JP2009078380A - Hydraulically transferred body, and method of manufacturing hydraulically transferred body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydraulically transferred body which is short in the period of time required for curing a coating layer, can be manufactured in a short-time process, and is excellent in adhesion to a transfer object in the entire part of the layer including a printing layer and the coating layer, and to provide a method of manufacturing the hydraulically transferred body. <P>SOLUTION: The hydraulically transferred body comprises the transfer object, the printing layer formed by transferring a film for hydraulic transfer to the surface of the transfer object, and coating layer formed from a curable coating material composition on the surface of the printing layer, wherein the composition is an active ray curable coating material composition containing (A) a compound having an ethylenically unsaturated group and an isocyanate group in one molecule, (B) an ethylenically unsaturated group-containing compound other than the above component (A), and (C) a photopolymerization initiator. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hydraulic transfer member having a coating layer made of an active energy ray-curable coating composition and a method for producing the hydraulic transfer member.

  Conventionally, printing by a hydraulic transfer method has been performed as one of printing methods for automobile interior parts, home appliances, office supplies, indoor decorations, and the like. In the hydraulic transfer method, a transfer film having a predetermined water-insoluble printing pattern on a water-soluble film is sequentially supplied and floated on the water surface flowing in the transfer tank, and the transfer film is wetted with water. Then, while contacting the transfer film, the article to be printed (transfer object) such as a plastic molded product is immersed in water in the transfer tank, and the printing pattern on the transfer film is transferred to the surface of the article using water pressure. This is a method for forming a printing layer.

  Since the printing surface by such a hydraulic transfer method is generally poor in water resistance, chemical resistance, weather resistance, durability against external mechanical shock, and high-quality feeling, the printed surface is finished with a transparent coating composition. Is generally applied.

  For example, Patent Document 1 discloses a curable resin composition comprising a polyol resin having a specific structure and an isocyanate compound in a hydraulic transfer body obtained by coating a printed film formed on a surface by hydraulic transfer with a curable resin composition. An invention relating to a hydraulic transfer body in which the printed film is coated with an article is disclosed. The present invention has an advantage that it is excellent in terms of sharpness, durability, luxury feeling, and the like.

  Patent Document 2 discloses a monofunctional cyclic (meth) acrylate monomer, a bifunctional (meth) acrylate monomer having a specific viscosity, a trifunctional or higher (meth) acrylate monomer and / or a trifunctional or higher functional. An invention relating to a method for forming a topcoat on the surface of a substrate provided with a decoration layer, using a topcoat coating composition for a decoration layer, comprising a (meth) acrylate oligomer at a specific blending ratio is disclosed. Yes. The present invention has an advantage that the surface of the substrate can be spray-coated without using special equipment or diluting with a solvent.

JP-A-9-11700 JP 2005-170980 A

  However, the hydraulic transfer body described in Patent Document 1 has a problem in that it takes a long time to cure the coating layer. Further, the topcoat forming method described in Patent Document 2 has a problem in that the adhesion of the entire layer including the decorative layer and the topcoat layer to the substrate is not sufficiently satisfied.

  The present invention has been made in view of the above circumstances, and the object of the present invention is that the time required for curing the coating layer is short, it can be produced in a short time, and the printing layer and the coating layer are provided. The present invention provides a hydraulic transfer body in which the entire layer is excellent in adherence to the transfer target and a method for producing the hydraulic transfer body.

  As a result of intensive studies on a method for solving the above problems, the present inventor has an ethylenically unsaturated group and an isocyanate group in one molecule as a curable coating composition for forming a coating layer of a hydraulic transfer body. It has been found that the above problems can be solved by using an active energy ray-curable coating composition containing a compound, and the present invention has been completed.

  That is, the present invention has a transferred body, a printed layer formed by transferring a hydraulic transfer film onto the surface of the transferred body, and a coating layer formed from a curable coating composition on the surface of the printed layer. A hydraulic transfer body, wherein the curable coating composition is (A) a compound having an ethylenically unsaturated group and an isocyanate group in one molecule, (B) an ethylenically unsaturated group-containing compound other than the component (A) And (C) a hydraulic transfer member, which is an active energy ray-curable coating composition containing a photopolymerization initiator. Further, the present invention provides (A) a compound having an ethylenically unsaturated group and an isocyanate group in one molecule on the surface of the printing layer of the transfer target having a printing layer formed by transferring a hydraulic transfer film, (B) Applying an active energy ray-curable coating composition containing an ethylenically unsaturated group-containing compound other than the component (A), and (C) a photopolymerization initiator, followed by irradiation with active energy rays The present invention relates to a method for producing a hydraulic transfer body, wherein a layer is formed.

  According to the present invention, the time required for curing of the coating layer is short, and it can be manufactured in a short time, and the entire layer including the printing layer and the coating layer has excellent adhesion to the transfer target. And a method for producing the hydraulic transfer body.

  The hydraulic transfer body of the present invention is a transferred body, a printed layer formed by transferring a hydraulic transfer film to the surface of the transferred body, and a coating formed from a curable coating composition on the surface of the printed layer. A hydraulic transfer body having a layer, wherein the curable coating composition is (A) a compound having an ethylenically unsaturated group and an isocyanate group in one molecule, (B) an ethylenically unsaturated group other than the component (A). A hydraulic transfer body, which is an active energy ray-curable coating composition containing a group-containing compound and (C) a photopolymerization initiator.

  The transfer target is not particularly limited, and conventionally known ones can be used. For example, materials such as plastic such as polypropylene resin and ABS resin, metal, wood, glass and the like can be mentioned. Further, it may be a processed product, a molded product or the like made of the above material. The transfer target can be waterproofed as necessary so that the shape does not collapse when submerged in water. In addition, a primer layer can be provided on the surface of the transferred material as necessary in order to sufficiently adhere the print layer to the transferred material. As the resin for forming the primer layer, a conventional resin can be used without limitation as the primer layer, and examples thereof include a urethane resin, an epoxy resin, and an acrylic resin.

  The printing layer is formed by transferring a hydraulic transfer film onto the surface of the transfer object. The hydraulic transfer film is not particularly limited. For example, a hydraulic transfer film in which a hydrophobic printing pattern is formed on a support film composed of a water-soluble or water-swellable resin can be used. Although it does not specifically limit as a support body film, Polyvinyl alcohol is preferable from the point which is easy to melt | dissolve in water, and is easy to obtain. Although the thickness of a support body film is not specifically limited, About 10-200 micrometers is preferable.

  The transfer method is not particularly limited. For example, there is a method in which a transfer target is pressed against a hydraulic transfer film floated in a tank containing water, and the print pattern of the hydraulic transfer film is transferred to the transfer target using water pressure. When the support film remains on the printed layer after the transfer, the transferred object on which the printed layer is formed can be washed with water as necessary in order to remove the support film.

  The coating layer can be formed, for example, by applying a curable coating composition to the surface of the printing layer, drying as necessary, and then irradiating with active energy rays.

  Further, for example, a printing layer and a coating layer can be obtained by irradiating an active energy ray after transferring a hydraulic transfer film obtained by laminating a support film, a layer made of a curable coating composition, and a printing pattern in this order to a transfer target. Can be formed at once.

  In the present invention, the curable coating composition used for forming the coating layer comprises (A) a compound having an ethylenically unsaturated group and an isocyanate group in one molecule, (B) an ethylenic component other than the component (A). It is an active energy ray-curable coating composition containing an unsaturated group-containing compound and (C) a photopolymerization initiator.

  Including the compound (A) having an ethylenically unsaturated group and an isocyanate group in one molecule (hereinafter sometimes abbreviated as “component (A)”) in the active energy ray-curable coating composition This is effective in improving brittleness and improving the adhesion between the printed layer and the coating layer, and by these effects, the adhesion of the entire layer including the printed layer and the coating layer to the transfer medium is improved. The above effect is presumed to be obtained when the component (A) contained in the active energy ray-curable coating composition penetrates into the printing layer and is cured in the printing layer.

  Examples of the component (A) include isocyanate methyl (meth) acrylate, isocyanate ethyl (meth) acrylate, isocyanate propyl (meth) acrylate, isocyanate octyl (meth) acrylate, p-methacryloxy-α, α′-dimethylbenzyl isocyanate, m -Acryloxy-α, α'-dimethylbenzyl isocyanate, m- or p-isopropenyl-α, α'-dimethylbenzyl isocyanate and the like.

  Moreover, as a component (A), the reaction product of a polyisocyanate compound and a hydroxyalkyl (meth) acrylate can be mentioned, for example. Moreover, the reaction product of a polyisocyanate compound, a hydroxyalkyl (meth) acrylate, and a polyol compound etc. can be mentioned, for example. In these reactions, the equivalent ratio of the isocyanate group contained in the polyisocyanate compound and the hydroxyl group contained in the hydroxyalkyl (meth) acrylate and the polyol compound is isocyanate group: hydroxyl group = 1.0: 0.1. -1.0: 0.9, preferably 1.0: 0.2-1.0: 0.7.

  The polyisocyanate compound is a compound having two or more free isocyanate groups in one molecule. Examples of the polyisocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and lysine diisocyanate; hydrogenated xylylene diisocyanate, cyclohexylene diisocyanate, methylene bis (cyclohexyl isocyanate), and isophorone. Alicyclic diisocyanates such as diisocyanate; aromatic diisocyanates such as tolylene diisocyanate, phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate; 2-isocyanatoethyl-2 , 6-Diisocyanatocaproate, 3-iso Triisocyanate compounds such as cyanatomethyl-1,6-hexamethylene diisocyanate and 4-isocyanatomethyl-1,8-octamethylene diisocyanate (commonly called triaminononane triisocyanate); two or more free isocyanates in one molecule Dimer (uretdione) or trimer (isocyanurate) of an isocyanate compound having a group; an isocyanate compound having two or more free isocyanate groups in one molecule, a polyhydric alcohol, and a low molecular weight polyester Examples thereof include prepolymers obtained by urethanation reaction under conditions of excess isocyanate groups with resin or water. These can be used alone or in combination of two or more.

  Examples of the hydroxyalkyl (meth) acrylate include alkyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Examples thereof include hydroxyalkyl (meth) acrylates having 2 to 7 carbon atoms. Other examples include pentaerythritol triacrylate. These can be used alone or in combination of two or more.

  The polyol compound is a compound having two or more hydroxyl groups in one molecule. Examples of the polyol compound include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, glycerin, di- or more Examples include polyglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like. These can be used alone or in combination of two or more.

  In the present invention, in particular, as component (A), in addition to the above-mentioned effects, there is an ethylenically unsaturated group and an isocyanate group in one molecule from the viewpoint of adhesion after a moisture resistance test, and the ethylenically unsaturated group and isocyanate. It is preferable to use the compound (A-1) (hereinafter sometimes abbreviated as “component (A-1)”) having two or more of at least one group.

  The molecular weight of component (A) is not particularly limited. For example, the molecular weight is preferably 200 to 3,000, more preferably 300 to 2,000. When the molecular weight of component (A) is within these ranges, a hydraulic transfer body excellent in terms of adhesion to the transfer target of the entire layer including the printing layer and the coating layer can be obtained.

  Moreover, the isocyanate content (NCO content) of the component (A) is not particularly limited. For example, the NCO content is preferably 1 to 30%, more preferably 2 to 20%. When the NCO content of the component (A) is not less than the lower limit of these ranges, a hydraulic transfer body excellent in terms of adhesion to the transfer target of the entire layer including the printing layer and the coating layer can be obtained, Moreover, when the NCO content of the component (A) is not more than the upper limit of these ranges, a hydraulic transfer body excellent in terms of appearance after the moisture resistance test can be obtained.

  The ethylenically unsaturated group-containing compound (B) (hereinafter sometimes abbreviated as “component (B)”) is a compound other than the component (A), and has an ethylenically unsaturated double group in its chemical structure. The compound is not particularly limited as long as the compound has at least one bond.

  Examples of the component (B) include esterified products of monohydric alcohol and (meth) acrylic acid. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and the like. Moreover, for example, an esterified product of a polyhydric alcohol and (meth) acrylic acid can be used. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, Di (meth) acrylate compounds such as neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate; glycerin tri ( Tri) (tri) such as acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate Acrylate compounds; tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; other examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Furthermore, urethane (meth) acrylate resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin and the like can be mentioned. The urethane (meth) acrylate resin here is a resin having no isocyanate group, unlike the component (A). The urethane (meth) acrylate resin is prepared by, for example, using a polyisocyanate compound, a hydroxylalkyl (meth) acrylate, and a polyol compound as raw materials, and reacting them in an amount such that the hydroxyl group is equimolar or excessive with respect to the isocyanate group. Obtainable. What was mentioned above is mentioned as a polyisocyanate compound, hydroxyalkyl (meth) acrylate, and a polyol compound. These components (B) can be used alone or in combination of two or more.

  As the component (B), a bifunctional or higher functional ethylenically unsaturated group-containing compound is preferable from the viewpoints of curability of the active energy ray-curable coating composition and appearance and flexibility of the coating layer.

  In addition, the component (B) preferably has a hydroxyl value of 200 mgKOH / g or less from the viewpoint of the pot life of the active energy ray-curable coating composition. In this specification, the hydroxyl value (mgKOH / g) is expressed in mg of potassium hydroxide when the amount of hydroxyl group contained in 1 g of the sample is converted into potassium hydroxide. The molecular weight of potassium hydroxide is 56.1.

  Component (B) is a urethane (meth) acrylate resin having a weight average molecular weight of 500 to 8,000 and / or a polyester (meth) acrylate resin having a weight average molecular weight of 500 to 8,000 (from the viewpoint of flexibility of the coating layer). B-1) (hereinafter sometimes abbreviated as “component (B-1)”) is particularly preferable. Component (B-1) preferably has a hydroxyl value of 10 mgKOH / g or less from the viewpoint of the pot life of the active energy ray-curable coating composition. The compounding quantity of a component (B-1) is not specifically limited. Preferably, it is 40-95 weight part in 100 weight part of component (B) from the point of balance of sclerosis | hardenability and the flexibility of a multilayer.

  In this specification, the weight average molecular weight is a value obtained by converting the weight average molecular weight measured by gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) based on the weight average molecular weight of polystyrene. Columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (both manufactured by Tosoh Corporation, trade names) ), Mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 cc / min, detector: RI.

  Component (B) is, for example, an ethylenically unsaturated group-containing resin (B-2) (hereinafter “component (B-2)”) having a weight average molecular weight of 10,000 to 100,000 included in component (B). Can be used in combination with the other component (B). The combined use of the ethylenically unsaturated group-containing resin is preferable from the viewpoint of coating workability such as sagging property and repellency of the coating layer. Examples of the ethylenically unsaturated group-containing resin include an ethylenically unsaturated group-containing acrylic resin. The ethylenically unsaturated group-containing acrylic resin can be produced, for example, by adding an ethylenically unsaturated group-containing carboxylic acid such as acrylic acid to an acrylic resin having an epoxy group. The weight average molecular weight of the component (B-2) is preferably 20,000 to 80,000. The compounding quantity of a component (B-2) is not specifically limited. Preferably, it is 5 to 50 parts by weight in 100 parts by weight of component (B).

  The compounding quantity of a component (A) and a component (B) is not specifically limited. For example, the weight ratio of component (A) to component (B) is preferably component (A): component (B) = 2: 98 to 50:50, more preferably 4:96 to 30:70. is there. When the component (A) is at least the lower limit in these ranges, a hydraulic transfer body excellent in adhesion to the transfer target of the entire layer including the printing layer and the coating layer can be obtained. Further, when the component (A) is not more than the upper limit in these ranges, a hydraulic transfer body excellent in adhesion after the moisture resistance test can be obtained.

  Examples of the photopolymerization initiator (C) include α-diketones such as benzyl and diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2, 4 -Thioxanthones such as diethylthioxanthone, 2-isopropylthioxanthone, thioxanthone-4-sulfonic acid; Benzophenones such as benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone; Michler's ketone Acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxybenzophenone, 2,2′-dimethyl Xyl-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Acetophenones such as butane-1-one, α-isohydroxyisobutylphenone, α, α′-dichloro-4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylacetophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide Acylphosphine oxides such as bis (acyl) phosphine oxide; quinones such as anthraquinone and 1,4-naphthoquinone; phenacyl chloride, trihalomethylphenylsulfone, tris (trihalomethyl) -s-triazine, etc. Androgenic compounds; peroxides such as di -t- butyl peroxide and the like. These can be used as one or a mixture of two or more.

  Examples of commercially available photopolymerization initiators (C) include IRGACURE-184, 261, 500, 651, 907, CGI-1700 (trade name, manufactured by Ciba Specialty Chemicals), Darocur-1173, 1116, 2959, 1664, 4043 (trade name, manufactured by Merck Japan), KAYACURE-DETX, MBP, DMBI, EPA, OA (trade name, Nippon Kayaku Co., Ltd.), VICURE-10, 55 (trade name, manufactured by STAUFFER Co., LTD.), Lucirin TPO (trade name, manufactured by BASF), TRIGONAL ) P1 [trade name, manufactured by AKZO Co., LTD.], SANDORAY 1000 [trade name, manufactured by SANDOZ Co., LTD.], DEAP [trade] Name, manufactured by APJOHN Co., LTD.], CANTACURE-PDO, ITX, EPD [trade name, manufactured by WARD BLEKINSOP Co., LTD.], Etc. be able to.

  The photopolymerization initiator (C) is preferably one or a mixture of two or more of thioxanthones, acetophenones and acylphosphine oxides from the viewpoint of photocurability, and acetophenones and acylphosphine oxides. Particularly preferred are mixtures with

  Although content of a photoinitiator (C) is not specifically limited, Preferably it is 0.5-10 weight part with respect to 100 weight part of total amounts of the said component (A) and component (B). More preferably, it is 1 to 5 parts by weight. When content of a photoinitiator (C) is more than the lower limit of this range, the coating layer excellent in photocurability can be obtained. Moreover, when it is below the upper limit of this range, the coating layer excellent in deep part sclerosis | hardenability and coating-material cost can be obtained.

  The active energy ray-curable coating composition may contain an ultraviolet absorber from the viewpoint of improving the weather resistance of the hydraulic transfer body. The ultraviolet absorber has an action of suppressing deterioration of the coating layer by absorbing incident light and converting light energy into a harmless form such as heat. The ultraviolet absorber can be used in combination with a light stabilizer described later.

  As the ultraviolet absorber, conventionally known ones can be used, and for example, a triazine-based absorbent, a benzotriazole-based absorbent, a salicylic acid derivative-based absorbent, a benzophenone-based absorbent, and the like can be used.

  Specific examples of the triazine-based absorbent include 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -1,3,5-triazine, 2- [4 ((2-hydroxy-3-dodecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 4-((2-Hydroxy-3-tridecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- ( 2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like.

  Specific examples of the benzotriazole-based absorbent include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-amylphenyl) benzotriazole 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- {2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -teto Hydro) -5'-methylphenyl} benzotriazole, and the like.

  Specific examples of the salicylic acid derivative-based absorbent include phenyl salicylate, p-octylphenyl salicylate, 4-tert-butylphenyl salicylate, and the like.

  Specific examples of the benzophenone-based absorbent include 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2 -Hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone Sodium 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2- Hydroxybe Zophenone, resorcinol monobenzoate, 2,4-dibenzoylresorcinol, 4,6-dibenzoylresorcinol, hydroxydodecylbenzophenone, 2,2′-dihydroxy-4 (3-methacryloxy-2-hydroxypropoxy) benzophenone Can do.

  As the ultraviolet absorber, a triazine-based absorber is preferably used from the viewpoint of deep curability.

  The compounding amount of the ultraviolet absorber is usually preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, particularly 100 parts by weight of the total amount of the component (A) and the component (B). Preferably it exists in the range of 0.3-3 weight part. These ranges are significant in terms of weather resistance and yellowing resistance.

  The active energy ray-curable coating composition can contain a light stabilizer from the viewpoint of improving the weather resistance of the hydraulic transfer body. The light stabilizer is used as a radical chain inhibitor that traps active radical species generated during the deterioration process of the coating layer, and includes, for example, a hindered amine light stabilizer. The light stabilizer can be used in combination with the ultraviolet absorber.

  Among these, hindered piperidines are mentioned as light stabilizers that exhibit an excellent light stabilizing action. Examples of hindered piperidines include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and bis ( N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4-benzoyloxy-2,2 ′, 6,6′-tetramethylpiperidine, bis (1,2,2,6, Monomer type such as 6-pentamethyl-4-piperidyl) {[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl} butyl malonate; poly {[6- (1,1 , 3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [( , 2,6,6-tetramethyl-4-piperidyl) iminol]} and the like; polyesters of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and succinic acid Examples thereof include, but are not limited to, polyester-bonded types.

  The blending amount of the light stabilizer is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, particularly preferably 100 parts by weight of the total amount of the component (A) and the component (B). Preferably it exists in the range of 0.3-2 weight part. These ranges are significant in terms of weather resistance and yellowing resistance.

  The active energy ray-curable coating composition contains a resin having a weight average molecular weight of 5,000 to 100,000 which is a component other than the above and has an isocyanate-reactive group and does not have an ethylenically unsaturated group. be able to. Including a resin having a weight average molecular weight of 5,000 to 100,000 having an isocyanate-reactive group and having no ethylenically unsaturated group means that the coating layer has a coating workability such as sagging property and repellency and moisture resistance. From the viewpoint of the appearance after the property test. Examples of the resin include resins such as acrylic resin, polyester resin, and urethane resin. Moreover, as an isocyanate reactive group, a hydroxyl group is mentioned, for example. When the isocyanate-reactive group is a hydroxyl group, the hydroxyl value is preferably 10 to 200 mgKOH / g. The weight average molecular weight of the resin is preferably 10,000 to 80,000.

  The blending amount of such a resin is not particularly limited. Preferably, it is 5-40 weight part with respect to 100 weight part of total amounts of a component (A) and a component (B). The lower limit of this range is significant in terms of coating workability such as sagging and repellency of the coating layer, and the upper limit of this range is significant in terms of appearance.

  The active energy ray-curable coating composition may be blended with various additives as necessary, and may be diluted with a solvent if desired. Examples of the additive include a polymerization inhibitor, an antioxidant, an antifoaming agent, a surface conditioner, a plasticizer, and a colorant.

  Examples of the solvent used for dilution include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, methyl benzoate, and methyl propionate; ethers such as tetrahydrofuran, dioxane, and dimethoxyethane; Examples include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; aromatic hydrocarbons and aliphatic hydrocarbons. These can be used in appropriate combination for the purpose of adjusting the viscosity of the paint, adjusting the coating property, and the like.

  The nonvolatile content of the active energy ray-curable coating composition is not particularly limited. For example, it is preferably 20 to 100% by weight, and more preferably 40 to 70% by weight. When the non-volatile content is not less than the lower limit of these ranges, it is excellent in terms of smoothness of the coating layer and shortening of the drying time.

  The amount of ethylenically unsaturated groups in the active energy ray-curable coating composition is not particularly limited, but the amount of ethylenically unsaturated groups in the nonvolatile content in the active energy ray-curable coating composition is 1.0 to 4.0 mol / kg is preferable from the viewpoint of curability and flexibility.

  The NCO content of the active energy ray-curable coating composition is not particularly limited, but the NCO content in the nonvolatile content in the active energy ray-curable coating composition is 0.1 to 10%. preferable. The lower limit of the above range is significant in terms of adhesion to the transfer target of the entire layer including the printing layer and the coating layer, and the upper limit of the above range is significant in terms of adhesion after the water resistance test.

  The amount of hydroxyl groups in the active energy ray-curable coating composition is not particularly limited, but the amount of hydroxyl groups in the nonvolatile content in the active energy ray-curable coating composition is 1 to 50 mgKOH / g in terms of hydroxyl value. It is preferable from the point of pot life.

  In the hydraulic transfer body of the present invention, for example, the active energy ray-curable coating composition is applied to the surface of the print layer of the transfer target having a print layer formed by transferring a hydraulic transfer film, and then the active energy is applied. It can manufacture by irradiating a line | wire and forming a coating layer.

  The method for applying the active energy ray-curable coating composition to the surface of the printing layer is not particularly limited. For example, roller coating, roll coater coating, spin coater coating, curtain roll coater coating, slit coater coating, spray coating. , Electrostatic coating, dip coating, silk printing, spin coating and the like. When the transfer object is a three-dimensional object such as a molded product, spray coating is preferable.

  When forming a coating layer from the said active energy ray curable coating composition, it can dry as needed. The drying is not particularly limited as long as the solvent that is added can be removed. For example, the drying time can be 3 to 10 minutes at a drying temperature of 20 to 100 ° C.

  The film thickness of a coating layer is suitably set according to the objective. For example, the film thickness is preferably 10 to 100 μm, and more preferably 20 to 70 μm. When the film thickness is not less than the lower limit of these ranges, a hydraulic transfer body excellent in smoothness and appearance can be obtained, and when it is not more than the upper limit of these ranges, a hydraulic transfer body excellent in curability can be obtained. Obtainable.

After the active energy ray-curable coating composition is applied to the surface of the printing layer, active energy ray irradiation is performed to form a coating layer. The irradiation source and irradiation amount of active energy ray irradiation are not particularly limited. For example, the active energy ray irradiation source includes ultra-high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, sunlight and the like. Dose, for example preferably 5~20,000J / m ^2, more preferably include a range of 100~10,000J / m ^2.

  The active energy ray irradiation may be performed in an air atmosphere or in an inert gas atmosphere. Examples of the inert gas include nitrogen and carbon dioxide. Active energy ray irradiation in an inert gas atmosphere is preferable from the viewpoint of curability.

  After performing active energy ray irradiation, the hydraulic transfer body on which a coating layer is formed may be heat-treated as necessary. The heat treatment can be performed at a drying temperature of 60 to 100 ° C. for 3 to 10 minutes, for example.

  The hydraulic transfer body of the present invention is used for automobile interior parts such as instrument panels, dashboards, handles, center consoles, door trims, etc .; low-power parts such as various audio and computer cases; home appliances, office supplies, indoor decorations, etc. It is useful as a hydraulic transfer body.

  Hereinafter, the present invention will be described in more detail with reference to examples. “Part” and “%” indicate “part by weight” and “% by weight” unless otherwise specified.

(Production Example 1)
582 parts of Sumidur N3300 (trade name, manufactured by Sumika Bayer Urethane Co., Ltd., HDI isocyanurate, NCO content 22%) are charged into the flask and heated to 60 ° C. with stirring under air bubbling. did. 232 parts of 2-hydroxyethyl acrylate at 60 ° C. (hydroxyl group amount is 2 mol: equivalent ratio of isocyanate group contained in Sumidur N3300 and hydroxyl group contained in the compound is 3: 2), methoxyphenol 0.41 And 0.08 part dibutyltin dilaurate were added dropwise over 2 hours. Furthermore, reaction was continued for 4 hours after completion | finish of dripping, and compound a-1 applicable to the component (A-1) of about 100% of non volatile matters, NCO content 5.2%, and molecular weight 1100 was obtained.

(Production Example 2)
The flask was charged with 222 parts of isophorone diisocyanate (isocyanate group amount: 2 mol) and heated to 60 ° C. with stirring under air bubbling. 116 parts of 2-hydroxyethyl acrylate at 60 ° C. (hydroxyl group amount is 1 mol: equivalent ratio of isocyanate group contained in the isophorone diisocyanate and hydroxyl group contained in the compound is 2: 1), 0.17 part of methoxyphenol And 0.04 part of dibutyltin dilaurate was added dropwise over 2 hours. Further, the reaction was continued for 4 hours after completion of the dropwise addition to obtain a compound a-2 having a nonvolatile content of about 100%, an NCO content of 12%, and a molecular weight of 400.

(Production Example 3)
Laromar LR-9000 [trade name, manufactured by BASF, a compound having at least one ethylenically unsaturated group and two isocyanate groups in one molecule, NCO content 15%, molecular weight 800] 5 parts, Ebecryl 8402 (product Name, manufactured by Daicel Cytec Co., Ltd., urethane acrylate resin having two ethylenically unsaturated groups, weight average molecular weight 1,000, hydroxyl value 10 mgKOH / g or less) 85 parts, Aronix M-305 (trade name, manufactured by Toagosei Co., Ltd.) Pentaerythritol triacrylate, hydroxyl value 188 mg KOH / g) 10 parts, 50% acrylic resin solution (Note 1) 20 parts, Irgacure-184 (trade name, manufactured by Ciba Specialty Chemicals, acetophenone polymerization initiator) 1 part, Lucillin TPO (Product name, BS Off Co., acylphosphine oxides polymerization initiator) 1 part, TINUVIN 400 (trade name, manufactured by Ciba Specialty Chemicals, triazine-based UV absorber, 85% solids) 1.18 parts, Hostavin 3058 LIQ. (Trade name, manufactured by CRALIANT, light stabilizer) 0.5 part, BYK-310 (trade name, manufactured by BYK CHEMIE INTERNATIONALGMBH, surface conditioner, solid content 25%) 0.20 part, 103.22 parts butyl acetate Were mixed uniformly to obtain an active energy ray-curable coating composition No. 1.

  (Note 1) 50% acrylic resin solution: hydroxyl group having a weight average molecular weight of 50,000 obtained by polymerizing 60 parts of methyl methacrylate, 20 parts of n-butyl acrylate, 19 parts of 2-hydroxyethyl methacrylate and 1 part of acrylic acid. Acrylic resin solution comprising an acrylic resin containing, hydroxyl value per resin content 82 mgKOH / g, non-volatile content 50%.

(Production Examples 4 to 22)
Active energy ray-curable coating compositions No. 2 to No. 20 were obtained in the same manner as in Production Example 3 except that the formulations shown in Tables 1 and 2 were followed.

(Note 2) Ebecryl 884 (trade name, manufactured by Daicel Cytec, polyester acrylate resin having three ethylenically unsaturated groups, weight average molecular weight 3,000, hydroxyl value of 10 mgKOH / g or less)
(Note 3) IRR 214-K (trade name, Daicel Cytec, tricyclodecane dimethanol diacrylate, hydroxyl value of 10 mg KOH / g or less)
(Note 4) 50% resin solution b: weight average molecular weight 50 obtained by adding 5 parts of acrylic acid to an acrylic resin obtained by polymerizing 60 parts of methyl methacrylate, 20 parts of n-butyl acrylate, and 20 parts of glycidyl methacrylate. Resin solution consisting of 1,000 ethylenically unsaturated group-containing acrylic resin, 50% non-volatile content
(Note 5) Sumidur N3300 (trade name, manufactured by Sumika Bayer Urethane Co., Ltd., HDI isocyanurate)
(Note 6) The amount of ethylenically unsaturated groups, NCO content, and amount of hydroxyl groups in the table all represent amounts in the nonvolatile content of the active energy ray-curable coating composition.

Example 1
The active energy ray-curable coating composition No. 1 obtained in Production Example 3 is spray-coated on the surface of the print layer of an ABS resin transfer body having a print layer formed by transferring a hydraulic transfer film. Applied. After coating, drying is performed at 80 ° C. for 5 minutes, followed by irradiation with active energy rays (irradiation time is about 10 seconds) at a dose of 5,000 J / m ^{2 with} a metal halide lamp in a nitrogen gas atmosphere. A hydraulic transfer body having a 40 μm coating layer was obtained.
The coated surface state after coating was subjected to the following evaluation, and the obtained hydraulic transfer body was subjected to the following evaluation and test. The test results are shown in Table 3.

(Examples 2 to 17 and Comparative Examples 1 to 3)
A hydraulic transfer body having a 40 μm-thick coating layer was obtained in the same manner as in Example 1 except that the active energy ray-curable coating compositions No. 2 to No. 20 were used. In addition to the evaluation, the obtained hydraulic transfer body was subjected to the following evaluation and test. The test results are shown in Tables 3 and 4.

(Comparative Example 4)
On the surface of the ABS resin transfer body having a printing layer formed by transferring a hydraulic transfer film, the PG60 topcoat clear base (trade name, manufactured by Kansai Paint Co., Ltd. Main component) and Retan PG60 Curing agent (trade name, manufactured by Kansai Paint Co., Ltd., curing agent, isocyanate group-containing compound) is uniformly mixed at 10 to 1 (weight ratio) by spray coating. Applied. After coating, drying was performed at 80 ° C. for 30 minutes to obtain a hydraulic transfer body having a coating layer with a thickness of 40 μm.
The coated surface state after coating was subjected to the following evaluation, and the obtained hydraulic transfer body was subjected to the following evaluation and test. The test results are shown in Table 4.

(Coating workability)
The coated surface state after spray coating was observed visually and evaluated according to the following evaluation criteria.
◎ Very good with no abnormalities such as sagging and repelling ○ Very good with no abnormalities such as sagging and repelling × Abnormalities such as sagging and repelling

(Initial appearance)
The initial appearance of the hydraulic transfer body obtained in each of the examples and comparative examples was visually observed and evaluated according to the following evaluation criteria.
A: Both smoothness and glossiness are good. ○: One of smoothness and glossiness is slightly inferior, but the other is good. Δ: Smoothness and glossiness are slightly inferior. X: At least one of smoothness and glossiness is inferior.

(Initial adhesion)
In the hydraulic transfer body obtained in each of the examples and comparative examples, a knife is used to cut about 11 mm in length and width in a width of about 1.5 mm, and 100 pieces are formed in a goblet shape. Created a square. Subsequently, a cellophane adhesive tape having a width of 24 mm was closely attached to 100 squares, and the squares that were not peeled off when the tape was strongly peeled off were counted and evaluated according to the following criteria.
：: 100 pieces ◯: 99 to 95 pieces Δ: 94 to 50 pieces ×: less than 50 pieces Note that all the peelings were cohesive peelings of the printing layer.

(Appearance after moisture resistance test)
The hydraulic transfer body obtained in each of the examples and comparative examples was left in a blister box with a relative humidity of 95% RH or higher at 50 ° C. for 10 days, and the appearance of the hydraulic transfer body after standing was visually observed. The following criteria were evaluated in comparison with the hydraulic transfer body before the test.
◎: No change in appearance ○: No change in appearance but no problem △: Appreciable change in appearance with blistering or whitening ×: Appreciable change in appearance with blistering or whitening

(Adhesion after moisture resistance test)
The hydraulic transfer bodies obtained in each of the examples and comparative examples were left in a blister box having a relative humidity of 95% RH or higher at 50 ° C. for 10 days. The hydraulic transfer body after standing was taken out of the blister box and left for one day. Using a knife, the hydraulic transfer body was cut at a width of about 1.5 mm in length and width to reach 11 transfer bodies, and 100 squares were created in a goblet shape. Subsequently, a cellophane adhesive tape having a width of 24 mm was closely attached to 100 squares, and the squares that were not peeled off when the tape was strongly peeled off were counted and evaluated according to the following criteria.
：: 100 pieces ◯: 99 to 95 pieces Δ: 94 to 50 pieces ×: less than 50 pieces Note that all the peelings were cohesive peelings of the printing layer.

(Appearance after weather resistance test)
The hydraulic transfer body obtained in each of the examples and comparative examples was irradiated for 600 hours in accordance with the accelerated weathering test of 9.8.1 (Sunshine carbon arc lamp type) of JIS K 5400. The appearance after irradiation was visually observed and compared with a hydraulic transfer body before the test and evaluated according to the following criteria.
◎: No change in appearance ○: Slight decrease in gloss is observed, but no problem Δ: Significant decrease in gloss is observed ×: Significant decrease in gloss is observed

(Adhesion after weather resistance test)
The hydraulic transfer body obtained in each of the examples and comparative examples was irradiated for 600 hours in accordance with the accelerated weathering test of 9.8.1 (Sunshine carbon arc lamp type) of JIS K 5400. A knife was used for the irradiated water pressure transfer body, and cuts reaching 11 transfer bodies were made vertically and horizontally with a width of about 1.5 mm, and 100 squares were created in a goblet shape. Subsequently, a cellophane adhesive tape having a width of 24 mm was closely attached to 100 squares, and the squares that were not peeled off when the tape was strongly peeled off were counted and evaluated according to the following criteria.
：: 100 pieces ◯: 99 to 95 pieces Δ: 94 to 50 pieces ×: less than 50 pieces Note that all the peelings were cohesive peelings of the printing layer.

Claims (6)

A hydraulic transfer body having a transferred body, a printed layer formed by transferring a hydraulic transfer film onto the surface of the transferred body, and a coating layer formed from a curable coating composition on the surface of the printed layer. The curable coating composition is (A) a compound having an ethylenically unsaturated group and an isocyanate group in one molecule, (B) an ethylenically unsaturated group-containing compound other than the component (A), and (C). A hydraulic transfer body, which is an active energy ray-curable coating composition containing a photopolymerization initiator. 2. The hydraulic transfer according to claim 1, wherein the component (A) is a compound having an ethylenically unsaturated group and an isocyanate group in one molecule and having at least one of at least one of the ethylenically unsaturated group and the isocyanate group. body. The hydraulic transfer body according to claim 1 or 2, wherein the component (B) contains a urethane (meth) acrylate resin having a weight average molecular weight of 500 to 8,000. (A) a compound having an ethylenically unsaturated group and an isocyanate group in one molecule, (B) the component, on the surface of the print layer of the transfer target having a print layer formed by transferring a hydraulic transfer film; Applying an active energy ray-curable coating composition containing an ethylenically unsaturated group-containing compound other than (A) and (C) a photopolymerization initiator, and then irradiating the active energy ray to form a coating layer. A method for producing a hydraulic transfer member. 5. The hydraulic transfer according to claim 4, wherein the component (A) is a compound having an ethylenically unsaturated group and an isocyanate group in one molecule and having two or more of at least one of the ethylenically unsaturated group and the isocyanate group. Body manufacturing method. The method for producing a hydraulic transfer body according to claim 4 or 5, wherein the component (B) contains a urethane (meth) acrylate resin having a weight average molecular weight of 500 to 8,000.