or more of them are combined. Furthermore, printing can be repeated two or more times.

Gravure offset printing can be performed by a conventional method. Printing conditions are also not particularly limited and can be selected as appropriate.

In the present invention, it is preferable that the gravure plate cylinder and/or blanket cylinder used in gravure offset printing be washed with water.

Furthermore, the temperature of the printing substrate (building board) during printing is 40 to 70°C, and the temperature of the printing substrate (building board) during printing and the temperature of the printing substrate (building board) when printing are (B) The absolute value of the difference from the MFT (minimum film forming temperature) of the water-dispersible resin is preferably 15°C or less, more preferably less than 13°C, particularly preferably 10°C or less.

The thickness of the ink layer is not particularly limited, and can be appropriately determined depending on the gravure offset printing machine used, the purpose, etc.

After performing gravure offset printing and forming an ink layer, one or more clear layers may be formed as a surface protective layer on the ink layer, if necessary. When the ink layer is formed only on a part of the surface of the building board base material or the colored layer, it is preferable that the clear layer is also formed on the building board base material or the colored layer.

Here, the clear layer is a transparent layer that allows at least the ink layer formed therebelow to be visually recognized. The clear layer may be colored or not, as long as the ink layer formed thereunder can be visually recognized.

The clear layer usually preferably contains a highly transparent resin.

The resin contained in the clear layer is not particularly limited, and any resin commonly used for clear layers or surface protective layers of building boards can be used. Examples of resins included in the clear layer include acrylic resins (including copolymer resins such as acrylic styrene resins, acrylic urethane resins, and acrylic silicone resins), silicone resins, polyester resins, polyurethane resins, fluororesins, phenolic resins, Examples include melamine resin and alkyd resin. Among these, acrylic resins, silicone resins, polyurethane resins, and fluororesins are preferred. One type of resin may be used alone, or two or more types may be used in combination.

In particular, as long as the resin contained in the clear layer directly laminated on the ink layer formed from the ink composition of the present invention has the required transparency, the resin contained in the ink layer, that is, the ink of the present invention It is preferable that the resin is the same type as the water-dispersible resin (B) contained in the composition, or a resin that has better weather resistance. By using the same type of resin, better adhesion between the clear layer and the ink layer and other properties tend to be obtained.

The clear layer can also further contain fluororesin powder. Here, the fluororesin powder is a powdered fluororesin that maintains its powder shape even in the clear layer.

The fluororesin powder contained in the clear layer is not particularly limited as long as it is a resin containing fluorine, and any known powder can be used. One type of fluororesin powder may be used alone, or two or more types may be used in combination.

When using fluororesin powder, the content of fluororesin powder in the clear layer is not particularly limited and can be selected as appropriate, for example, from 0.5 to 10% by volume.

The clear layer may further contain inorganic particles, preferably inorganic particles having a Vickers hardness of 500 or more. Note that Vickers hardness can be measured according to JIS Z 2244:2009.

The inorganic particles contained in the clear layer are not particularly limited, and any known inorganic particles can be used. Examples of the inorganic particles contained in the clear layer include silica, alumina, boron nitride, zircon, and diamond. The inorganic particles may be used alone or in combination of two or more.

When inorganic particles are used, the content of the inorganic particles in the clear layer is not particularly limited and can be selected as appropriate, for example, from 0.1 to 30% by volume.

The average thickness of the clear layer (when two or more clear layers are formed, the total thickness of all the clear layers) is not particularly limited and can be selected as appropriate, for example, from 3 to 40 μm. be able to.

The clear layer can be formed by a known method, and includes, for example, the above-mentioned resin and a solvent (water or organic solvent) on an ink layer, etc., and optionally fluororesin powder and/or It can be formed by applying a coating composition for forming a clear layer that further contains inorganic particles and forming a film by drying or curing.

The coating composition for forming a clear layer can be prepared by stirring and mixing the respective components until they become uniform by a known method. The content of the solvent in the coating composition for forming a clear layer is not particularly limited, and can be appropriately selected. In addition, the coating composition for forming a clear layer may contain various additives, such as film-forming aids, wetting agents, viscosity modifiers, antifoaming agents, dispersants, surfactants, emulsifiers, and anti-settling agents, as necessary. , an anti-skinning agent, an anti-sagging agent, a leveling agent, a plasticizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a preservative, a hardening accelerator, an extender, a matting agent, and the like.

The coating composition for forming a clear layer can be applied by a known method, such as a spray method, an air spray method, an airless spray method, a roll coating method, a bar coating method, a blade coating method, a knife coating method, and a dipping method. It can be carried out by a method such as a dipping method, a flow coating method, or an electrostatic coating method. The coating conditions, drying method and drying conditions, curing method and curing conditions of the coating composition for forming a clear layer are not particularly limited, and can be appropriately selected.

After forming the clear layer, one or more overcoat layers may be further formed on the clear layer, if necessary.

Here, the overcoat layer is a general term for functional layers formed on the clear layer, such as a hydrophilic layer made of colloidal silica, a water repellent layer made of alkylsilane, etc., a photocatalytic layer made of titanium oxide, etc. These include, but are not limited to.

The building board of the present invention has an ink layer formed from the ink composition of the present invention by gravure offset printing on a base material (building board base material), and has a high-quality printed image. Furthermore, the ink layer or the laminated film including the colored layer, clear layer, and overcoat layer formed as desired has excellent physical properties such as adhesion and weather resistance. Therefore, the building board of the present invention can be suitably used in a wide range of applications.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, unless otherwise specified, "parts" and "%" in the present examples represent "parts by mass" and "% by mass", respectively.

In Examples and Comparative Examples, measurements and evaluations were performed in the following manner.

<SP value (solubility parameter) of water-dispersible resin and organic solvent>
The SP values of the water-dispersible resin and organic solvent contained in the prepared water-dispersible resin dispersion were determined by the Hoy method, that is, according to the literature [K. L. Hoy, J. Paint Technology, 42, [541], 76 (1970)].

<MFT (minimum film forming temperature) of water-dispersible resin>
The MFT (minimum film forming temperature) of the water-dispersible resin contained in the prepared water-dispersible resin dispersion is 30-30 for water-dispersible resin dispersions 1 to 4 and 6 according to JIS K 6828-2:2003. In the range of 70°C, in the case of water-dispersible resin dispersion 5, in the range of 60 to 90°C, on a smooth stainless steel hot plate with a linear temperature gradient of 0.5°C/cm. Then, the prepared water-dispersible resin dispersion was uniformly applied using an applicator so that the film thickness was 0.2 mm, and the resin dispersion was dried by flowing dry air at room temperature to form a film. The boundary position of the part where a uniform film without cracks was formed was visually confirmed, and the temperature was determined as MFT. The water-dispersible resin dispersions to be measured are all emulsions in which the solvent (dispersion medium) is water and the water-dispersible resin content (solid content) is 40% by mass.

<Minimum film forming temperature (MFT) lowering ability when adding 1% by mass of organic solvent to water-dispersible resin solid content>
The organic solvent was added to the prepared water-dispersible resin dispersion so that the content of the organic solvent was equivalent to 1/10 (mass ratio) of the content of the water-dispersible resin contained in the water-dispersible resin dispersion. An emulsion was prepared by adding and mixing a solvent. Then, for the prepared emulsion, the MFT (MFT when 10% by mass of organic solvent is added) is determined in the same manner as the measurement of the MFT (minimum film forming temperature) of the water-dispersible resin described above, and the value is calculated based on the amount of organic solvent added. The value divided by (=10) was defined as the MFT when 1% by mass of organic solvent was added.
Then, the difference between the MFT of the water-dispersible resin and the MFT when 1% by mass of the organic solvent was added was calculated, and the MFT lowering ability when the organic solvent was added at 1% by mass with respect to the water-dispersible resin was calculated.

<Surface tension of ink composition at 20°C>
After adjusting the temperature of the prepared ink composition to 20° C., the surface tension was measured by the platinum plate method using an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science.

<Viscosity of ink composition at 30°C>
After adjusting the temperature of the prepared ink composition to 30° C., the ink composition was placed in an Iwata type viscosity cup (NK-2) until it wore out, and the time required for the ink composition to fall continuously from the pilot hole was measured.

<Water washability of ink composition>
After circulating the prepared ink composition in a gravure offset printing machine for 1 hour, tap water was poured from the shower head for 3 minutes to wash away the ink from the gravure plate cylinder and blanket cylinder, and the water was wiped off with a paper rag. The adhesion of ink to the rag was visually confirmed and evaluated according to the following criteria. Note that the evaluation was performed under an atmosphere of 23° C. and 50% RH.
◎: No ink adhesion was observed on both the gravure plate cylinder and the blanket cylinder.
○: Slight ink adhesion can be observed on either the gravure plate cylinder or the blanket cylinder.
Δ: Slight ink adhesion can be observed on both the gravure plate cylinder and the blanket cylinder.
×: Ink adhesion can be clearly observed on at least one of the gravure plate cylinder or the blanket cylinder.

<Coloring properties of ink composition>
The prepared ink composition was circulated in a gravure offset printing machine for 1 hour, and the density of the printed image was visually confirmed 10 minutes and 1 hour after the start of circulation, and evaluated according to the following criteria. Note that the evaluation was performed under an atmosphere of 23° C. and 50% RH.
○: No difference is observed between the image printed after 10 minutes and the image printed after 1 hour.
Δ: The image printed after 1 hour is slightly lighter.
×: The printed image is clearly lighter in the image printed after 1 hour.

<Adhesion of building boards>
The adhesion of the manufactured building board was determined by cutting the laminated film (colored layer, ink layer, and clear layer) of the building board at 4 mm intervals vertically and horizontally using a cutter knife in accordance with JIS K 5600-5-6:1999. , make 25 squares, paste Sellotape (registered trademark; manufactured by Nichiban Co., Ltd.) on top of it, rub firmly with your fingertips to press it, then peel off the Sellotape and count the squares of the remaining laminated film. , evaluated according to the following criteria. Note that the evaluation was performed under an atmosphere of 23° C. and 50% RH.
○: Classification 0 to 1 (the edges of the cut are completely smooth, there is no peeling in any grid, and the residual rate of the laminated film is 95 to 99%).
Δ: Classification 2 (residual rate of laminated film is 85% or more and less than 95%).
×: Classification 3 to 5 (either the residual rate of the laminated film is 0% or more and less than 85%, or the degree of peeling still cannot be classified).

<Weather resistance of building boards>
The weather resistance of the manufactured building boards was determined by conducting an accelerated weather resistance test in accordance with JIS K 5600-7-7:2008 using a weather meter Ci4000 (manufactured by Atlas Corporation), and after conducting the test for up to 1000 hours. The appearance of the laminated film of the building board was visually observed, and the adhesion of the laminated film was evaluated in the same manner as in <Adhesiveness of Building Board> above, and the evaluation was made according to the following criteria. Note that the evaluation was performed under an atmosphere of 23° C. and 50% RH.
〇: No appearance abnormalities such as blistering, whitening, or cracks are observed, and the adhesion is classified as 0 to 1 (the cut edges are completely smooth, there is no peeling in any grid, and the residual rate of the laminated film is 95-99%).
Δ: Abnormal appearance such as blistering, whitening, and cracks is not observed, and the adhesion is classified as 2 to 3 (residual rate of laminated film is 65% or more and less than 95%).
×: Appearance abnormalities such as blistering, whitening, and cracks are observed, and the adhesion is classified as 4 to 5 (either the residual rate of the laminated film is 0% or more and less than 65%, or the degree of peeling still cannot be classified).

[Examples 1 to 36, Comparative Examples 1 to 14]
<Preparation of water-dispersible resin dispersions 1, 2, 4, and 5>
In a reactor equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 250 parts of ion-exchanged water, 1 part of sodium bicarbonate (pH adjuster), and polyoxyethylene-1-(allyloxymethyl) alkyl ether were added. After charging 3 parts of sulfate ester ammonium salt (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name "Aqualon KH10"; reactive surfactant) and raising the temperature to 80 ° C. while purging the inside of the reactor with nitrogen, 1 part of potassium persulfate (polymerization initiator) was added. Next, an emulsion (A) prepared in advance by stirring and mixing in a separate container with the formulation shown in Table 1 was continuously added dropwise over 4 hours. After the dropwise addition was completed, stirring was continued at 80°C for 5 hours, then cooled to room temperature, and the pH was adjusted to 8.5 with 28% ammonia water. , 2, 4, 5) were obtained.

<Preparation of water-dispersible resin dispersion 3>
In a reactor equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 250 parts of ion-exchanged water, 1 part of sodium bicarbonate (pH adjuster), and polyoxyethylene alkyl ether ammonium sulfate salt (Daiichi Kogyo Seiyaku Co., Ltd.) were added. 3 parts of Hytenol N-08 (product name: non-reactive surfactant) made by the company, and heated to 80°C while purging the inside of the reactor with nitrogen. agent) was added. Next, an emulsion (A) prepared in advance by stirring and mixing in a separate container with the formulation shown in Table 1 was continuously added dropwise over 4 hours. After the dropwise addition was completed, stirring was continued at 80° C. for 5 hours, then cooled to room temperature, and the pH was adjusted to 8.5 with 28% aqueous ammonia to obtain a water-dispersible resin dispersion 3 (resin 3).

<Preparation of water-dispersible resin dispersion 6>
In a reactor equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 250 parts of ion-exchanged water, 1 part of sodium bicarbonate (pH adjuster), and polyoxyethylene-1-(allyloxymethyl) alkyl ether were added. After charging 3 parts of sulfate ester ammonium salt (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name "Aqualon KH10"; reactive surfactant) and raising the temperature to 80 ° C. while purging the inside of the reactor with nitrogen, 1 part of potassium persulfate (polymerization initiator) was added. Next, the emulsion (A) prepared in advance by stirring and mixing in a separate container with the formulation shown in Table 1 was continuously added dropwise over 2 hours, and then, the emulsion (A) was prepared in advance by stirring and mixing in a separate container with the formulation shown in Table 1. The prepared emulsion (B) was continuously added dropwise over 2 hours. After completion of the dropwise addition, stirring was continued at 80° C. for 5 hours, then cooled to room temperature, and the pH was adjusted to 8.5 with 28% ammonia water to obtain water-dispersible resin dispersion 6 (resin 6).

Table 1 shows the results of measuring the SP value (solubility parameter) and MFT (minimum film forming temperature) of the water-dispersible resins (resins 1-6) contained in the prepared water-dispersible resin dispersions 1-6.

なお、表１中の数値は質量部であり、表１中の略語は、次のとおりである。
・ＭＭＡ：メチルメタクリレート
・ＥＨＡ：２－エチルヘキシルアクリレート
・ＳＴ：スチレン
・ＭＡＡ：メタクリル酸
・ＣＨＭＡ：シクロヘキシルメタクリレート
・ＫＢＭ５０３：３－メタクリロイルオキシプロピルトリメトキシシラン（信越化学工業株式会社製）
・ＫＨ１０：第一工業製薬株式会社製、商品名「アクアロンＫＨ１０」
・ＮＦ０８：第一工業製薬株式会社製、商品名「ハイテノールＮ－０８」

The numerical values in Table 1 are parts by mass, and the abbreviations in Table 1 are as follows.
・MMA: Methyl methacrylate ・EHA: 2-ethylhexyl acrylate ・ST: styrene ・MAA: methacrylic acid ・CHMA: cyclohexyl methacrylate ・KBM503: 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
・KH10: Manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name “Aqualon KH10”
・NF08: Manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name “Hitenol N-08”

<Preparation of colored layer forming coating compositions 1 to 7>
After mixing the raw material components shown in Table 2 with titania beads, they were uniformly dispersed using a bead mill. After dispersion, the titania beads were removed to obtain colored layer forming coating compositions 1 to 7 (paints 1 to 7).

なお、表２中の数値は質量部であり、樹脂１～６（調製した水分散性樹脂分散液１～６）以外の表２中の原料成分は、次のとおりである。
・白色顔料：酸化チタン
・黒色顔料：カーボンブラック
・赤色顔料：赤色酸化鉄
・黄色顔料：黄色酸化鉄
・青色顔料：酸化コバルト
・ウレタン樹脂：株式会社アデカ製、商品名「アデカボンタイターＨＵＸ－４０１」；固形分３７％のウレタン樹脂エマルション
・成膜助剤：ブチルセロソルブ
・シリコーン系表面調整剤：ビックケミー・ジャパン株式会社製、商品名「ＢＹＫ３４７」
・粘度調整剤：ダウケミカルカンパニー社製、商品名「プライマルＡＳＥ－６０」（ポリカルボン酸系増粘剤）
・防腐剤：ロンザ・ジャパン株式会社製、商品名「プロキセルＤＡＣ」（ベンツイソチアゾリン系防腐剤）
・消泡剤：ビックケミー・ジャパン株式会社、商品名「ＢＹＫ－１７８５」（シリコーン系消泡剤）

The numerical values in Table 2 are parts by mass, and the raw material components in Table 2 other than Resins 1 to 6 (prepared water-dispersible resin dispersions 1 to 6) are as follows.
・White pigment: titanium oxide ・Black pigment: carbon black ・Red pigment: red iron oxide ・Yellow pigment: yellow iron oxide ・Blue pigment: cobalt oxide ・Urethane resin: Manufactured by ADEKA Co., Ltd., product name "ADEKA BONTITER HUX-401"”; Urethane resin emulsion with a solid content of 37%/Film-forming aid: Butyl cellosolve/Silicone surface conditioner: Manufactured by BYK-Chemie Japan Co., Ltd., product name: “BYK347”
・Viscosity modifier: Manufactured by Dow Chemical Company, product name “Primal ASE-60” (polycarboxylic acid thickener)
・Preservative: Manufactured by Lonza Japan Co., Ltd., product name “Proxel DAC” (benzisothiazoline preservative)
・Defoaming agent: BYK-Chemie Japan Co., Ltd., product name “BYK-1785” (silicone antifoaming agent)

<Preparation of ink compositions 1 to 38>
After mixing the raw material components shown in Tables 3 to 6 and zirconia beads (φ0.5 mm), they were uniformly dispersed in a bead mill. After dispersion, the zirconia beads were removed to obtain ink compositions 1 to 38 (inks 1 to 38).

The boiling point and SP value (solubility parameter) at 1 atm of the organic solvent contained in the prepared ink composition, the ability to lower the minimum film forming temperature (MFT) when 1% by mass is added to the water-dispersible resin solid content, and the ink The results of measuring the surface tension at 20°C and viscosity at 30°C of the compositions are shown in Tables 3 to 6.

なお、表３～６中の数値は質量部であり、樹脂１～６（調製した水分散性樹脂分散液１～６）と有機溶剤と水以外の表３～６中の原料成分は、次のとおりである。
・白色顔料：酸化チタン
・黒色顔料：カーボンブラック
・黄色顔料：黄色酸化鉄
・赤色顔料：赤色酸化鉄
・青色顔料：酸化コバルト
・シリコーン系表面調整剤：ビックケミー・ジャパン株式会社製、商品名「ＢＹＫ３４７」
・粘度調整剤：ダウケミカルカンパニー社製、商品名「プライマルＡＳＥ－６０」（ポリカルボン酸系増粘剤）
・防腐剤：ロンザ・ジャパン株式会社製、商品名「プロキセルＤＡＣ」（ベンツイソチアゾリン系防腐剤）
・消泡剤：サンノプコ株式会社製、商品名「ＳＮデフォーマー１３１４」（シリコーン系消泡剤）
・紫外線吸収剤：ＢＡＳＦ株式会社製、商品名「Ｔｉｎｕｖｉｎ１１３０」（ベンズトリアゾール系紫外線吸収剤）
・光安定剤：ＢＡＳＦ株式会社製、商品名「Ｔｉｎｕｖｉｎ２９２」（ヒンダードアミン系光安定剤）

The numbers in Tables 3 to 6 are parts by mass, and the raw material components in Tables 3 to 6 other than resins 1 to 6 (prepared water-dispersible resin dispersions 1 to 6), organic solvent, and water are as follows. It is as follows.
・White pigment: titanium oxide ・Black pigment: carbon black ・Yellow pigment: yellow iron oxide ・Red pigment: red iron oxide ・Blue pigment: cobalt oxide ・Silicone surface conditioner: BYK Chemie Japan Co., Ltd., product name "BYK347" ”
・Viscosity modifier: Manufactured by Dow Chemical Company, product name “Primal ASE-60” (polycarboxylic acid thickener)
・Preservative: Manufactured by Lonza Japan Co., Ltd., product name “Proxel DAC” (benzisothiazoline preservative)
・Defoaming agent: Manufactured by San Nopco Co., Ltd., product name "SN Deformer 1314" (silicone-based defoaming agent)
・Ultraviolet absorber: manufactured by BASF Corporation, product name “Tinuvin1130” (benztriazole ultraviolet absorber)
・Light stabilizer: manufactured by BASF Corporation, product name “Tinuvin292” (hindered amine light stabilizer)

<Manufacture of building boards>
Apply a water-based sealer (manufactured by Dainippon Toyo Co., Ltd., product name ``Water-based Mighty Sealer Multi'') using air spray to the surface of a slate board (manufactured by TP Giken Co., Ltd.) measuring 150 mm long x 70 mm wide x 4 mm thick. A base material was prepared by applying the coating to an amount of 100 g/m ² and drying it at room temperature for 2 hours.

Next, with the surface temperature of the base material adjusted to 60°C, colored layer forming coating compositions 1 to 1 shown in Tables 7 to 11 were applied to the sealer-coated surface of the base material using an airless sprayer. 7 (Paints 1 to 7) was applied in an amount of 120 g/m ² (corresponding to a dry film thickness of 30 μm). After coating, it was dried at 80° C. for 10 minutes to form a colored layer. Note that the surface temperature of the base material was measured using an infrared radiation type non-contact thermometer.

Next, with the surface temperature of the base material adjusted to the temperature shown in Tables 7 to 11, ink composition 1 shown in Tables 7 to 11 was applied to the surface of the base material on which the colored layer was formed using a gravure offset printing machine. ~38 (inks 1 to 38) were painted. Thereafter, it was dried at 80° C. for 10 minutes to form an ink layer. Note that the surface temperature of the base material was measured using an infrared radiation type non-contact thermometer.

Next, with the surface temperature of the base material adjusted to 60°C, a water-based acrylic clear paint (manufactured by Dainippon Toyo Co., Ltd., product name "V"Ceran") was applied in an amount of 80 g/m ² (equivalent to a dry film thickness of 25 μm). After coating, it was dried at 80° C. for 20 minutes to form a surface protective layer (clear layer). Note that the surface temperature of the base material was measured using an infrared radiation type non-contact thermometer.

Tables 7 to 11 show the results of measuring the water washability and coloring properties of the ink compositions used to manufacture the building boards, and the adhesion and weather resistance of the manufactured building boards.

According to the present invention, there is provided a gravure offset printing ink composition for building boards, which can be printed satisfactorily on building boards by gravure offset printing, and capable of stable continuous printing, and a gravure offset printing method. can do. Moreover, according to the present invention, it is possible to provide a building board printed by gravure offset printing using this gravure offset printing ink composition for building boards.

Claims (14)

A water-based ink composition used for gravure offset printing of building boards, the composition comprising:
(A) a colorant, (B) a water-dispersible resin, (C) water, and (D) a boiling point at 1 atm of 180°C or higher, and an SP value (solubility parameter) determined by the Hoy method. an organic solvent having a molecular weight of 10.5 or more;
(D) The content of the organic solvent having a boiling point of 180° C. or higher at 1 atm and an SP value of 10.5 or higher determined by the Hoy method is 3 to 20% by mass. , a gravure offset printing ink composition for building boards. The organic solvent (D) having a boiling point of 180° C. or higher at 1 atm and an SP value determined by the Hoy method of 10.5 or higher is added in an amount of 1% by mass to the water-dispersible resin (B). The gravure offset printing ink composition for building boards according to claim 1, wherein the gravure offset printing ink composition for building boards has a minimum film forming temperature (MFT) lowering ability of 3°C or less. (D) The organic solvent having a boiling point at 1 atm of 180° C. or higher and an SP value determined by the Hoy method of 10.5 or higher is a diol compound having 6 or less carbon atoms. The gravure offset printing ink composition for building boards according to claim 1 or 2. The gravure offset for building boards according to any one of claims 1 to 3, wherein the water-dispersible resin (B) is obtained by performing a polymerization reaction in the presence of a reactive emulsifier. Printing ink composition. The gravure offset printing ink composition for building boards according to any one of claims 1 to 4, further comprising (E) a silicone-based surface conditioner. The gravure offset printing ink composition for building boards according to any one of claims 1 to 5, which has a surface tension of 19 to 40 mN/m at 20°C. The gravure offset printing ink composition for building boards according to any one of claims 1 to 6, which has a viscosity at 30°C of 10 to 50 seconds on an Iwata cup viscometer. A gravure offset printing method, comprising printing on a printing substrate by gravure offset printing using the gravure offset printing ink composition for building boards according to any one of claims 1 to 7. 9. The gravure offset printing method according to claim 8, wherein the gravure plate cylinder and/or the blanket cylinder used in gravure offset printing is washed with water. The temperature of the printing substrate during printing is 40 to 70°C, and
The absolute value of the difference between the temperature of the printing substrate during printing and the MFT (minimum film forming temperature) of the water-dispersible resin (B) in the gravure offset printing ink composition for building boards is 15 The gravure offset printing method according to claim 8 or 9, characterized in that the temperature is below .degree. A building board comprising a base material and an ink layer formed from the gravure offset printing ink composition for building boards according to any one of claims 1 to 7. The building board according to claim 11 , further comprising a colored layer between the base material and the ink layer. The building board according to claim 11 or 12 , further comprising a clear layer on the ink layer. The building board according to claim 13 , further comprising an overcoat layer on the clear layer.