JP6697771B1 - Painted building material manufacturing method and resulting painted building material - Google Patents

Abstract

An object of the present invention is to provide a method for producing a coated building material having excellent cellophane tape (registered trademark) resistance and stain resistance on the surface of the coated building material, and a coated building material obtained from the method. A method for producing a coating building material having an active energy ray-curable coating on a substrate, wherein the double bond equivalent is 100 to 750 g/mol and the weight average molecular weight is 10,000 to on the substrate. A step of applying a coating composition containing 100,000 acrylic (meth)acrylate resin, a compound having an acryloyl group and a siloxane skeleton and/or a compound having a fluoroalkyl group, and silica to form a coating film of the coating composition. (1) and the step (2) of irradiating the coating film obtained in the step (1) with an active energy ray of 80 to 500 mJ/cm 2 at least once in a gas atmosphere having an oxygen concentration of less than 8%. A method of manufacturing a painted building material, which is characterized in that [Selection diagram] None

Description

The present invention relates to a method for producing a coated building material such as a decorative sheet having an active energy ray-curable film, which has sufficient surface strength and excellent stain resistance, and a coated building material obtained by the method.

2. Description of the Related Art In recent years, decorative sheets have been widely used in furniture and floor materials inside buildings such as houses, and various surface coatings have been applied for the purpose of protection and beauty. Most of them use gravure printing, and examples of the ink used for gravure printing include active energy ray-curable inks containing an acrylate resin and the like. Above all, a photopolymerization initiator is added to a composition containing an acrylate resin as a main component, and the photopolymerization initiator reacts to generate radicals by irradiating with ultraviolet rays among the active energy rays, whereby the polymerization proceeds and the crosslinked structure is formed. Is a method of obtaining a coating film.

Examples of the required coating film physical properties include stain resistance, scratch resistance, and cellophane tape (registered trademark) resistance.
Cellotape resistance (registered trademark) is a decorative sheet when the decorative sheet is actually processed at the construction site, such as a memo sheet or a temporary fixing for positioning with the tape. It refers to the resistance of the surface. In order to express them, the composition and the layer structure of the decorative sheet are devised, and it has been tried to obtain a coating film having the required performance in a short time by performing ultraviolet irradiation.
For example, an active energy ray having a melting point of 40° C. or lower is used by using a thermoplastic organic compound such as an acrylic alkyd resin having a glass transition temperature in the range of 60 to 300° C., other polyester resin, urethane resin, and fibrin resin. An invention of a laminate for a decorative sheet, which substantially consists of an ultraviolet curable resin composition and a photopolymerization initiator, has been made (for example, Patent Document 1).
However, it is still insufficient in terms of cellophane tape (registered trademark) resistance associated with the surface strength of the laminate and stain resistance.
Further, in curing by irradiation of ultraviolet rays in the air, curing inhibition is likely to occur due to oxygen in the air, and particularly the portion closer to the surface layer is significantly affected. Therefore, the surface layer is insufficiently cured, and the coating film performance is significantly reduced.

In addition, an active energy ray-curable coating building material has been disclosed by a process of irradiating the surface of a coating film having an active energy ray-polymerizable oligomer, a monomer, and a polymerization initiator with a specific intensity of ultraviolet rays in a gas atmosphere with an oxygen concentration of less than 8% (For example, Patent Document 2).
However, although the curing efficiency of the coating film surface is improving, the present invention is directed to a wood material such as oak as a base material, and is not related to a coating building material for a decorative sheet, and is required for a decorative sheet. It does not combine cellophane tape (registered trademark) resistance and stain resistance.
In addition, in the case of the conventional additive, a phenomenon in which the additive component is desorbed from the cured coating film surface layer occurs due to physical factors such as friction, resulting in deterioration of coating film performance. Especially in gravure printing, when the coated printed material is wound up with a roll, the front surface and the back surface of the printed material are in contact with each other, and the additive components that should be on the front surface adhere to the back surface, which causes the printed material to be printed during construction. However, there is a problem that it cannot be sufficiently adhered to the member.

JP, 2008-44150, A JP-A-2005-305294

  The subject of the present invention relates to a method for producing a coated building material having excellent cellophane tape (registered trademark) resistance and stain resistance on the surface of the coated building material, and a coated building material obtained from the method.

  The present inventors provide a method for producing a coating building material having an active energy ray-curable coating on a substrate, a specific acrylic (meth)acrylate resin, a compound having an acryloyl group and a siloxane skeleton, and/or Alternatively, a step (1) of forming a coating film using a coating composition containing a compound having a fluoroalkyl group and silica, and the coating film obtained in the step (1) can be applied with a specific strength under a specific atmosphere. The above-mentioned problem has been solved by the two-step method for manufacturing a coated building material by the step (2) of irradiating once with active energy rays.

That is, the present invention is a method for producing a coating building material having an active energy ray-curable coating on a substrate, wherein the double bond equivalent is 100 to 750 g/mol and the weight average molecular weight is 10,000 on the substrate. A coating composition containing 100 to 100,000 acrylic (meth)acrylate resin, a compound having an acryloyl group and a siloxane skeleton and/or a compound having a fluoroalkyl group, and silica is applied to form a coating film of the coating composition. A step (1), and a step (2) of irradiating the coating film obtained in the step (1) with an active energy ray of 80 to 500 mJ/cm ² at least once under a gas atmosphere having an oxygen concentration of less than 8%. The present invention relates to a method for producing a painted building material, which is characterized by having

  The present invention also relates to a method for producing a coated building material, wherein the acrylic (meth)acrylate resin has a glass transition temperature (Tg) in the range of 40 to 130°C and a hydroxyl value of 5 to 300 mgKOH/g.

  The present invention also relates to a method for producing a coated building material, wherein the silica is wet silica having an average particle diameter of 0.1 to 25 µm and/or dry silica having an average particle diameter of 0.1 to 3 µm.

  The present invention also relates to a method for producing a coated building material further containing a polyfunctional (meth)acrylate and/or a urethane (meth)acrylate resin.

  The present invention also relates to a coated building material obtained by the manufacturing method.

  According to the method for producing a painted building material of the present invention, it is possible to provide a painted building material having excellent Sellotape (registered trademark) property and stain resistance on the surface of the painted building material.

The method for producing a coating building material of the present invention is a method for producing a coating building material having an active energy ray-curable coating on a base material, wherein the double bond equivalent is 100 to 750 g/mol on the base material, and the weight is A coating composition containing an acrylic (meth)acrylate resin having an average molecular weight of 10,000 to 100,000, a compound having an acryloyl group and a siloxane skeleton and/or a compound having a fluoroalkyl group, and silica, and a coating composition. The step (1) of producing the coating film and the coating film obtained in the step (1) are irradiated with an active energy ray of 30 to 1000 mJ/cm ² at least once under a gas atmosphere having an oxygen concentration of less than 8%. It has a step (2) of
First, the coating composition will be described.

  Examples of the monomer component constituting the acrylic (meth)acrylate resin used in the coating composition include monofunctional monomers such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene, and N-vinylprolidone, and polyfunctional monomers. Functional monomers such as trimethylolpropane (meth)acrylate, hexanediol (meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth) Examples thereof include acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol (meth)acrylate and the like.

The double bond equivalent of the acrylic (meth)acrylate resin must be in the range of 100 to 750 g/mol. When the double bond equivalent of the acrylic (meth)acrylate is less than 100 g/mol, the volume shrinkage during curing is large, and the coating film may be cracked due to bending or distortion, and the workability may be deteriorated due to close crosslinking. To do. Further, if it exceeds 750 g/mol, there is a tendency that the physical properties such as hardness after the reaction are insufficient due to lack of reactive groups, and it is more preferably in the range of 200 to 400 g/mol, and in the range of 200 to 300 g/mol. More preferable.
The double bond equivalent of the acrylic (meth)acrylate resin is defined by the following formula.
“Double bond equivalent”=“molecular weight of one molecule of acrylic (meth)acrylate resin”/“number of double bonds”
The weight average molecular weight of the acrylic (meth)acrylate must be in the range of 10,000 to 100,000. If the weight average molecular weight of the acrylic (meth)acrylate is 10,000 or more, tack is less likely to remain in the coating film, and tack-free only in the drying step is facilitated. The viscosity of the product does not become too high, and it is possible to avoid the problem that a sufficient coating amount cannot be obtained because the dilution during coating is too effective. Further, from the viewpoint of workability, it is more preferably 10,000 to 50,000, further preferably 10,000 to 30,000.
The weight average molecular weight is measured by GPC in terms of polystyrene.

Furthermore, the glass transition temperature (Tg) of the acrylic (meth)acrylate is preferably in the range of 40 to 130° C., and if it is 40° C. or higher, a sufficient strength can be obtained after curing when formed into a coating film. If the temperature is 130° C. or lower, the tendency that the brittleness appears when the coating film is formed and the workability is lowered can be suppressed. Further, the hydroxyl value of the acrylic (meth)acrylate is preferably in the range of 5 to 300 mgKOH/g, and when it is 5 mgKOH/g or more, the dispersion of the matting agent such as wet silica does not decrease and the low gloss is maintained. If it is 300 mgKOH/g or less, the tendency that the stain resistance is lowered can be suppressed.
The glass transition temperature (Tg) is measured by using a differential scanning calorimeter and scanning under a nitrogen atmosphere with a cooling device in a temperature range of −80 to 450° C. and a temperature rising temperature of 10° C./min. It is a thing.

  The content of the acrylic (meth)acrylate is preferably 20 to 85% by mass of the total solid content in the coating composition from the viewpoint of suitable coatability and curability of the coated surface, and 25 to 80% by mass. % Is more preferable.

  Next, the compound having an acryloyl group and a siloxane skeleton and/or a compound having a fluoroalkyl group used in the coating composition in the method for producing a coated building material of the present invention will be described.

A typical example of the compound having an acryloyl group and a siloxane skeleton is silicone (meth)acrylate which is a (meth)acrylate having a silicone skeleton.
The silicone (meth)acrylate will be specifically described below with some examples.

  Examples of the silicone (meth)acrylate include a silicone (meth)acrylate represented by the following general formula (1) having a propyl (meth)acrylate structure at both ends or one end, and a silicone represented by the following general formula (2). An epoxy (meth)acrylate etc. are mentioned.

In the general formula (1), R1 is a (meth)acryloyl group, R2 is a (meth)acryloyl group or a methyl group, and p is an integer of 0 or more.
In the general formula (2), l is an integer of 0 or more, m is an integer of 1 or more, n is an integer of 0 or more, and R3, R4, and R5 are each independently hydrogen or a methyl group. is there.

When the molecular weight of the silicone (meth)acrylate represented by the above general formula (1) is too large, the compatibility with other polymerizable components decreases. On the other hand, if the molecular weight is too small, it becomes difficult to obtain the effects of improving water repellency and scratch resistance. Therefore, the weight average molecular weight of the silicone (meth)acrylate represented by the general formula (1) is preferably about 500 to 2000.
Examples of commercially available products of such silicone (meth)acrylates include FM-0711, FM-0721, FM-0725, FM-7711, and FM-7721 of "Silaplane (registered trademark)" series manufactured by JNC. FM-7725; X-22-2445, X-22-174ASX, X-22-174BX, X-22-174DX, KF-2012, X-22-2426, X-22-2475, manufactured by Shin-Etsu Chemical Co., Ltd. X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, X-22-164E; BY16-152C manufactured by Toray Dow Corning and the like can be mentioned. ..

  Examples of commercially available products of the silicone epoxy (meth)acrylate represented by the general formula (2) include Rad2011 and Rad2100 (polysiloxane acrylate Cas number: 125445) of "Tego (registered trademark)" series manufactured by Evonik Japan. 52-9), Rad2500 (polydimethylsiloxane acrylate Cas number: 125445-52-9), Rad2700 (acrylic modified polysiloxane Cas number: 157811-87-5) and the like.

  As the silicone (meth)acrylate, other than the above, for example, a (meth)acrylate obtained by modifying both ends of polydimethylsiloxane with at least one of ethylene oxide and propylene oxide may be used. Examples of commercially available products thereof include X-22-1602 manufactured by Shin-Etsu Chemical Co., Ltd.; BYK-UV3500, BYK-UV3530 manufactured by Big Chemie Japan; Rad2200N of "Tego (registered trademark)" series manufactured by Evonik Japan. , Rad2250, Rad2300; EBECRYL 350 manufactured by Daicel Ornex Co., and the like.

  As the silicone (meth)acrylate, one having at least one of urethane (meth)acrylate and polyester (meth)acrylate and having a silicone skeleton may be used. Examples of the commercially available product include BYK-UV3570 manufactured by Big Chemie Japan; "Miramer (registered trademark)" series SIU100, SIU1000, SIU2400, SIP900 and the like manufactured by Miwon Specialty Chemical.

  Examples of commercially available silicone (meth)acrylates other than those described above include BYK-UV3505, 3530, 3575, and 3576 manufactured by BYK Japan KK; EBECRYL 1360 manufactured by Daicel Ornex.

  As the silicone (meth)acrylate, among the above, the silicone (meth)acrylate represented by the general formula (1) and the silicone epoxy (represented by the general formula (2) from the viewpoint of the stain resistance of the surface of the coated building material. Rad2011, Rad2100, Rad2500, and Rad2700 of "Tego (registered trademark)" manufactured by Evonik Japan, which is a (meth)acrylate, are preferable, and Rad2700 (acrylic modified polysiloxane Cas number: 157811-87-5) is particularly preferable.

In the coating composition, a compound having a fluoroalkyl group may be used instead of the compound having an acryloyl group and a siloxane skeleton, or a compound having an acryloyl group and a siloxane skeleton and a compound having a fluoroalkyl group. You may mix and use. The compound having a fluoroalkyl group is a compound represented by Chemical Formula 3.

^{_{R f - (R 6 -A)}} n ··· Formula 3

Here, R ^f is a fluorine compound segment, R ₆ is an alkanediyl group, an alkanetriyl group, and an ester structure, urethane structure, ether structure, or triazine structure derived from them, A is a reactive site, and n is a reactive site. 1 or 2.

The reactive site refers to a site that reacts with other components by external energy such as heat or light. As such a reactive site, an alkoxysilyl group and a silanol group in which an alkoxysilyl group is hydrolyzed from the viewpoint of reactivity, a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, etc. Can be mentioned. Of these, a vinyl group, an allyl group, an alkoxysilyl group, a silyl ether group, a silanol group, an epoxy group, and an acryloyl (methacryloyl) group are preferable from the viewpoint of reactivity and handling property.

An example of the compound having a fluoroalkyl group is the compound shown below. 3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropyltriisopropoxysilane, 3,3,3-trifluoropropyltrichlorosilane, 3,3,3-Trifluoropropyltriisocyanate silane, 2-perfluorooctyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 2-perfluorooctylethyltriisopropoxysilane, 2-perfluorooctylethyltri Chlorosilane, 2-perfluorooctylisocyanate silane, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3-perfluorobutyl 2-hydroxypropyl acrylate, 2-perfluorohexyl ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-per Fluorodecylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate, 3-perfluoro- 5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexadecafluorononyl acrylate, hexafluoro Butyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-perfluorobutylethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2 -Perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2- Hydroxypropyl methacrylate, 2-perfluoro-5-methyl Hexyl ethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, octafluoro Examples thereof include pentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluorobutyl methacrylate, and triacryloyl-heptadecafluorononenyl-pentaerythritol.
The fluorine compound may have a plurality of fluoropolyether moieties per molecule.

Examples of commercially available compounds having a fluoroalkyl group include RS-75 (manufactured by DIC Corporation), C10GACRY, C8HGOL (manufactured by Oil and Fat Products Co., Ltd.) and Optool DAC-HP (manufactured by Daikin Industries, Ltd.). Among them, RS-75 (manufactured by DIC Co., Ltd.) is particularly preferable because it has good stain resistance on the surface of the coated building material.

The addition amount of the compound having an acryloyl group and a siloxane skeleton and/or the compound having a fluoroalkyl group is preferably in the range of 0.1 to 10% by mass, more preferably 0.3 to 10% by mass based on the total solid content of the coating composition. It is in the range of 8% by mass. When the content is 0.1% by mass or more, the adhesion of the coating composition to the surface of the painted building material and the resistance to cellophane tape (registered trademark) can be maintained, and also the stain resistance can be provided. If it is 10% by mass or less, the tendency of set-off easily can be suppressed.

Amorphous silica is more preferable as the silica used in the coating composition. Examples of the amorphous silica include diatomaceous earth, activated clay and the like. Among the amorphous silicas, dry silica, wet silica, silica gel and the like can be used as the synthetic amorphous silica.
The silica used as the matting agent used in the coating composition is preferably wet silica produced by neutralization and decomposition reaction of an aqueous solution of sodium silicate with an acid or an alkali metal salt.

  The synthetic amorphous silica becomes a primary particle aggregate (secondary particle structure) by fusing or chemically bonding primary particles of 5 to 55 nm, which is the smallest constituent unit of the substance. Furthermore, the primary particle aggregates physically aggregate and exist as secondary aggregates, but the secondary aggregates are the primary particle aggregates (secondary particle structure) by giving physical shearing force in various media. Can be distributed up to. The average particle diameter of the present invention refers to an average secondary particle system that is a primary particle aggregate (secondary particle structure).

The average particle size of the wet silica used as the matting agent is 0.1 to 25 μm, preferably 0.3 to 20 μm, more preferably 0.5 to 15 μm, and further preferably 1 to 10 μm. When the average particle size is less than 0.05 μm, the primary particles having a smaller particle size are strongly bonded to each other and the specific surface area is also large, so that they have a high oil absorption performance and are sufficient when used as a coating composition. The fluidity cannot be obtained, and the matte effect is lowered, so that a high-grade feeling associated with a matte feeling cannot be obtained. When the average particle diameter is larger than 25 μm, stains are likely to be deteriorated due to dirt entering the irregularities on the surface, and gloss change and scratches due to particles falling off or burying are likely to occur.
The wet silica has a pore volume of 0.1 to 2.0 mL/g, preferably 1.5 to 2.0 mL/g. The apparent specific gravity is 0.1 to 1.5 g/mL, preferably 0.1 to 0.5 g/mL. The oil absorption amount is preferably 50 to 400 mL/100 g, and more preferably 200 to 400 mL/100 g. If the pore volume is less than 0.1 mL/g, the apparent specific gravity is 0.1 g/mL, and the oil absorption is less than 50 mL/100 g, it becomes difficult to obtain a sufficient matting effect. On the other hand, when the pore volume is 2.0 mL/g, the apparent specific gravity is 1.5 g/mL, and the oil absorption exceeds 400 mL/100 g, the matting effect is great, but the thickening effect increases more than necessary, and it is used as a coating agent. Is not preferable because the fluidity of the liquid tends to be impaired.

The content of the wet silica used as the matting agent in the present invention is 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 7% by mass based on the total amount of the coating composition. Is desirable. When the silica content is less than 0.01% by mass, a sufficient matting effect is not observed, and when it exceeds 10% by mass, the fluidity and transferability of the coating agent tend to be impaired, which is not preferable. Among them, wet silica having a specific surface area by the BET method of 50 to 500 m ² /g is preferable.

  Further, silica may be added as a scratch resistance improving additive that imparts scratch resistance. As silica added for imparting scratch resistance, dry silica produced by burning silicon tetrachloride gas in a gas phase is preferable. By adding dry silica as a scratch resistance improving additive to the wet silica as the matting agent, it is possible to improve the scratch resistance of the coated surface in addition to the appropriate low gloss.

  The average particle size of the dry silica as the scratch resistance improving additive is 0.1 to 3 μm, preferably 0.1 to 0.5 μm, and more preferably 0.1 to 0.25 μm.

When used as the scratch resistance improving additive, the content of the dry silica is preferably 10 to 30% by mass, and more preferably 15 to 20% by mass based on the total amount of the coating composition. If the silica content is less than 10% by mass, sufficient scratch resistance cannot be obtained, and if it exceeds 30% by mass, the sharpness and stain resistance of the coating agent tend to be impaired.
Above all, dry silica having a specific surface area by the BET method of 50 to 500 m ² /g is preferable.
Further, acrylic resin beads, silicone beads, or the like can be substituted as the scratch resistance improving additive. The acrylic resin beads and the silicone beads have an average particle size of 1 to 50 μm, preferably 1 to 30 μm, more preferably 1 to 10 μm, and the content thereof is preferably 3 to 15% by mass of the total amount of the coating composition. It is more preferable if it is -12% by mass.

Both wet silica used as a matting agent and dry silica used as a scratch resistance improving additive used in the present invention may be surface-modified.
The method of surface-treating the silica particles is not particularly limited and may be a known method. Examples thereof include those subjected to a surface difference treatment with wax or a silane coupling agent.

Examples of the base material used in the method for producing a painted building material of the present invention include paper and various films for decorative sheets, as well as wood and noncombustible materials.

The decorative sheet is a pattern layer formed by printing or applying a known ink such as acrylic, cellulose, vinyl, chlorinated polyolefin, chlorinated rubber or urethane printing ink or paint to a substrate such as paper. After being formed, a top coat layer for covering the pattern layer is provided, and the coating composition forms the top coat layer.
Examples of the base material for the decorative sheet include paper sheets such as thin paper, plain paper, reinforced paper, resin-impregnated paper, titanium paper, polyethylene terephthalate sheet, glycol modified polyethylene terephthalate sheet (PETG sheet), polyvinyl chloride sheet. Resin sheets such as polyethylene sheet, acrylonitrile butadiene styrene sheet, polypropylene sheet, and composite sheets of these can be used.
Further, as the wood base material of the wood decorative board, known materials such as plywood, particle board, hard board, MDF, etc., which have been conventionally used as wood base materials for decorative boards, furniture, building members and the like can be mentioned. In addition, it does not matter what manufacturing method these publicly known substrates are obtained.

  Further, examples of the non-combustible material that can be used as the base material include open board building materials made of gypsum board, gypsum board, calcium silicate board, and the like.

  In the method for producing a coated building material of the present invention, an acrylic (meth)acrylate resin having a double bond equivalent of 100 to 750 g/mol and a weight average molecular weight of 10,000 to 100,000 and an acryloyl group are provided on the base material. A coating building material through the step (1) of coating a coating composition containing a compound having a siloxane skeleton and/or a compound having a fluoroalkyl group, and silica, and first producing a coating film of the coating composition To manufacture.

  In the step (1) of producing a coating film of the coating composition, in producing the coating film, specific examples of coating/printing methods of the coating composition include coating methods such as roll coater and gravure. Adopt a coater, flexo coater, air doctor coater, blade coater, air knife coater, squeeze coater, impregnation coater, transfer roll coater, kiss coater, curtain coater, cast coater, spray coater, die coater, offset printer, screen printer, etc. can do.

Next, the coating film obtained in the step (1) has a step (2) of irradiating the coating film obtained in the step (1) with an active energy ray of 30 to 1000 mJ/cm ² at least once under a gas atmosphere having an oxygen concentration of less than 8%. It is possible to provide a coated building material that has excellent cellophane (registered trademark) property on the surface of the painted building material and stain resistance.
The gas atmosphere having an oxygen concentration of less than 8% is realized by injecting into the reaction vessel one or a mixture of two or more gases selected from nitrogen gas, carbon dioxide gas and argon gas together with air or alone. It is a thing.

The active energy ray in the step (2) of irradiating the active energy ray of 30 to 1000 mJ/cm ² at least once is an ionizing radiation or an electromagnetic wave such as an ultraviolet ray, an electron beam or a γ ray. Ultraviolet rays or electron beams are preferred.

When irradiating with ultraviolet rays in a gas atmosphere having an oxygen concentration of less than 8%, a known ultraviolet irradiating device equipped with a high pressure mercury lamp, an excimer lamp, a metal halide lamp or the like can be used. When the amount of ultraviolet light during curing is 80 mJ/cm ² or more, the curing efficiency is good, and when it is 1000 mJ/cm ² or less, it is preferable from the viewpoint of preventing damage to the substrate due to heat.

In the method for producing a coated building material having an active energy ray-curable coating of the present invention, a cured coating can be obtained by irradiating an active energy ray after coating the base material. The active energy rays include ultraviolet rays, electron rays, α rays, β rays, and ionizing radiation such as γ rays, and specific energy sources or curing devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, and Ultraviolet light emitting diode (UV-LED), carbon arc, metal halide lamp, xenon lamp, chemical lamp, low pressure mercury lamp, high pressure mercury lamp for copying, medium or high pressure mercury lamp, ultra high pressure mercury lamp, electrodeless lamp, metal halide lamp, natural light, etc. Examples thereof include ultraviolet rays used as a light source, electron beams from scanning type and curtain type electron beam accelerators, and the like.
In the coating composition used in the present invention, a curing reaction can be performed without leaving a sticky finish even if it is not a two-component curing type, by irradiating with active energy rays, preferably ultraviolet rays as described above. it can. For example, commercially available lamps such as H lamps, D lamps, and V lamps manufactured by Fusion System can be used.

When curing in an inert gas, there is little inhibition of curing by oxygen, and the above-mentioned acrylic (meth)
Acrylate resin, etc., the reaction of the radically polymerizable double bond of the main agent proceeds more and curing is sufficiently performed, and a compound having acryloyl group having an ultraviolet reactive group and a siloxane skeleton, for example, a siloxane skeleton such as a trimethylsilyl group, or the like, The fluorine portion of the compound having a fluoroalkyl group is sufficiently fixed on the surface of the coating film, and remains on the surface layer for a long time even after a certain period of time, which increases the resistance of the surface of the coating film on the decorative sheet, and it is resistant to cellophane tape (registered trademark). , And stain resistance can be further improved. The additive component that is sufficiently fixed does not easily come off even if it comes into contact with the back surface of the original fabric when the roll is wound in gravure printing.

  When using ultraviolet rays as the active energy ray in the method for producing a coating building material of the present invention, it is possible to utilize a publicly known photopolymerization initiator as a curing agent for the coating composition to be used, among which a radical polymerization type A photopolymerization initiator is preferable, and an α-hydroxyalkylketone-based photopolymerization initiator that does not cause coloration of the solution when the active energy ray-curable compound is dissolved and has little yellowing with time is included. Examples of the α-hydroxyalkylketone photopolymerization initiator include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropane. Examples include -1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, and the like. Further, a phenylglyoxolate photopolymerization initiator is also preferable. Examples of the phenylglyoxolate-based photopolymerization initiator include methylbenzoyl formate and the like. Of these, 1-hydroxycyclohexyl phenyl ketone is preferable.

  Further, as the other radical polymerization type photopolymerization initiator, a monoacylphosphine oxide photopolymerization initiator having an absorption wavelength in the long wavelength region of ultraviolet rays may be appropriately combined and used. The monoacylphosphine oxide-based photopolymerization initiators are 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2,6,6 except for bisacylphosphine oxides which are colored when dissolved in an active energy ray-curable compound. -Dimethoxybenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2-methylbenzoyl-diphenylphosphine oxide, pivaloyl Examples thereof include monoacylphosphine oxides such as phenylphosphinic acid isopropyl ester. Among them, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide is UV-having an emission wavelength at 385 nm or 395 nm. Having a UV absorption wavelength that matches the emission wavelength region of the LED is more preferable in that suitable curability can be obtained and the yellowing of the cured film is small.

  The above photopolymerization initiators may be used alone or in combination of two or more. The total content of the photopolymerization initiator in the coating composition is preferably in the range of 0.1 to 10 mass% with respect to the total amount of the composition containing the organic solvent. If the amount added is less than 0.1% by mass, it is difficult to obtain good curability, and if the amount added is more than 10% by mass, the amount of the initiator becomes excessive and the flowability as a coating agent is impaired, and processability It is not preferable because workability is reduced.

  Further, the curing rate can be increased by adding a tertiary amine compound selected from an aliphatic amine derivative and/or an amine benzoate derivative as a sensitizer. Tertiary amine compounds are known to increase reactivity and prevent reaction inhibition by oxygen. Suitable tertiary amine compounds include, for example, free alkylamines such as triethylamine, methyldiethanolamine, triethanolamine, aromatic amines such as 2-ethylhexyl-4-dimethylaminobenzoate, ethyl-4-dimethylaminobenzoate, and polyamines. Examples thereof include allylamine and polymeric amines as derivatives thereof. Active energy ray-polymerizable compounds, such as ethylene double bond unsaturated amines (eg, (meth)acrylated amines), have low odor, low volatility, and the ability to be incorporated into the polymer matrix by curing. It is considered preferable because it has a property of suppressing yellowing.

  The tertiary amine compound can be used in an amount of preferably 0.1 to 10% by mass, more preferably 0.3 to 3% by mass, based on the total amount of the coating composition containing an organic solvent.

  Further, the coating composition used in the method for producing a coated building material of the present invention further comprises an acrylic (meth) oligomer and/or a urethane (meth) acrylate for the purpose of improving scratch resistance of the coated surface using the composition. Resin may be added. The composition ratio when these acrylic (meth) oligomers and/or urethane (meth) acrylate resins are added is “3 when the acrylic (meth) acrylate/acrylic (meth) oligomer/urethane (meth) acrylate is used in combination. “Mass ratio range of solid content of other people” is 50 to 99% by mass of acrylic (meth)acrylate resin, 1 to 50% by mass of acrylic (meth)oligomer, and/or urethane (meth)acrylate resin. Is preferred. More preferably, it is 60 to 90 mass% of acrylic (meth)acrylate resin, and 10 to 40 mass% of acrylic (meth)oligomer and/or urethane (meth)acrylate resin. If the blending amount of the acrylic (meth) oligomer and/or urethane (meth) acrylate resin exceeds 50% by mass, the coating film becomes viscous and the tack-free property does not appear only in the drying step.

  Examples of the acrylic (meth) oligomer include trimethylolpropane (meth)acrylate, hexanediol (meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol. Hexa(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol (meth)acrylate and the like can be mentioned.

As a component constituting the urethane (meth)acrylate resin, a polyfunctional alcohol component, a compound having at least one alcoholic hydroxyl group and at least one (meth)acrylic acid ester or (meth)acrylamide in the molecule, a polyisocyanate compound Is mentioned.
As the polyfunctional alcohol component constituting the urethane (meth)acrylate resin, one or more kinds of compounds selected from the compounds exemplified below may be used alone or in combination of two or more kinds at an arbitrary ratio as necessary. You can

  Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, di(1,2-propylene glycol), tri(1,2-propylene glycol), 1,3-propylene glycol, 1,2 -Butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1, 3-propanediol, 1,5-pentanediol, 1,2-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,6-hexane Diol, 1,2-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1, 2-bis(hydroxymethyl)cyclohexane, 1,3-bis(hydroxymethyl)cyclohexane, 1,4-bis(hydroxymethyl)cyclohexane, bis(hydroxymethyl)tricyclodecane, 1,3-bis(hydroxymethyl)adamantane , 2,3-bis(hydroxymethyl) norbornane, 2,5-bis(hydroxymethyl) norbornane, 2,6-bis(hydroxymethyl) norbornane, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, bisphenol A Ethylene oxide adduct, neopentyl glycol monohydroxypivalate, spiroglycol (3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxospiro[5.5 ] Undecane), trimethylolethane, trimethylolpropane, ethylene oxide modified trimethylolpropane, tris(hydroxyethyl)isocyanuric acid, glycerin, ethylene oxide modified glycerin, propylene oxide modified glycerin, pentaerythritol, ethylene oxide modified pentaerythritol, propylene oxide Modified pentaerythritol, ditrimethylolpropane, ethylene oxide modified ditrimethylolpropane, propylene oxide modified ditrimethylolpropane, dipentaerythritol, ethylene oxide modified dipentaerythritol, propylene oxide modified dipentaerythr Examples include litol and refined castor oil.

As a compound for imparting a terminal radical-polymerizable unsaturated bond, which is a constituent component of a urethane (meth)acrylate resin, one or more alcoholic hydroxyl groups and one or more (meth)acrylic acid ester in a molecule are listed below. Examples thereof include compounds having (meth)acrylamide.
Examples of (meth)acrylic acid esters or (meth)acrylamides having one alcoholic hydroxyl group in the molecule include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth). Acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxymethylcyclohexylmethyl (meth)acrylate, α-hydroxymethyl methyl acrylate, α- Ethyl hydroxymethyl acrylate, ε-caprolactone modified 2-hydroxyethyl (meth)acrylate, γ-butyrolactone modified 2-hydroxyethyl (meth)acrylate, poly(ethylene glycol) mono(meth)acrylate, poly(propylene glycol) mono( (Meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth) Acrylate, glycerin (meth)acrylate stearate, glycerin (meth)acrylate oleate, glycerin di(meth)acrylate, glycerin acrylate methacrylate, bis[(meth)acryloyloxyethyl]isocyanuric acid, N-(2-hydroxyethyl)( (Meth)acrylamide etc. are mentioned. Examples of (meth)acrylic acid esters having two or more alcoholic hydroxyl groups include glycerin (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate and pentaerythritol di(meth)acrylate. ) Acrylate, ditrimethylolpropane di(meth)acrylate, dipentaerythritol tetra(meth)acrylate, (meth)acryloyloxyethyl bis(hydroxyethyl)isocyanuric acid and the like. Others, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl A compound group obtained by reacting an aliphatic diglycidyl ether such as ether with (meth)acrylic acid and generally called an epoxy acrylate can be used. It is also possible to introduce one or more compounds selected from the above as a compound having a 2-hydroxyl (meth)acrylic acid ester structure at both ends to introduce a radical polymerizable unsaturated bond into the urethane resin skeleton.

  Further, as an optional component, wax, plasticizer, dispersant, defoaming agent and the like can be contained.

  Examples of the solvent used in the coating composition used in the method for producing a coated building material of the present invention include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane, ethyl acetate, Butyl acetate, esters such as propyl acetate, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, and alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether. it can.

Further, the method for producing a coated building material of the present invention can be widely applied not only to building material applications but also to surface coating applications such as furniture, musical instruments, office supplies, sports equipment and toys.

Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the part and mass part in the following examples represent mass %.
The weight average molecular weight (in terms of polystyrene) of the present invention was measured by GPC using an HLC8220 system manufactured by Tosoh Corporation under the following conditions.
Separation column: Tosoh Co., Ltd. TSKgelGMHHR-N 4 is used. Column temperature: 40°C. Mobile layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml/min. Sample concentration: 1.0% by weight. Sample injection volume: 100 microliters. Detector: differential refractometer.
Further, the glass transition temperature (Tg) was measured using a differential scanning calorimeter (“DSC Q100” manufactured by TA Instruments Co., Ltd.) under a nitrogen atmosphere and a temperature range of −80 to 450° C. using a cooling device. Scanning was performed under the condition of a temperature of 10° C./min.
Further, the hydroxyl value of each acrylic acrylate resin is calculated by back titrating the residual acid with an alkali when the hydroxyl group in the resin is acetylated with an excess of acetyl reagent, and It is shown in mg of potassium (KOH), and is in accordance with JIS K0070.
Moreover, the average particle diameter of silica was measured using Nano particle UPA EX-150, a nano particle size distribution analyzer manufactured by Nikkiso Co., Ltd.

[Preparation Example 1 Preparation of coating composition 1]
Acrylic acrylate resin A (double bond equivalent 250 g/mol product, weight average molecular weight 25,000, Tg 56° C., hydroxyl value 113 mg KOH/g) Solid content 35 parts by mass, IGM 1-hydroxy-cyclohexyl-phenyl-ketone "Omnirad 184" 5 parts by mass, polymerization inhibitor dibutylhydroxytoluene (BHT) solid content 0.05 parts by mass, matting agent wet silica "Sylysia 350 average particle size 3.9 μm, apparent specific gravity 0.49 g/mL, oil absorption" 310 mL/100 g, pore volume 1.7 mL/g” 7 parts by mass, TEGO RAD2700 (acrylic modified polysiloxane Cas number: 157811-87-5) which is a compound (acryloyl polysiloxane) having an acryloyl group and a siloxane skeleton 2. 4 parts by mass and 15.5 parts by mass of methyl ethyl ketone were added and mixed by stirring with a stirrer for 1 hour. Further, 30 parts by mass of a mixed solvent of ethyl acetate and butyl acetate in a mass ratio of 7:3 were added and stirred to give a total of 94.95 parts by mass. Parts (solid content 49.45 parts by mass) of coating composition 1 was prepared. It was confirmed that the viscosity of the obtained coating composition 1 at 25° C. was 9.00 seconds by Zahn cup #4 (manufactured by Kyushu Co., Ltd.).

[Preparation Example 2 Preparation of coating composition 2]
Preparation Example 1 except that TEGO RAD2700 (acryl-modified polysiloxane Cas No. 157811-87-5), which is a compound (acryloyl polysiloxane) having an acryloyl group and a siloxane skeleton, in Preparation Example 1 was changed to 1.2 parts by mass. With the same composition as above, the mixture was stirred and mixed for 1 hour with a stirrer, and 28 parts by mass of a mixed solvent of ethyl acetate and butyl acetate in a mass ratio of 7:3 was added and stirred to give a total of 91.75 parts by mass (solid content 48.25 parts by mass). Coating composition 2) was prepared. It was confirmed that the viscosity of the obtained coating composition 2 at 25° C. was 9.51 seconds using Zahn cup #4 (manufactured by Riaisha Co., Ltd.).

[Preparation Example 3 Preparation of coating composition 3]
7 parts by mass of delusterant wet silica “Thylysia 350 average particle size 3.9 μm, apparent specific gravity 0.49 g/mL, oil absorption 310 mL/100 g, pore volume 1.7 mL/g” of Preparation Example 1 Wet silica “Nipgel AZ-204 average particle diameter 1.3 μm, apparent specific gravity 0.12 g/mL, oil absorption 355 mL/100 g, pore volume 2.0 mL/g” With the same composition, stir and mix with a stirrer for 1 hour, and further add 38 parts by mass of a mixed solvent of ethyl acetate and butyl acetate in a mass ratio of 7:3, and stir to give a total of 102.95 parts by mass (solid content 49.45 parts by mass). Coating Composition 3 was prepared. It was confirmed that the viscosity of the obtained coating composition 3 at 25° C. was 9.64 seconds using Zahn cup #4 (manufactured by Riaisha Co., Ltd.).

[Preparation Example 4 Preparation of coating composition 4]
Further, 7 parts by mass of the matting agent wet silica “Thylysia 350 average particle size 3.9 μm, apparent specific gravity 0.49 g/mL, oil absorption amount 310 mL/100 g, pore volume 1.7 mL/g” of Preparation Example 1 was further scratch resistant. Dry silica as an improving additive, “AEROSIL R972 (hydrophobic dry silica having a structure changed after surface treatment with dimethyldichlorosilane) manufactured by Nippon Aerosil Co., Ltd., average particle diameter 0.25 μm” 7 parts by mass was added, and methyl ethyl ketone 27. Except that the amount was changed to 5 parts, the mixture was mixed with the same composition as in Preparation Example 1 with a stirrer for 1 hour, 46 parts by mass of a mixed solvent of ethyl acetate and butyl acetate in a mass ratio of 7:3 was added, and the mixture was stirred. The coating composition 4 of 95 mass parts (solid content 49.45 mass parts) was produced. It was confirmed that the viscosity of the obtained coating composition 4 at 25° C. was 9.29 seconds using Zahn cup #4 (manufactured by Riaisha Co., Ltd.).

[Preparation Example 5 Preparation of coating composition 5]
Acrylic acrylate resin A of Preparation Example 1 (double bond equivalent 250 g/mol product, weight average molecular weight 25,000, Tg 56°C, hydroxyl value 113 mgKOH/g) was changed to 28 parts by mass, and further urethane acrylate Miramer PU610 (aliphatic urethane acrylate). An average functional group number of 6 and a weight average molecular weight of 1800) were added in an amount of 7 parts by mass, and the mixture was changed to 22.5 parts of methyl ethyl ketone. The mixture was stirred and mixed for 1 hour with a stirrer using the same composition as in Preparation Example 1, and ethyl acetate and butyl acetate were further mixed. 16 parts by mass of a mixed solvent having a mass ratio of 7:3 was added and stirred to prepare 87.95 parts by mass (solid content 49.45 parts by mass) of coating composition 5. It was confirmed that the viscosity of the obtained coating composition 5 at 25° C. was 9.25 seconds using Zahn cup #4 (manufactured by Riaisha Co., Ltd.).

[Preparation Example 6 Preparation of coating composition 6]
Instead of 35 parts by mass of acrylic acrylate resin A (double bond equivalent 250 g/mol product, weight average molecular weight 25,000, Tg 56° C., hydroxyl value 113 mgKOH/g) of Preparation Example 1, acrylic acrylate resin B (double bond equivalent). 550 products g/mol product, weight average molecular weight 25,000, Tg 85° C., hydroxyl value 50 mgKOH/g) Solid content 35.7 parts by mass except that the mixture was the same as in Preparation Example 1 and stirred and mixed for 1 hour with a stirrer. Then, 42 parts by mass of a mixed solvent of ethyl acetate and butyl acetate in a mass ratio of 7:3 was added and stirred to prepare a total of 107.65 parts by mass (solid content 50.15 parts by mass) of Coating Composition 6. It was confirmed that the viscosity of the obtained coating composition 6 at 25° C. was 9.92 seconds using Zahn cup #4 (manufactured by Riaisha Co., Ltd.).

[Preparation Example 7 Preparation of coating composition 7]
35 parts by mass of acrylic acrylate resin A (double bond equivalent 250 g/mol product, weight average molecular weight 25,000, Tg 56° C., hydroxyl value 113 mgKOH/g) of Preparation Example 1 was reduced to 28 parts by mass, and further, Toagosei Co., Ltd. ) Manufactured by Aronix M-402 (mixture of dipentaerythritol which is a pentafunctional polymerizable acrylate monomer and hexaacrylate which is a hexafunctional polymerizable acrylate monomer, and the proportion of pentaacrylate in the product is 30 to 40% by mass). Aside from the addition of 7 parts by mass, the same composition as in Preparation Example 1 was stirred and mixed for 1 hour with a stirrer, and 16 parts by mass of a mixed solvent of ethyl acetate and butyl acetate in a mass ratio of 7:3 were added and stirred, for a total of 87 The coating composition 7 of 0.95 mass part (solid content 49.45 mass part) was produced. It was confirmed that the viscosity of the obtained coating composition 7 at 25° C. was 9.25 seconds using Zahn cup #4 (manufactured by Riaisha Co., Ltd.).

[Preparation Example 8 Preparation of coating composition 8]
A compound having a fluoroalkyl group in place of 2.4 parts by mass of TEGO RAD2700 (acrylic modified polysiloxane, Cas number: 157811-87-5), which is a compound (acryloyl polysiloxane) having an acryloyl group and a siloxane skeleton of Preparation Example 1. MEGAFACE RS-75 (manufactured by DIC Corporation), which is a solid content of 0.48 parts by mass, is stirred and mixed for 1 hour with a stirrer with the same composition as in Preparation Example 1, and further the mass of ethyl acetate and butyl acetate. 22 parts by mass of a mixed solvent having a ratio of 7:3 was added and stirred to prepare a total of 85.03 parts by mass (solid content 47.53 parts by mass) of coating composition 8. It was confirmed that the viscosity of the obtained coating composition 8 at 25° C. was 9.74 seconds using Zahn cup #4 (manufactured by Riaisha Co., Ltd.).

[Preparation Example 9 Preparation of coating composition 9]
Using the stirrer with the same formulation as in Preparation Example 1, except that 0.48 parts by mass of Megafac RS-75 (manufactured by DIC Corporation), which is a compound having a fluoroalkyl group in Preparation Example 8, was changed to 0.24 parts by mass. After stirring and mixing for 1 hour, 22 parts by mass of a mixed solvent of ethyl acetate and butyl acetate in a mass ratio of 7:3 was added and stirred to obtain a total of 84.79 parts by mass (solid content 47.29 parts by mass) of the coating composition 9. It was made. It was confirmed that the viscosity of the obtained coating composition 9 at 25° C. was 9.82 seconds using Zahn cup #4 (manufactured by Riaisha Co., Ltd.).

[Preparation Example 10 Preparation of coating composition 10]
BASF's 1-hydroxy-cyclohexyl-phenyl-ketone "Omnirad 184" of Preparation Example 1 was changed to 2.5 parts by mass except that the mixing ratio was changed to 2.5 parts by mass. Further, 30 parts by mass of a mixed solvent of ethyl acetate and butyl acetate in a mass ratio of 7:3 was added and stirred to prepare a total of 92.45 parts by mass (solid content 46.95 parts by mass) of Coating Composition 10. It was confirmed that the viscosity of the obtained coating composition 10 at 25° C. was 9.99 seconds using Zahn Cup #4 (manufactured by Riaisha Co., Ltd.).

[Preparation Example 11 Preparation of coating composition 11]
Stirring and mixing for 1 hour with a stirrer without adding TEGO RAD2700 (acrylic modified polysiloxane Cas No. 157811-87-5) which is a compound (acryloyl polysiloxane) having an acryloyl group and a siloxane skeleton in the formulation of Preparation Example 1 Then, 30 parts by mass of a mixed solvent of ethyl acetate and butyl acetate in a mass ratio of 7:3 was added and stirred to prepare a total of 92.55 parts by mass (solid content 47.05 parts by mass) of Coating Composition 11. It was confirmed that the viscosity of the obtained coating composition 11 at 25° C. was 9.00 seconds by Zahn cup #4 (manufactured by Riaisha Co., Ltd.).

[Preparation Example 12 Preparation of coating composition 12]
Stirring for 1 hour with a stirrer without adding TEGO RAD2700 (acrylic modified polysiloxane Cas No. 157811-87-5) which is a compound (acryloyl polysiloxane) having an acryloyl group and a siloxane skeleton in the formulation of Preparation Example 5 Then, 40 parts by mass of a mixed solvent of ethyl acetate and butyl acetate in a mass ratio of 7:3 was added and stirred to prepare a total of 102.25 parts by mass (solid content 47.75 parts by mass) of Coating Composition 12. It was confirmed that the viscosity of the obtained coating composition 12 at 25° C. was 9.82 seconds using Zahn cup #4 (manufactured by Riaisha Co., Ltd.).

[Preparation Example 13 Preparation of coating composition 13]
Stirring for 1 hour with a stirrer without adding TEGO RAD2700 (acrylic modified polysiloxane Cas No. 157811-87-5) which is a compound (acryloyl polysiloxane) having an acryloyl group and a siloxane skeleton in the formulation of Preparation Example 6 Then, 42 parts by mass of a mixed solvent of ethyl acetate and butyl acetate in a mass ratio of 7:3 was added and stirred to prepare a total of 105.25 parts by mass (solid content 47.75 parts by mass) of Coating Composition 13. It was confirmed that the viscosity of the obtained coating composition 13 at 25° C. was 9.92 seconds using Zahn cup #4 (manufactured by Riaisha Co., Ltd.).

[Preparation Example 14 Preparation of coating composition 14]
Stirring for 1 hour with a stirrer without adding TEGO RAD2700 (acrylic modified polysiloxane Cas No. 157811-87-5) which is a compound (acryloyl polysiloxane) having an acryloyl group and a siloxane skeleton in the formulation of Preparation Example 7 Then, 16 parts by mass of a mixed solvent of ethyl acetate and butyl acetate at a mass ratio of 7:3 was added and stirred to prepare a total of 85.55 parts by mass (solid content 47.05 parts by mass) of Coating Composition 14. It was confirmed that the viscosity of the obtained coating composition 14 at 25° C. was 9.25 seconds using Zahn Cup #4 (manufactured by Kyushu Co., Ltd.).

<Preparation of decorative sheet>
[Examples 1 to 10]
Prepare black ink paper as a base material, polyethylene terephthalate film for easy adhesion treatment (hereinafter PET film, A4300 manufactured by Toyobo Co., Ltd. A4300 thickness 100 μm), and use the bar coater (4 μm) to prepare in Preparation Examples 1 to 10 above. Each of the coating compositions 1 to 10 was applied, and then ultraviolet irradiation was performed once by a high pressure mercury lamp to cure the coating composition film. Using a UV irradiation device (GS Yuasa Corporation) equipped with an air-cooled high-pressure mercury lamp (output 120 W/cm1 lamp) and a belt conveyor, put the developed material on the conveyor and pre-irradiate it with ultraviolet light in the chamber atmosphere. After introducing nitrogen gas so that the oxygen concentration remained at 1% or less, the coating composition film was cured by passing it directly under the lamp (irradiation distance: 11 cm) at a speed of 25 meters per minute.
It was confirmed that the ultraviolet irradiation amount was 40 mJ/cm ² using an ultraviolet integrated photometer (manufactured by GS Yuasa Corporation, industrial UV checker UVR-N1).

[Comparative Examples 1 to 10]
In the same manner as in Examples 1 to 10, a solid black paper and a polyethylene terephthalate film (hereinafter, PET film, manufactured by Toyobo Co., Ltd., A4300 thickness 100 μm) were prepared as a base material, and coating compositions 1 to 10 were applied to a bar. After coating each with a coater (4 μm), UV irradiation was performed under the same conditions except that no nitrogen gas was introduced at all under the same conditions.
It was confirmed that the ultraviolet irradiation amount was 40 mJ/cm ² using an ultraviolet integrated photometer (manufactured by GS Yuasa Corporation, industrial UV checker UVR-N1).

[Comparative Examples 11 to 14]
In the same manner as in Examples 1 to 10, solid black paper as a substrate, and a polyethylene terephthalate film (hereinafter, PET film, manufactured by Toyobo Co., Ltd., A4300 thickness 100 μm) for easy adhesion were prepared, and coating compositions 11 to 14 were applied to a bar. After applying each with a coater (4 μm), nitrogen gas was introduced so that the oxygen concentration in the atmosphere in the chamber pre-irradiated with ultraviolet rays remained at 1% or less in the same manner as in Examples 1 to 10, and then the lamp was used. The coating composition film was cured by passing it directly underneath (irradiation distance: 11 cm) at a speed of 25 meters per minute.
It was confirmed that the ultraviolet irradiation amount was 40 mJ/cm ² using an ultraviolet integrated photometer (manufactured by GS Yuasa Corporation, industrial UV checker UVR-N1).

〔Evaluation methods〕
The evaluation method of the decorative sheet by the manufacturing method of the coating building material of this invention is shown.

[Evaluation item 1: Cellotape resistance (registered trademark)]
Apply cellophane tape to the coating composition cured film on the surface of the decorative sheet that uses solid black paper as the base material, and rapidly peel it off 10 times, and then visually judge the appearance condition of the printed film. It was evaluated in 7 steps.
(Evaluation criteria)
7: No peeling of the printed film was observed.
6: 95% or more of the printed film remained in the black solid paper in the area ratio. 5: 80% or more and less than 95% of the printed film in the area ratio remained on the black solid paper.
4: 60% or more and less than 80% of the printed film as an area ratio remained on the black solid paper.
3: 40% or more and less than 60% of the printed film as an area ratio remained on the black solid paper.
2: 20% or more and less than 40% of the printed film as an area ratio remained on the black solid paper.
1: Less than 20% of the printed film by area ratio remained on the black solid paper.

[Evaluation item 2: Contamination resistance]
Contamination resistance of decorative sheet surface using PET film as base material According to JAS Contamination A, the decorative sheet sample was placed horizontally, and then a commercially available oil-based black magic (extremely thick) was placed on the surface of the sample. The used wire was drawn back and forth 3 times, and after leaving it to stand for 10 minutes to dry, the work of wiping the cloth with isopropyl alcohol and wiping was repeated 4 times, and the stain mark was visually evaluated in the following 7 stages.
(Evaluation criteria)
7: No stain marks are found on the printed film.
6: A trace of contamination can be confirmed very slightly.
5: A trace of contamination can be confirmed.
A trace of medium pollution of 4:5 and 3 can be confirmed.
3: Contamination marks can be confirmed.
2:1 and 3 moderate stains can be seen.
1: The printed film can be clearly confirmed.

Table 1 shows the preparation examples of the coating compositions 1 to 14, and Tables 2 to 4 show the evaluation results of the decorative sheet using the same.
In addition, all the numerical values in Table 1 are described as solid contents except for the organic solvent.

  The decorative sheet produced by the method for producing a painted building material of the present invention has excellent resistance to cellophane tape (registered trademark) and stain resistance on the surface of the painted building material.

Claims (5)

A method for producing a coating building material having an active energy ray-curable coating on a base material,
On a substrate, the double bond equivalent 100~750g / mol, compounds having a weight average molecular weight has a 10,000 to 100,000 of acrylic (meth) acrylate resin, an acryloyl group and a siloxane skeleton, containing 及 beauty silica (1) of applying a coating composition to form a coating film of the coating composition,
The coating film obtained in the step (1) includes a step (2) of irradiating an active energy ray of 30 to 1000 mJ/cm ² at least once in a gas atmosphere having an oxygen concentration of less than 8%. A method of manufacturing a painted building material ,
A method for producing a coated building material, wherein the compound having an acryloyl group and a siloxane skeleton is a silicone epoxy (meth)acrylate represented by the general formula (2).

However, in the general formula (2), l is an integer of 0 or more, m is an integer of 1 or more, n is an integer of 0 or more, and R3, R4, and R5 are each independently hydrogen or a methyl group. Is.

The method for producing a coated building material according to claim 1, wherein the acrylic (meth)acrylate resin has a glass transition temperature (Tg) in the range of 40 to 130° C. and a hydroxyl value of 5 to 300 mgKOH/g.
The method for producing a coated building material according to claim 1 or 2, wherein the silica is wet silica having an average particle diameter of 0.1 to 25 µm and/or dry silica having an average particle diameter of 0.1 to 3 µm.
Furthermore, the manufacturing method of the coating building material as described in any one of Claims 1-3 containing a polyfunctional (meth)acrylate and/or a urethane (meth)acrylate resin.
  A coated building material obtained by the manufacturing method according to any one of claims 1 to 4.