JP2005305294A - Active-energy-ray-hardenable coated building material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active-energy-ray-hardenable coated building material having a hardenable film which has high stain resistance and scratch resistance and is low in residual smelling of substances having a strong odor. <P>SOLUTION: This material has the hardenable film on a wooden base material. The film is formed through a first process of applying an active-energy-ray-hardenable coating composition containing an active-energy-ray-polymerizable oligomer or monomer and a polymerization initiator onto the wooden base material at 25°C in a gas atmosphere of an oxygen concentration of 21% at a film thickness of 1-100 μm, while the surface of the film remains unhardened on irradiation with UV rays in an intensity of 100 mJ/cm<SP>2</SP>, and a second process of irradiating the resultant body with active energy rays in an intensity of 80-500 mJ/cm<SP>2</SP>in a gas atmosphere of an oxygen concentration of lower than 8%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an active energy ray-curable coating building material having a cured film of an active energy ray-curable coating composition that is excellent in stain resistance, scratch resistance, and reduction of residual surface odor.

  Conventionally, the surface of base materials such as paper, plastic, glass, metal, wood, and ceramic has been coated to protect the surface by adding various functions and design features such as high hardness and stain resistance. Yes. In recent years, the demand for active energy ray-curable high non-volatile paints has been increasing in response to environmental problems. Among them, a wood base material such as flooring is used, and a coating film of a product laid on the floor is often exposed to scratches and contamination, so a coating having high hardness and excellent stain resistance is required.

  Furthermore, in recent years, interest in symbiosis with pets has increased, and interior building materials for pet-symbiotic housing have been attracting attention. The coating film of products laid on the floor has scratch resistance due to claw scratches, etc., and contamination resistance due to manure, etc. In addition to being excellent in coating, a coating excellent in reducing residual odor on the surface is required.

  As a paint composition for forming a coating film for a wood material having excellent stain resistance, a wood material paint composition using a silicone-modified active energy ray-curable compound and a particulate material is known (for example, a patent) Reference 1). Moreover, the wood furniture coating composition which consists of a composition which has a photocurable methacrylate resin and a photocurable fluorine-containing resin is known (for example, refer patent document 2). However, there is a demand for a material that exhibits sufficient suitability for particularly strong pollutants such as hair dye resistance. Furthermore, there is a need for a coating composition that forms a cured film having a reduced residual odor of a strong odor substance.

Japanese Patent Laid-Open No. 2003-213211 JP 2003-111586 A

  An object of the present invention is a coating building material having a cured film on a wood-based substrate, which is resistant to contamination, particularly stain resistance to hair dyeing liquid, and scratch resistance, particularly scratch resistance to steel wool. An object of the present invention is to provide a coated building material having a cured film of an active energy ray-curable coating composition that is excellent and further has a reduced residual odor with a strong odor substance.

  As a result of intensive studies, the present inventors applied an active energy ray-curable coating composition having specific curing conditions to the surface of a wooden base material, and irradiated active energy rays in a gas atmosphere having an oxygen concentration of less than 8%. As a result, it was found that a coating film excellent in contamination resistance, scratch resistance and reduction in residual odor was obtained, and the present invention was achieved.

That is, the present invention is a coating building material having an active energy ray-curable film on a wood base material, the cured film having an active energy ray-polymerizable oligomer and / or monomer, a polymerization initiator, and a coating film An active energy ray-curable coating composition whose coating surface is uncured when irradiated with ultraviolet rays of 100 mJ / cm ² at a temperature of 25 ° C. in a gas atmosphere having a thickness of 1 to 100 μm and an oxygen concentration of 21% is applied to a wooden substrate. Active energy ray curing characterized by being a cured film formed by a coating step and a step of irradiating 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%. Providing mold-painted building materials.

The present invention is a coating building material excellent in stain resistance, wherein the surface hue change (ΔE) of the cured film after 1 hour after applying the hair dyeing solution to the surface of the cured film by the above means is less than 0.5. , painted building materials gloss value reduction of the cured film surface when was 50 reciprocate under conditions surface steel wool 1 cm ² per 8N / cm ² of the above-described cured film is excellent in surface hardness is less than 20%, more The coating building material which has an active energy ray hardening-type membrane | film | coat with which the residual odor of the surface after apply | coating a strong odor substance and wiping off was reduced can be provided.

  With the active energy ray-curable coating building material of the present invention, the coating building material has a cured film that has excellent contamination resistance and scratch resistance, and further has reduced odor on the surface of the coating film after applying and wiping off a strong odor substance. Can be provided.

The active energy ray-curable painted building material of the present invention is a painted building material having a cured film on a wooden base material, and the cured film has an active energy ray-polymerizable oligomer and / or monomer and a polymerization initiator. An active energy ray-curable coating composition whose coating surface is uncured when irradiated with ultraviolet rays of 100 mJ / cm ² at a temperature of 25 ° C. in a gas atmosphere having a coating film thickness of 1 to 100 μm and an oxygen concentration of 21%, Coating which is a cured film formed by a step of coating on a material and a step of irradiating 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% It is a building material. Each component requirement is explained in full detail below.

  Among the active energy ray-polymerizable monomers used in the active energy ray-curable coating composition used for the coating building material of the present invention, monofunctional monomers include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. , Lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) Acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene group Cole (meth) acrylate, nonylphenoxyethyl (meth) acrylate, nonylphenoxytetraethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, butoxytriethylene glycol ( (Meth) acrylate, 2-ethylhexyl polyethylene glycol (meth) acrylate, nonylphenyl polypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, glycidyl (meth) acrylate, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate , Polypropylene glycol (meth) acrylate, epichlorohi Phosphorus (hereinafter abbreviated as ECH) modified butyl (meth) acrylate, ECH modified phenoxy (meth) acrylate, ethylene oxide (hereinafter abbreviated as EO) modified phthalic acid (meth) acrylate, EO modified succinic acid (meth) acrylate, caprolactone modified 2 -Hydroxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, morpholino (meth) acrylate, EO-modified phosphoric acid (meth) acrylate and the like.

  As bifunctional monomers, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate 1,9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO modified Neopentyl glycol di (meth) acrylate, propylene oxide (hereinafter abbreviated as PO) modified neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, E H-modified bisphenol A di (meth) acrylate, EO-modified bisphenol S di (meth) acrylate, hydroxypivalate ester neopentyl glycol diacrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol diacrylate, neopentyl glycol-modified trimethylolpropane di (Meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, dicyclopentenyl diacrylate, EO-modified dicyclopentenyl di (meth) acrylate, di (meth) acryloyl isocyanurate, and the like.

  Examples of trifunctional or higher polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, ECH Modified trimethylolpropane tri (meth) acrylate, ECH-modified glycerol tri (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy Penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Rate, caprolactone-modified dipentaerythritol hexa (meth) acrylate.

  As the active energy ray polymerizable oligomer, conventionally known oligomers can be used. Among them, typical examples include bisphenol A type, novolak type, polyhydric alcohol type, polybasic acid type, polybutadiene type epoxy ( Examples thereof include (meth) acrylate, polyester type, and polyether type urethane (meth) acrylate. In the present invention, it is preferable to use an active energy ray polymerizable oligomer in combination in order to improve coating suitability.

  These oligomer components can be used in one or a mixture of two or more as required. The content at this time is preferably 5 to 30% by mass.

  Other active energy ray polymerizable compounds that can be used in the present invention include, for example, N-vinylpyrrolidone, N-vinylcarbazole, styrene, 4-methylstyrene, α-methylstyrene, 1,4-divinylbenzene, diallyl phthalate. And maleimide compounds described in JP-A-11-124403 and JP-A-11-124404, which can be used as necessary.

  Examples of the hydrogen abstraction type polymerization initiator used as a polymerization initiator in the present invention include conventionally known benzophenone, acetophenone, diethoxyacetophenone, benzyl, benzoylbenzoic acid, Michler's ketone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, and the like. Is mentioned.

  Examples of the polymerization initiator that can be used in the present invention include photocleavable types such as benzoin ethyl ether, benzyldimethyl ketal, hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methylphenyl ketone. Among these hydrogen abstraction type and photocleavage type polymerization initiators, one or two or more types can be used in combination.

  The blending ratio of the polymerization initiator in the resin composition comprising the active energy ray polymerizable monomer and oligomer component and the polymerization initiator is preferably 1 to 15% by mass in 100% by mass of the resin composition.

  In addition, these polymerization initiators can be used in combination with known and commonly used photosensitizers. When using together, it is preferable that it is 1-15 mass% in 100 mass% of resin compositions.

  When low gloss is intended, wax, matte beads, or the like can be added. When added, the blending ratio is preferably 0.1 to 15% by mass in 100% by mass of the coating composition.

  The active energy ray-curable coating composition used for the active energy ray-curable coating building material of the present invention is further provided with various functions within a range that does not depart from the object of the present invention, if necessary. Additives such as pigments, lubricants, plasticizers, antifoaming agents, antioxidants, coupling agents, organic solvents and chelating agents can be added.

  Production of the active energy ray-curable coating composition used for the active energy ray-curable coating building material of the present invention can be carried out by a conventionally known method. As an example, an active energy ray polymerizable monomer and / or oligomer, a polymerization initiator, and, if necessary, a coating additive can be prepared in this order by mixing, stirring, and the like.

  Although the viscosity range of the active energy ray-curable coating composition used for the active energy ray-curable coating building material of the present invention varies depending on the coating method, it is preferably 40 to 1000 mPa · s at a liquid temperature of 25 ° C.

  The volatile content of the coating composition used in the active energy ray-curable coating building material of the present invention is the temperature of the coating composition before curing or heating, except for the components involved in polymerization by the active energy ray in the coating composition. The other components are called non-volatile components.

  The nonvolatile content of the active energy ray-curable coating composition used for the active energy ray-curable coating building material of the present invention is preferably 90 to 100% by mass. The present invention provides a coating and building material having a cured film with reduced residual odor with respect to a strong odor substance, using a highly non-volatile coating composition capable of addressing environmental problems, having excellent contamination resistance and scratch resistance. it can.

The active energy ray-curable coating building material of the present invention has an active energy ray of 80 to 500 mJ / in a gas atmosphere having an oxygen concentration of less than 8% after the step of applying the active energy ray-curable coating composition to the substrate surface. It is formed by a step of irradiating at least once with cm ² .

  The surface uncured surface curing property of the present invention refers to a state in which a finger is pressed against an ultraviolet irradiation coating film with a weight of about 50 g and a finger is applied with a paint or a fingerprint mark is left on the coating film. A state without these is called tack-free.

  The gas atmosphere having an oxygen concentration of less than 8% according to the present invention is realized by injecting one or two kinds of mixed gases selected from nitrogen gas, carbon dioxide gas, and argon gas into the reaction vessel together with air or alone. It is what is done.

  The active energy ray used in the irradiation process in the process of producing the active energy ray-curable coating building material of the present invention is an ionizing radiation, an electromagnetic wave or the like, such as an ultraviolet ray, an electron beam, or a γ ray. preferable.

  When irradiating ultraviolet rays in a gas atmosphere having an oxygen concentration of less than 8%, a known ultraviolet irradiation device equipped with a high-pressure mercury lamp, excimer lamp, metal halide lamp, or the like can be used. In view of preventing damage to the substrate due to heat and the like, the ultraviolet irradiation amount at the time of curing preferably does not exceed 2.0 times the irradiation amount to be tack-free by performing ultraviolet curing alone, and is generally about 1.5. More preferably, it is about double.

  When irradiating an electron beam in a gas atmosphere having an oxygen concentration of less than 8%, a known electron beam irradiation apparatus can be used. The amount of electron beam irradiation at the time of curing is preferably not more than 2.0 times the amount of irradiation to be tack-free by carrying out electron beam curing alone, from the viewpoint of preventing damage to the coating film and the substrate. It is more preferable that the amount of irradiation is the same as the irradiation amount that is tack-free by performing electron beam curing.

  The active energy ray-curable coating building material of the present invention is preferably used for building materials such as floor materials and wall materials in which the active energy ray-curable coating composition is coated on a wooden base material. As the woody base material, plate materials such as oak, hippo and beech are arbitrarily used. The cured film of the painted building material of the present invention has been difficult with conventional wood-based substrates, and has high stain resistance such as hair dyeing stain resistance and high scratch resistance such as steel wool resistance, and further has an odor. It has a significant effect on the reduction of residual odor for strong substances.

  The active energy ray-curable coating composition used for the active energy ray-curable coating building material of the present invention is suitably used as an overcoat on the above-mentioned base material, after being subjected to undercoating, intermediate coating, etc., if necessary. Used.

  As a coating method of the active energy ray curable coating composition in the process of producing the active energy ray curable coating building material of the present invention, a conventionally known method can be applied. There are coat, bar coat, flow coat and dip coat.

  The coating amount when the active energy ray-curable coating composition is applied by the above-described coating method is preferably 1 to 100 μm, more preferably 1 to 20 μm, as a cured coating film.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these. In the following, unless otherwise specified, the numbers in the table represent parts by mass.

(Pretreatment of substrate)
A base material is used as a base material, a UV sealing paint is applied as an undercoat, and 20 μm is applied as a dry film thickness, followed by UV curing, and a UV sanding paint is applied as an intermediate coating, and 20 μm is applied as a dry film thickness and UV cured. . Thereafter, sanding and pretreatment were performed.

Example 1
60 parts of trifunctional urethane acrylate oligomer, 20 parts of trimethylolpropane triacrylate, 10 parts of 1,6-hexanediol dimethacrylate, 5 parts of Irgacure 184, 5 parts of polyethylene wax, and 5 parts of polyethylene wax A paint was prepared. Using the above-mentioned pretreated base material, a natural roll coater was applied so that the dry film thickness was 10 μm, and the base material having a cured film was irradiated with 160 mj / cm ² ultraviolet rays in an atmosphere with an oxygen concentration of 4%. Obtained.

(Example 2)
65 parts of a trifunctional urethane acrylate oligomer, 20 parts of trimethylolpropane triacrylate, 10 parts of 1,6-hexanediol dimethacrylate, and 5 parts of Irgacure 184 were blended, and a paint was prepared with a dispersion stirrer. Using the above-mentioned pretreated base material, a natural roll coater was applied so that the dry film thickness was 10 μm, and the base material having a cured film was irradiated with 160 mj / cm ² ultraviolet rays in an atmosphere with an oxygen concentration of 4%. Obtained.

(Comparative Example 1)
The same paint as in Example 2 described above, “65 parts trifunctional urethane acrylate oligomer, 20 parts trimethylolpropane triacrylate, 10 parts 1,6-hexanediol dimethacrylate, 5 parts Irgacure 184, "Paint" was prepared with a dispersion stirrer. Using the above-mentioned pretreated base material, a natural roll coater is applied so that the dry film thickness is 10 μm, and the base material has a cured film by irradiation with 320 mj / cm ² ultraviolet rays in the air (oxygen concentration 21%). Got.

  Each of the obtained cured coating films was tested according to the method described below.

(1) Gloss measurement Gloss was measured with VG2000 (manufactured by Nippon Denshoku), and the result was shown as 0 to 100 gloss. The gloss measurement conditions were an incident angle of 60 degrees and a reflection angle of 60 degrees.

(2) Scratch resistance test After the steel wool # 0 (manufactured by Nippon Steel Wool) was reciprocated 50 times under the conditions of 1 cm ² and 8.0 N / cm ^{2 on} the surface of the coating material to be coated, the surface gloss was obtained under the conditions described above. Was measured to evaluate the rate of gloss reduction.

(3) Contamination resistance test After applying a hair dyeing solution (Bigu Cream Tone 7G, manufactured by Hoyu Co., Ltd.) to the surface of the paint coating, left for 1 hour, wiped off with water and detergent, and then SE2000 (Nippon Denshoku) The surface Lab value before and after the test was measured and ΔE was calculated to evaluate the degree of contamination.

(4) Residual odor resistance test After applying a curry powder solution (manufactured by SB Foods Co., Ltd., 0.5% aqueous solution of SB curry powder) on the surface of the paint coating, leaving it for 1 hour, wiping with water, The degree of odor remaining on the surface was evaluated, and the result was expressed as (good) ◎ -−- △ -x (bad).

  From the above results, coating under specific conditions and active energy ray irradiation are resistant to contamination, especially stain resistance to hair dyeing liquid and scratch resistance, particularly scratch resistance to steel wool, curry, etc. It turns out that it is effective in reduction of the residual odor of a substance with strong odor.

With the active energy ray-curable coating building material according to the present invention, it is possible to provide various coating building materials that are excellent in stain resistance, scratch resistance, and residual odor resistance.

Claims (6)

A coated building material having an active energy ray-curable film on a wood-based substrate, the cured film having an active energy ray-polymerizable oligomer and / or monomer, a polymerization initiator, and a coating film thickness of 1 to 100 μm, A step of coating an active energy ray-curable coating composition having an uncured coating surface when irradiated with ultraviolet rays of 100 mJ / cm ² at a temperature of 25 ° C. in a gas atmosphere having an oxygen concentration of 21% on a wooden substrate; An active energy ray-curable coating building material, which is a cured film formed by a step of irradiating 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%. 2. The active energy ray-curable coating according to claim 1, wherein the inert gas contained in the gas having an oxygen concentration of less than 8% is one or more inert gases selected from nitrogen gas, carbon dioxide gas, and argon gas. Building materials. The active energy ray-curable painted building material according to claim 1 or 2, wherein the active energy ray in the irradiation step is ultraviolet light. 4. The active energy ray-curable coating building material according to claim 1, wherein the cured film has a surface gloss value of 60 to 100. The active energy ray curable type according to any one of claims 1 to 4, wherein the surface hue change (ΔE) of the cured film after 1 hour of applying the hair dyeing solution to the surface of the cured film is less than 0.5. Painted building material. The gloss value reduction of the cured film surface when steel wool is reciprocated 50 times on the surface of the cured film described above under the condition of 8 N / cm ² per 1 cm ² is less than 20%. Active energy ray curable paint building material.